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Sample records for amorphous calcium carbonate

  1. Apatite Formation from Amorphous Calcium Phosphate and Mixed Amorphous Calcium Phosphate/Amorphous Calcium Carbonate.

    PubMed

    Ibsen, Casper J S; Chernyshov, Dmitry; Birkedal, Henrik

    2016-08-22

    Crystallization from amorphous phases is an emerging pathway for making advanced materials. Biology has made use of amorphous precursor phases for eons and used them to produce structures with remarkable properties. Herein, we show how the design of the amorphous phase greatly influences the nanocrystals formed therefrom. We investigate the transformation of mixed amorphous calcium phosphate/amorphous calcium carbonate phases into bone-like nanocrystalline apatite using in situ synchrotron X-ray diffraction and IR spectroscopy. The speciation of phosphate was controlled by pH to favor HPO4 (2-) . In a carbonate free system, the reaction produces anisotropic apatite crystallites with large aspect ratios. The first formed crystallites are highly calcium deficient and hydrogen phosphate rich, consistent with thin octacalcium phosphate (OCP)-like needles. During growth, the crystallites become increasingly stoichiometric, which indicates that the crystallites grow through addition of near-stoichiometric apatite to the OCP-like initial crystals through a process that involves either crystallite fusion/aggregation or Ostwald ripening. The mixed amorphous phases were found to be more stable against phase transformations, hence, the crystallization was inhibited. The resulting crystallites were smaller and less anisotropic. This is rationalized by the idea that a local phosphate-depletion zone formed around the growing crystal until it was surrounded by amorphous calcium carbonate, which stopped the crystallization. PMID:27460160

  2. Phase transitions in biogenic amorphous calcium carbonate

    NASA Astrophysics Data System (ADS)

    Gong, Yutao

    Geological calcium carbonate exists in both crystalline phases and amorphous phases. Compared with crystalline calcium carbonate, such as calcite, aragonite and vaterite, the amorphous calcium carbonate (ACC) is unstable. Unlike geological calcium carbonate crystals, crystalline sea urchin spicules (99.9 wt % calcium carbonate and 0.1 wt % proteins) do not present facets. To explain this property, crystal formation via amorphous precursors was proposed in theory. And previous research reported experimental evidence of ACC on the surface of forming sea urchin spicules. By using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), we studied cross-sections of fresh sea urchin spicules at different stages (36h, 48h and 72h after fertilization) and observed the transition sequence of three mineral phases: hydrated ACC → dehydrated ACC → biogenic calcite. In addition, we unexpectedly found hydrated ACC nanoparticles that are surrounded by biogenic calcite. This observation indicates the dehydration from hydrated ACC to dehydrated ACC is inhibited, resulting in stabilization of hydrated ACC nanoparticles. We thought that the dehydration was inhibited by protein matrix components occluded within the biomineral, and we designed an in vitro assay to test the hypothesis. By utilizing XANES-PEEM, we found that SM50, the most abundant occluded matrix protein in sea urchin spicules, has the function to stabilize hydrated ACC in vitro.

  3. Structural Characteristics of Synthetic Amorphous Calcium Carbonate

    SciTech Connect

    Michel, F. Marc; MacDonald, Jason; Feng, Jian; Phillips, Brian L.; Ehm, Lars; Tarabrella, Cathy; Parise, John B.; Reeder, Richard J.

    2008-08-06

    Amorphous calcium carbonate (ACC) is an important phase involved in calcification by a wide variety of invertebrate organisms and is of technological interest in the development of functional materials. Despite widespread scientific interest in this phase a full characterization of structure is lacking. This is mainly due to its metastability and difficulties in evaluating structure using conventional structure determination methods. Here we present new findings from the application of two techniques, pair distribution function analysis and nuclear magnetic resonance spectroscopy, which provide new insight to structural aspects of synthetic ACC. Several important results have emerged from this study of ACC formed in vitro using two common preparation methods: (1) ACC exhibits no structural coherence over distances > 15 {angstrom} and is truly amorphous; (2) most of the hydrogen in ACC is present as structural H{sub 2}O, about half of which undergoes restricted motion on the millisecond time scale near room temperature; (3) the short- and intermediate-range structure of ACC shows no distinct match to any known structure in the calcium carbonate system; and (4) most of the carbonate in ACC is monodentate making it distinctly different from monohydrocalcite. Although the structure of synthetic ACC is still not fully understood, the results presented provide an important baseline for future experiments evaluating biogenic ACC and samples containing certain additives that may play a role in stabilization of ACC, crystallization kinetics, and final polymorph selection.

  4. Disordered amorphous calcium carbonate from direct precipitation

    DOE PAGESBeta

    Farhadi Khouzani, Masoud; Chevrier, Daniel M.; Güttlein, Patricia; Hauser, Karin; Zhang, Peng; Hedin, Niklas; Gebauer, Denis

    2015-06-01

    Amorphous calcium carbonate (ACC) is known to play a prominent role in biomineralization. Different studies on the structure of biogenic ACCs have illustrated that they can have distinct short-range orders. However, the origin of so-called proto-structures in synthetic and additive-free ACCs is not well understood. In the current work, ACC has been synthesised in iso-propanolic media by direct precipitation from ionic precursors, and analysed utilising a range of different techniques. The data suggest that this additive-free type of ACC does not resemble clear proto-structural motifs relating to any crystalline polymorph. This can be explained by the undefined pH value inmore » iso-propanolic media, and the virtually instantaneous precipitation. Altogether, this work suggests that aqueous systems and pathways involving pre-nucleation clusters are required for the generation of clear proto-structural features in ACC. Experiments on the ACC-to-crystalline transformation in solution with and without ethanol highlight that polymorph selection is under kinetic control, while the presence of ethanol can control dissolution re-crystallisation pathways.« less

  5. Disordered amorphous calcium carbonate from direct precipitation

    SciTech Connect

    Farhadi Khouzani, Masoud; Chevrier, Daniel M.; Güttlein, Patricia; Hauser, Karin; Zhang, Peng; Hedin, Niklas; Gebauer, Denis

    2015-06-01

    Amorphous calcium carbonate (ACC) is known to play a prominent role in biomineralization. Different studies on the structure of biogenic ACCs have illustrated that they can have distinct short-range orders. However, the origin of so-called proto-structures in synthetic and additive-free ACCs is not well understood. In the current work, ACC has been synthesised in iso-propanolic media by direct precipitation from ionic precursors, and analysed utilising a range of different techniques. The data suggest that this additive-free type of ACC does not resemble clear proto-structural motifs relating to any crystalline polymorph. This can be explained by the undefined pH value in iso-propanolic media, and the virtually instantaneous precipitation. Altogether, this work suggests that aqueous systems and pathways involving pre-nucleation clusters are required for the generation of clear proto-structural features in ACC. Experiments on the ACC-to-crystalline transformation in solution with and without ethanol highlight that polymorph selection is under kinetic control, while the presence of ethanol can control dissolution re-crystallisation pathways.

  6. Calcium carbonate polyamorphism and its role in biomineralization: how many amorphous calcium carbonates are there?

    PubMed

    Cartwright, Julyan H E; Checa, Antonio G; Gale, Julian D; Gebauer, Denis; Sainz-Díaz, C Ignacio

    2012-11-26

    Although the polymorphism of calcium carbonate is well known, and its polymorphs--calcite, aragonite, and vaterite--have been highly studied in the context of biomineralization, polyamorphism is a much more recently discovered phenomenon, and the existence of more than one amorphous phase of calcium carbonate in biominerals has only very recently been understood. Here we summarize what is known about polyamorphism in calcium carbonate as well as what is understood about the role of amorphous calcium carbonate in biominerals. We show that consideration of the amorphous forms of calcium carbonate within the physical notion of polyamorphism leads to new insights when it comes to the mechanisms by which polymorphic structures can evolve in the first place. This not only has implications for our understanding of biomineralization, but also of the means by which crystallization may be controlled in medical, pharmaceutical, and industrial contexts. PMID:23124964

  7. Amorphous Calcium Carbonate Based-Microparticles for Peptide Pulmonary Delivery.

    PubMed

    Tewes, Frederic; Gobbo, Oliviero L; Ehrhardt, Carsten; Healy, Anne Marie

    2016-01-20

    Amorphous calcium carbonate (ACC) is known to interact with proteins, for example, in biogenic ACC, to form stable amorphous phases. The control of amorphous/crystalline and inorganic/organic ratios in inhalable calcium carbonate microparticles may enable particle properties to be adapted to suit the requirements of dry powders for pulmonary delivery by oral inhalation. For example, an amorphous phase can immobilize and stabilize polypeptides in their native structure and amorphous and crystalline phases have different mechanical properties. Therefore, inhalable composite microparticles made of inorganic (i.e., calcium carbonate and calcium formate) and organic (i.e., hyaluronan (HA)) amorphous and crystalline phases were investigated for peptide and protein pulmonary aerosol delivery. The crystalline/amorphous ratio and polymorphic form of the inorganic component was altered by changing the microparticle drying rate and by changing the ammonium carbonate and HA initial concentration. The bioactivity of the model peptide, salmon calcitonin (sCT), coprocessed with alpha-1-antitrypsin (AAT), a model protein with peptidase inhibitor activity, was maintained during processing and the microparticles had excellent aerodynamic properties, making them suitable for pulmonary aerosol delivery. The bioavailability of sCT after aerosol delivery as sCT and AAT-loaded composite microparticles to rats was 4-times higher than that of sCT solution. PMID:26692360

  8. Bivalves build their shells from amorphous calcium carbonate

    NASA Astrophysics Data System (ADS)

    Jacob, D. E.; Wirth, R.; Soldati, A. L.; Wehrmeister, U.

    2012-04-01

    One of the most common shell structures in the bivalve class is the prism and nacre structure. It is widely distributed amongst both freshwater and marine species and gives cultured pearls their sought-after lustre. In freshwater bivalves, both shell structures (prism and nacre) consist of aragonite. Formation of the shell form an amorphous precursor phase is a wide-spread strategy in biomineralization and presents a number of advantages for the organisms in the handling of the CaCO3 material. While there is already evidence that larval shells of some mollusk species use amorphous calcium carbonate (ACC) as a transient precursor phase for aragonite, the use of this strategy by adult animals was only speculated upon. We present results from in-situ geochemistry, Raman spectroscopy and focused-ion beam assisted TEM on three species from two different bivalve families that show that remnants of ACC can be found in shells from adult species. We show that the amorphous phase is not randomly distributed, but is systematically found in a narrow zone at the interface between periostracum and prism layer. This zone is the area where spherulitic CaCO3- structures protrude from the inner periostracum to form the initial prisms. These observations are in accordance with our earlier results on equivalent structures in freshwater cultured pearls (Jacob et al., 2008) and show that the original building material for the prisms is amorphous calcium carbonate, secreted in vesicles at the inner periostracum layer. Quantitative temperature calibrations for paleoclimate applications using bivalve shells are based on the Mg-Ca exchange between inorganic aragonite (or calcite) and water. These calibrations, thus, do not take into account the biomineral crystallization path via an amorphous calcium carbonate precursor and are therefore likely to introduce a bias (a so-called vital effect) which currently is not accounted for. Jacob et al. (2008) Geochim. Cosmochim. Acta 72, 5401-5415

  9. How does an amorphous surface influence molecular binding?--ovocleidin-17 and amorphous calcium carbonate.

    PubMed

    Freeman, Colin L; Harding, John H; Quigley, David; Rodger, P Mark

    2015-07-14

    Atomistic molecular dynamics simulations of dehydrated amorphous calcium carbonate interacting with the protein ovocleidin-17 are presented. These simulations demonstrate that the amorphisation of the calcium carbonate surface removes water structure from the surface. This reduction of structure allows the protein to bind with many residues, unlike on crystalline surfaces where binding is strongest when only a few residues are attached to the surface. Basic residues are observed to dominate the binding interactions. The implications for protein control over crystallisation are discussed. PMID:26009013

  10. Increased calcium absorption from synthetic stable amorphous calcium carbonate: Double-blind randomized crossover clinical trial in post-menopausal women

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Calcium supplementation is a widely recognized strategy for achieving adequate calcium intake. We designed this blinded, randomized, crossover interventional trial to compare the bioavailability of a new stable synthetic amorphous calcium carbonate (ACC) with that of crystalline calcium carbonate (C...

  11. The mineral phase in the cuticles of two species of Crustacea consists of magnesium calcite, amorphous calcium carbonate, and amorphous calcium phosphate.

    PubMed

    Becker, Alexander; Ziegler, Andreas; Epple, Matthias

    2005-05-21

    The cuticules (shells) of the woodlice Porcellio scaber and Armadillidium vulgare were analysed with respect to their content of inorganic material. It was found that the cuticles consist of crystalline magnesium calcite, amorphous calcium carbonate (ACC), and amorphous calcium phosphate (ACP), besides small amounts of water and an organic matrix. It is concluded that the cuticle, which constitutes a mineralized protective organ, is chemically adapted to the biological requirements by this combination of different materials. PMID:15877152

  12. Synthesis of novel amorphous calcium carbonate by sono atomization for reactive mixing.

    PubMed

    Kojima, Yoshiyuki; Kanai, Makoto; Nishimiya, Nobuyuki

    2012-03-01

    Droplets of several micrometers in size can be formed in aqueous solution by atomization under ultrasonic irradiation at 2 MHz. This phenomenon, known as atomization, is capable of forming fine droplets for use as a reaction field. This synthetic method is called SARM (sono atomization for reactive mixing). This paper reports on the synthesis of a novel amorphous calcium carbonate formed by SARM. The amorphous calcium carbonate, obtained at a solution concentration of 0.8 mol/dm(3), had a specific surface area of 65 m(2)/g and a composition of CaCO(3)•0.5H(2)O as determined using thermogravimetric/differential thermal analysis (TG-DTA). Because the ACC had a lower hydrate composition than conventional amorphous calcium carbonate (ACC), the ACC synthesized in this paper was very stable at room temperature. PMID:21788149

  13. A solvothermal method for synthesizing monolayer protected amorphous calcium carbonate clusters.

    PubMed

    Sun, Shengtong; Gebauer, Denis; Cölfen, Helmut

    2016-05-19

    A solvothermal method was developed for synthesizing organic monolayer protected amorphous calcium carbonate clusters using 10,12-pentacosadiynoic acid as ligand, ethanol as solvent and NaHCO3 decomposition as CO2 source, which can be extended to synthesize other monolayer protected mineral clusters. PMID:27161807

  14. In vitro synthesis and stabilization of amorphous calcium carbonate (ACC) nanoparticles within liposomes

    SciTech Connect

    Tester, Chantel C.; Brock, Ryan E.; Wu, Ching-Hsuan; Krejci, Minna R.; Weigand, Steven; Joester, Derk

    2012-02-07

    We show that amorphous calcium carbonate (ACC) can be synthesized in phospholipid bilayer vesicles (liposomes). Liposome-encapsulated ACC nanoparticles are stable against aggregation, do not crystallize for at least 20 h, and are ideally suited to investigate the influence of lipid chemistry, particle size, and soluble additives on ACC in situ.

  15. Amorphous calcium carbonate controls avian eggshell mineralization: A new paradigm for understanding rapid eggshell calcification.

    PubMed

    Rodríguez-Navarro, Alejandro B; Marie, Pauline; Nys, Yves; Hincke, Maxwell T; Gautron, Joel

    2015-06-01

    Avian eggshell mineralization is the fastest biogenic calcification process known in nature. How this is achieved while producing a highly crystalline material composed of large calcite columnar single crystals remains largely unknown. Here we report that eggshell mineral originates from the accumulation of flat disk-shaped amorphous calcium carbonate (ACC) particles on specific organic sites on the eggshell membrane, which are rich in proteins and sulfated proteoglycans. These structures known as mammillary cores promote the nucleation and stabilization of a amorphous calcium carbonate with calcitic short range order which predetermine the calcite composition of the mature eggshell. The amorphous nature of the precursor phase was confirmed by the diffuse scattering of X-rays and electrons. The nascent calcitic short-range order of this transient mineral phase was revealed by infrared spectroscopy and HRTEM. The ACC mineral deposited around the mammillary core sites progressively transforms directly into calcite crystals without the occurrence of any intermediate phase. Ionic speciation data suggest that the uterine fluid is equilibrated with amorphous calcium carbonate, throughout the duration of eggshell mineralization process, supporting that this mineral phase is constantly forming at the shell mineralization front. On the other hand, the transient amorphous calcium carbonate mineral deposits, as well as the calcite crystals into which they are converted, form by the ordered aggregation of nanoparticles that support the rapid mineralization of the eggshell. The results of this study alter our current understanding of avian eggshell calcification and provide new insights into the genesis and formation of calcium carbonate biominerals in vertebrates. PMID:25934395

  16. Dehydration and crystallization of amorphous calcium carbonate in solution and in air

    PubMed Central

    Ihli, Johannes; Wong, Wai Ching; Noel, Elizabeth H.; Kim, Yi-Yeoun; Kulak, Alexander N.; Christenson, Hugo K.; Duer, Melinda J.; Meldrum, Fiona C.

    2014-01-01

    The mechanisms by which amorphous intermediates transform into crystalline materials are poorly understood. Currently, attracting enormous interest is the crystallization of amorphous calcium carbonate, a key intermediary in synthetic, biological and environmental systems. Here we attempt to unify many contrasting and apparently contradictory studies by investigating this process in detail. We show that amorphous calcium carbonate can dehydrate before crystallizing, both in solution and in air, while thermal analyses and solid-state nuclear magnetic resonance measurements reveal that its water is present in distinct environments. Loss of the final water fraction—comprising less than 15% of the total—then triggers crystallization. The high activation energy of this step suggests that it occurs by partial dissolution/recrystallization, mediated by surface water, and the majority of the particle then crystallizes by a solid-state transformation. Such mechanisms are likely to be widespread in solid-state reactions and their characterization will facilitate greater control over these processes. PMID:24469266

  17. Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule

    PubMed Central

    Politi, Yael; Metzler, Rebecca A.; Abrecht, Mike; Gilbert, Benjamin; Wilt, Fred H.; Sagi, Irit; Addadi, Lia; Weiner, Steve; Gilbert, P. U. P. A.

    2008-01-01

    Sea urchin larval spicules transform amorphous calcium carbonate (ACC) into calcite single crystals. The mechanism of transformation is enigmatic: the transforming spicule displays both amorphous and crystalline properties, with no defined crystallization front. Here, we use X-ray photoelectron emission spectromicroscopy with probing size of 40–200 nm. We resolve 3 distinct mineral phases: An initial short-lived, presumably hydrated ACC phase, followed by an intermediate transient form of ACC, and finally the biogenic crystalline calcite phase. The amorphous and crystalline phases are juxtaposed, often appearing in adjacent sites at a scale of tens of nanometers. We propose that the amorphous-crystal transformation propagates in a tortuous path through preexisting 40- to 100-nm amorphous units, via a secondary nucleation mechanism. PMID:18987314

  18. Nanoporous Structure and Medium-Range Order in Synthetic Amorphous Calcium Carbonate

    SciTech Connect

    Goodwin, Andrew L.; Michel, F. Marc; Phillips, Brian L.; Keen, David A.; Dove, Martin T.; Reeder, Richard J.

    2010-12-03

    We adopt a reverse Monte Carlo refinement approach, using experimental X-ray total scattering data, to develop a structure model for synthetic, hydrated amorphous calcium carbonate (ACC). The ACC is revealed to consist of a porous calcium-rich framework that supports interconnected channels containing water and carbonate molecules. The existence of a previously unrecognized nanometer-scale channel network suggests mechanisms of how additives can be accommodated within the structure and provide temporary stabilization, as well as influence the crystallization process. Moreover, while lacking long-range order, the calcium-rich framework in the ACC contains similar Ca packing density to that present in calcite, aragonite, and vaterite, yielding clues of how the amorphous material converts into the different crystalline forms. Our results provide a new starting point for advancing our understanding of biomineralization as well as the development of biomimetic approaches to next-generation materials synthesis.

  19. Microwave hydrothermal transformation of amorphous calcium carbonate nanospheres and application in protein adsorption.

    PubMed

    Qi, Chao; Zhu, Ying-Jie; Chen, Feng

    2014-03-26

    Calcium carbonate and calcium phosphate are the main components of biominerals. Among all of the forms of biominerals, amorphous calcium carbonate (ACC) and amorphous calcium phosphate (ACP) are the most important forms because they play a pivotal role in the process of biomineralization and are the precursors to the crystalline polymorphs. In this work, we first synthesized ACC in vitro using adenosine 5'-triphosphate disodium salt (ATP) as the stabilizer and investigated the transformation of the ACC under microwave hydrothermal conditions, and ACC/ACP composite nanospheres and carbonated hydroxyapatite (CHA) nanospheres were successfully prepared. In this novel strategy, ATP has two main functions: it serves as the stabilizer for ACC and the phosphorus source for ACP and CHA. Most importantly, the morphology and the size of the ACC precursor can be well-preserved after microwave heating, so it provides a new method for the preparation of calcium phosphate nanostructured materials using phosphorus-containing biomolecule-stabilized ACC as the precursor. Furthermore, the as-prepared ACC/ACP composite nanospheres have excellent biocompatibility and high protein adsorption capacity, indicating that they are promising for applications in biomedical fields such as drug delivery and protein adsorption. PMID:24568728

  20. A transparent hybrid of nanocrystalline cellulose and amorphous calcium carbonate nanoparticles

    NASA Astrophysics Data System (ADS)

    Gebauer, Denis; Oliynyk, Vitaliy; Salajkova, Michaela; Sort, Jordi; Zhou, Qi; Bergström, Lennart; Salazar-Alvarez, German

    2011-09-01

    Nanocellulose hybrids are promising candidates for biodegradable multifunctional materials. Hybrids of nanocrystalline cellulose (NCC) and amorphous calcium carbonate (ACC) nanoparticles were obtained through a facile chemical approach over a wide range of compositions. Controlling the interactions between NCC and ACC results in hard, transparent structures with tunable composition, homogeneity and anisotropy.Nanocellulose hybrids are promising candidates for biodegradable multifunctional materials. Hybrids of nanocrystalline cellulose (NCC) and amorphous calcium carbonate (ACC) nanoparticles were obtained through a facile chemical approach over a wide range of compositions. Controlling the interactions between NCC and ACC results in hard, transparent structures with tunable composition, homogeneity and anisotropy. Electronic supplementary information (ESI) available: Additional experimental procedures and results. See DOI: 10.1039/c1nr10681c

  1. Controlled synthesis of crystalline calcium carbonate aggregates with unusual morphologies involving the phase transformation from amorphous calcium carbonate

    SciTech Connect

    Tang Hua; Yu Jiaguo Zhao Xiufeng

    2009-04-02

    Peanut-shaped CaCO{sub 3} aggregates, featured of two dandelion-like heads built up from rod-like subunits, have been synthesized via a facile precipitation reaction between Na{sub 2}CO{sub 3} and CaCl{sub 2} at ambient temperature in the presence of magnesium ions and ethanol solvent. The as-prepared products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectrometry (ICP-AES). The results show that a high magnesium concentration and ethanol solvent are necessary for the formation of the unusual peanut-like aggregates. In addition, a multistep phase transformation process from amorphous calcium carbonate (ACC) to a mixture of ACC and calcite and ultimately to calcite and aragonite was observed in the formation process of the unusual structures. A possible mechanism for the formation of the unusual peanut-shape aggregates has been proposed and discussed.

  2. Calcium Carbonate Storage in Amorphous Form and Its Template-Induced Crystallization

    SciTech Connect

    Han, T Y; Aizenberg, J

    2007-08-31

    Calcium carbonate crystallization in organisms often occurs through the transformation from the amorphous precursor. It is believed that the amorphous phase could be temporarily stabilized and stored, until its templated transition to the crystalline form is induced. Here we develop a bio-inspired crystallization strategy that is based on the above mechanism. Amorphous calcium carbonate (ACC) spherulitic particles are formed and stabilized on a self-assembled monolayer (SAM) of hydroxy-terminated alkanethiols on Au surface. The ACC is stored as a reservoir for ions and is induced to crystallize on command by introducing a secondary surface that is functionalized with carboxylic acid-terminated SAM. This secondary surface acts as a template for oriented and patterned nucleation. Various oriented crystalline arrays and micropatterned films are formed. We also show that the ACC phase can be doped with foreign ions (e.g. Mg) and organic molecules (e.g. dyes) and that these dopants later function as growth modifiers of calcite crystals and become incorporated into the crystals during the transformation process of ACC to calcite. We believe that our strategy opens the way of using a stabilized amorphous phase as a versatile reservoir system that can be converted in a highly controlled fashion to a crystalline form upon contacting the nucleating template.

  3. Amorphous Calcium Carbonate Precipitation by Cellular Biomineralization in Mantle Cell Cultures of Pinctada fucata

    PubMed Central

    Xiang, Liang; Kong, Wei; Su, Jingtan; Liang, Jian; Zhang, Guiyou; Xie, Liping; Zhang, Rongqing

    2014-01-01

    The growth of molluscan shell crystals is generally thought to be initiated from the extrapallial fluid by matrix proteins, however, the cellular mechanisms of shell formation pathway remain unknown. Here, we first report amorphous calcium carbonate (ACC) precipitation by cellular biomineralization in primary mantle cell cultures of Pinctada fucata. Through real-time PCR and western blot analyses, we demonstrate that mantle cells retain the ability to synthesize and secrete ACCBP, Pif80 and nacrein in vitro. In addition, the cells also maintained high levels of alkaline phosphatase and carbonic anhydrase activity, enzymes responsible for shell formation. On the basis of polarized light microscopy and scanning electron microscopy, we observed intracellular crystals production by mantle cells in vitro. Fourier transform infrared spectroscopy and X-ray diffraction analyses revealed the crystals to be ACC, and de novo biomineralization was confirmed by following the incorporation of Sr into calcium carbonate. Our results demonstrate the ability of mantle cells to perform fundamental biomineralization processes via amorphous calcium carbonate, and these cells may be directly involved in pearl oyster shell formation. PMID:25405357

  4. Stabilization of amorphous calcium carbonate by phosphate rich organic matrix proteins and by single phosphoamino acids.

    PubMed

    Bentov, Shmuel; Weil, Simy; Glazer, Lilah; Sagi, Amir; Berman, Amir

    2010-08-01

    Stable amorphous calcium carbonate (ACC) is a unique material produced naturally exclusively as a biomineral. It was demonstrated that proteins extracted from biogenic stable ACC induce and stabilize synthetic ACC in vitro. Polyphosphate molecules were similarly shown to induce amorphous calcium carbonate formation in vitro. Accordingly, we tested the hypothesis that biogenic ACC induction and stabilization is mediated by the phosphorylated residues of phosphoproteins. We show that extracellular organic matrix extracted from gastroliths of the red claw crayfish Cherax quadricarinatus induce stable ACC formation in vitro. The proteinaceous fraction of this organic matrix is highly phosphorylated and is incorporated into the ACC mineral phase during precipitation. We have identified the major phosphoproteins of the organic matrix and showed that they have high calcium binding capacity. Based on the above, in vitro precipitation experiments with single phosphoamino acids were performed, indicating that phosphoserine or phosphothreonine alone can induce the formation of highly stable ACC. The results indicate that phosphoproteins may play a major role in the control of ACC formation and stabilization and that their phosphoamino acid moieties are key components in this process. PMID:20416381

  5. ATP-stabilized amorphous calcium carbonate nanospheres and their application in protein adsorption.

    PubMed

    Qi, Chao; Zhu, Ying-Jie; Lu, Bing-Qiang; Zhao, Xin-Yu; Zhao, Jing; Chen, Feng; Wu, Jin

    2014-05-28

    Calcium carbonate is a common substance found in rocks worldwide, and is the main biomineral formed in shells of marine organisms and snails, pearls and eggshells. Amorphous calcium carbonate (ACC) is the least stable polymorph of calcium carbonate, which is so unstable under normal conditions that it is difficult to be prepared in vitro because it rapidly crystallizes to form one of the more stable polymorphs in aqueous solution. Herein, we report the successful synthesis of highly stable ACC nanospheres in vitro using adenosine 5'-triphosphate disodium salt (ATP) as a stabilizer. The effect of ATP on the stability of ACC nanospheres is investigated. Our experiments show that ATP plays an unique role in the stabilization of ACC nanospheres in aqueous solution. Moreover, the as-prepared ACC nanospheres are highly stable in phosphate buffered saline for a relatively long period of time (12 days) even under relatively high concentrations of calcium and phosphate ions. The cytotoxicity tests show that the as-prepared highly stable ACC nanospheres have excellent biocompatibility. The highly stable ACC nanospheres have high protein adsorption capacity, implying that they are promising for applications in biomedical fields such as drug delivery and protein adsorption. PMID:24578276

  6. Investigating the Role of Carbonate Ion Concentration on the Magnesium Content of Amorphous Calcium Carbonate

    NASA Astrophysics Data System (ADS)

    Blue, C.; Dove, P. M.; Han, N.

    2011-12-01

    The fields of biomineralization and carbonate geochemistry are undergoing a paradigm shift with the realization that the formation of calcite with diverse compositions and textures can be understood within the framework of multiple pathways to mineralization. Many organisms do not form their skeletons via the classical step-growth process, but instead mineralization occurs through a mesocrystal pathway that begins with the formation of amorphous calcium carbonate (ACC), which subsequently transforms to calcite. Little is known about factors that regulate this type of calcification because the last 50 years of research have focused almost entirely on step-growth processes. In particular, new findings indicate that the chemical signatures and properties of calcites that form via an amorphous pathway are significantly different. Variable temperature has been shown to influence the amount of magnesium that is incorporated into ACC, but the effect of alkalinity has not been constrained. Here, a flow-through method was developed to produce ACC within a geochemically relevant pH range and with a constant supersaturation, and to determine the effect of carbonate ion concentration on magnesium uptake. The experimental approach uses a high precision syringe pump to prepare ACC under specified and constant chemical conditions. This study used two syringes that contained: 1) 100 ml of MgCl2?6H2O and CaCl2?2H2O such that the Mg/Ca ratio is fixed at 5:1 (modern seawater), and 2) 100 ml of 60mM - 400mM NaHCO3. The initial sodium bicarbonate solutions were buffered to a pH of 9.75 using NaOH, and upon mixing with the 5:1 Mg/Ca solution the resulting pH range was 9.2 - 9.7. All experiments were performed at temperatures between 21.5 and 23 degrees Celsius. Solution and solids were collected on 0.20 micron filter paper with a vacuum pump running continuously. Experiments were typically conducted for an hour and a half and all samples were rinsed with distilled deionized water before

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

    PubMed

    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. PMID:26117783

  8. Calcium Carbonate

    MedlinePlus

    Calcium carbonate is a dietary supplement used when the amount of calcium taken in the diet is not ... for healthy bones, muscles, nervous system, and heart. Calcium carbonate also is used as an antacid to relieve ...

  9. Transformation of Mg-bearing amorphous calcium carbonate to Mg-calcite - In situ monitoring

    NASA Astrophysics Data System (ADS)

    Purgstaller, Bettina; Mavromatis, Vasileios; Immenhauser, Adrian; Dietzel, Martin

    2016-02-01

    The formation of Mg-bearing calcite via an amorphous precursor is a poorly understood process that is of relevance for biogenic and abiogenic carbonate precipitation. In order to gain an improved insight on the controls of Mg incorporation in calcite formed via an Mg-rich amorphous calcium carbonate (Mg-ACC) precursor, the precipitation of Mg-ACC and its transformation to Mg-calcite was monitored by in situ Raman spectroscopy. The experiments were performed at 25.0 ± 0.03 °C and pH 8.3 ± 0.1 and revealed two distinct pathways of Mg-calcite formation: (i) At initial aqueous Mg/Ca molar ratios ⩽ 1:6, Mg-calcite formation occurs via direct precipitation from solution. (ii) Conversely, at higher initial Mg/Ca molar ratios, Mg-calcite forms via an intermediate Mg-rich ACC phase. In the latter case, the final product is a calcite with up to 20 mol% Mg. This Mg content is significant higher than that of the Mg-rich ACC precursor phase. Thus, a strong net uptake of Mg ions from the solution into the crystalline precipitate throughout and also subsequent to ACC transformation is postulated. Moreover, the temporal evolution of the geochemical composition of the reactive solution and the Mg-ACC has no significant effect on the obtained "solubility product" of Mg-ACC. The enrichment of Mg in calcite throughout and subsequent to Mg-ACC transformation is likely affected by the high aqueous Mg/Ca ratio and carbonate alkalinity concentrations in the reactive solution. The experimental results have a bearing on the formation mechanism of Mg-rich calcites in marine early diagenetic environments, where high carbonate alkalinity concentrations are the rule rather than the exception, and on the insufficiently investigated inorganic component of biomineralisation pathways in many calcite secreting organisms.

  10. Genesis of amorphous calcium carbonate containing alveolar plates in the ciliate Coleps hirtus (Ciliophora, Prostomatea).

    PubMed

    Lemloh, Marie-Louise; Marin, Frédéric; Herbst, Frédéric; Plasseraud, Laurent; Schweikert, Michael; Baier, Johannes; Bill, Joachim; Brümmer, Franz

    2013-02-01

    In the protist world, the ciliate Coleps hirtus (phylum Ciliophora, class Prostomatea) synthesizes a peculiar biomineralized test made of alveolar plates, structures located within alveolar vesicles at the cell cortex. Alveolar plates are arranged by overlapping like an armor and they are thought to protect and/or stiffen the cell. Although their morphology is species-specific and of complex architecture, so far almost nothing is known about their genesis, their structure and their elemental and mineral composition. We investigated the genesis of new alveolar plates after cell division and examined cells and isolated alveolar plates by electron microscopy, energy-dispersive X-ray spectroscopy, FTIR and X-ray diffraction. Our investigations revealed an organic mesh-like structure that guides the formation of new alveolar plates like a template and the role of vesicles transporting inorganic material. We further demonstrated that the inorganic part of the alveolar plates is composed out of amorphous calcium carbonate. For stabilization of the amorphous phase, the alveolar vesicles, the organic fraction and the element phosphorus may play a role. PMID:23228488

  11. Transformation and Crystallization Energetics of Synthetic and Biogenic Amorphous Calcium Carbonate

    SciTech Connect

    Radha, A. V.; Forbes, Tori Z.; Killian, Christopher E.; Gilbert, P.U.P.A; Navrotsky, Alexandra

    2010-01-01

    Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC→anhydrous ACC ~ biogenic anhydrous ACC→vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO₂ sequestration.

  12. Stabilization and transformation of amorphous calcium carbonate: structural and kinetic studies

    NASA Astrophysics Data System (ADS)

    Schmidt, Millicent Promise

    Amorphous calcium carbonate (ACC) is a common transient precursor in the formation of more stable crystalline calcium carbonate minerals, most notably calcite, vaterite, and aragonite. Formation of ACC from calcium carbonate rich aqueous solution rather than direct crystallization of crystalline polymorphs by organisms provides several advantages: control of morphology, grain size, orientation, hardness, and other bulk properties as well as reduction of energy costs during growth cycles. Despite decades of study, stabilization and transformation mechanisms of synthetic and biogenic ACC remain unclear. In particular, the roles of H2O and inorganic phosphate in ACC structure and transformation, and the variables affecting transformation kinetics and polymorph selection are understudied. In this research, we addressed structure and kinetic behavior of ACC through four complementary investigations: two studies focus on synthetic ACC stabilization and two focus on synthetic and biogenic ACC transformation behavior in solution at ambient temperatures. We explored ACC stabilization via compositional and thermal analyses, X-ray scattering, X-ray absorption spectroscopy, and nuclear magnetic resonance spectroscopy. Transformation experiments used a novel method of in situ structural analysis that provided quantitative kinetic and structural data and allowed us to visualize the ACC transformation pathway. Results revealed the complexity of H2O structure in ACC samples synthesized from three methods, indicating that the distinct hydrous populations produced define ACC behavior. Transformation kinetics and polymorph selection were strongly affected by the hydration state and type of synthetic ACC reacted. In situ transformation experiments also showed differences in kinetic behavior due to reaction medium. The structural role of hydrous components was again evident in in situ transformation experiments for ACC from a biogenic lobster gastrolith (LG) reacted with water. LG

  13. Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate

    PubMed Central

    Radha, A. V.; Forbes, Tori Z.; Killian, Christopher E.; Gilbert, P. U. P. A.; Navrotsky, Alexandra

    2010-01-01

    Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC⇒anhydrous ACC ∼ biogenic anhydrous ACC⇒vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO2 sequestration. PMID:20810918

  14. Impact of sodium polyacrylate on the amorphous calcium carbonate formation from supersaturated solution.

    PubMed

    Liu, J; Pancera, S; Boyko, V; Gummel, J; Nayuk, R; Huber, K

    2012-02-21

    A detailed in situ scattering study has been carried out on the formation of amorphous calcium carbonate (ACC) particles modulated by the presence of small amounts of sodium polyacrylate chains. The work is aiming at an insight into the modulation of ACC formation by means of two polyacrylate samples differing in their molecular weight by a factor of 50. The ACC formation process was initiated by an in situ generation of CO(3)(2-) ions via hydrolysis of 10 mM dimethylcarbonate in the presence of 10 mM CaCl(2). Analysis of the formation process by means of time-resolved small-angle X-ray and light scattering in the absence of any additives provided evidence for a monomer addition mechanism for the growth of ACC particles. ACC formation under these conditions sets in after a lag-period of some 350 s. In the presence of sodium polyacrylate chains, calcium polyacrylate aggregates are formed during the lag-period, succeeded by a modulated ACC growth in a second step. The presence of anionic polyacrylate chains changed the shape of the growing particles toward loose and less homogeneous entities. In the case of low amounts (1.5-7.5 mg/L) of the long chain additive with 97 kDa, the size of the aggregates is comparable to the size of the successively formed hybrid particles. No variation of the lag-period has been observed in this case. Use of the short chain additive with 2 kDa enabled increase of the additive concentration up to 100 mg/L and resulted in a significant increase of the lag-period. This fact, together with the finding that the resulting hybrid particles remained stable in the latter case, identified short chain sodium polyacrylates as more efficient modulators than long chain polyacrylates. PMID:22256962

  15. Isotopic tracer evidence for the amorphous calcium carbonate to calcite transformation by dissolution-reprecipitation

    NASA Astrophysics Data System (ADS)

    Giuffre, Anthony J.; Gagnon, Alexander C.; De Yoreo, James J.; Dove, Patricia M.

    2015-09-01

    Observations that some biogenic and sedimentary calcites grow from amorphous calcium carbonate (ACC) raise the question of how this mineralization process influences composition. However, the detailed pathway and geochemical consequences of the ACC to calcite transformation are not well constrained. This experimental study investigated the formation of calcite from ACC by using magnesium and calcium stable isotope labeling to directly probe the transformation pathway and controls on composition. Four processes were considered: dissolution-reprecipitation, solid state transformation, and combinations of these end-members. To distinguish between these scenarios, ACC was synthesized from natural isotope abundance solutions and subsequently transferred to spiked solutions that were enriched in 43Ca and 25Mg for the transformation to calcite. Isotope measurements by NanoSIMS determined the 43Ca/40Ca, and 25Mg/24Mg ratios of the resulting calcite crystals. Analysis of the data shows the transformation is best explained by a dissolution-reprecipitation process. We find that when a small amount of ACC is transferred, the isotopic signals in the resulting calcite are largely replaced by the composition of the surrounding spiked solution. When larger amounts of ACC are transferred, calcite compositions reflect a mixture between the ACC and initial solution end-member. Comparisons of the measurements to the predictions of a simple mixing model indicate that calcite compositions (1) are sensitive to relative amounts of ACC and the surrounding solution reservoir and (2) are primarily governed by the conditions at the time of ACC transformation rather than the initial ACC formation. Shifts in calcite composition over the duration of the transformation period reflect the progressive evolution of the local solution conditions. This dependence indicates the extent to which there is water available would change the end point composition on the mixing line. While these findings have

  16. Spatial distribution of calcite and amorphous calcium carbonate in the cuticle of the terrestrial crustaceans Porcellio scaber and Armadillidium vulgare.

    PubMed

    Hild, Sabine; Marti, Othmar; Ziegler, Andreas

    2008-07-01

    The crustacean cuticle is an interesting model to study the properties of mineralized bio-composites. The cuticle consists of an organic matrix composed of chitin-protein fibres associated with various amounts of crystalline and amorphous calcium carbonate. It is thought that in isopods the relative amounts of these mineral polymorphs depend on its function and the habitat of the animal. In addition to the composition, the distribution of the various components should affect the properties of the cuticle. However, the spatial distribution of calcium carbonate polymorphs within the crustacean cuticle is unknown. Therefore, we analyzed the mineralized cuticles of the terrestrial isopods Armadillidium vulgare and Porcellio scaber using scanning electron-microscopy, electron probe microanalysis and confocal mu-Raman spectroscopic imaging. We show for the first time that the mineral phases are arranged in distinct layers. Calcite is restricted to the outer layer of the cuticle that corresponds to the exocuticle. Amorphous calcium carbonate is located within the endocuticle that lies below the exocuticle. Within both layers mineral is arranged in rows of granules with diameters of about 20 nm. The results suggest functional implications of mineral distribution that accord to the moulting and escape behaviour of the animals. PMID:18550385

  17. Calcium Carbonate.

    PubMed

    Al Omari, M M H; Rashid, I S; Qinna, N A; Jaber, A M; Badwan, A A

    2016-01-01

    Calcium carbonate is a chemical compound with the formula CaCO3 formed by three main elements: carbon, oxygen, and calcium. It is a common substance found in rocks in all parts of the world (most notably as limestone), and is the main component of shells of marine organisms, snails, coal balls, pearls, and eggshells. CaCO3 exists in different polymorphs, each with specific stability that depends on a diversity of variables. PMID:26940168

  18. Amorphous polyphosphate/amorphous calcium carbonate implant material with enhanced bone healing efficacy in a critical-size defect in rats.

    PubMed

    Wang, Xiaohong; Ackermann, Maximilian; Wang, Shunfeng; Tolba, Emad; Neufurth, Meik; Feng, Qingling; Schröder, Heinz C; Müller, Werner E G

    2016-01-01

    In this study the effect of amorphous calcium carbonate (ACC) microparticles and amorphous calcium polyphosphate (polyP) microparticles (termed aCa-polyP-MP) on bone mineral forming cells/tissue was investigated in vitro and in vivo. The ACC particles (termed ACC-P10-MP) were prepared in the presence of Na-polyP. Only the combinations of polyP and ACC microparticles enhanced the proliferation rate of human mesenchymal stem cells (MSCs). Gene expression studies revealed that ACC causes an upregulation of the expression of the cell membrane-associated carbonic anhydrase IX (CA IX; formation of ACC), while the transcript level of the alkaline phosphatase (ALP; liberation of orthophosphate from polyP) changes only relatively little. In contrast, aCa-polyP-MP primarily induces ALP expression. If both components are applied together a strong stimulation of expression of both marker genes is observed. In order to investigate whether ACC also enhances bone regeneration induced by polyP in vivo, the particles were encapsulated into PLGA (poly(d,l-lactide-co-glycolide)) microspheres (diameter ~800 μm) and implanted into rat critical-size calvarial defects. The studies revealed that animals that received aCa-polyP-MP microspheres showed an increased rate of regeneration compared to β-tri-calcium phosphate (β-TCP) controls. This effect is even accelerated if microspheres with both aCa-polyP-MP and ACC-P10-MP (1 : 1 weight ratio) are applied, resulting in an almost complete restoration of the defect area after 12 weeks. qRT-PCR analyses of tissue sections through the regeneration zone with microspheres containing both aCa-polyP-MP and ACC-P10-MP revealed a significantly higher upregulation of expression of the marker genes compared to each of the components alone. The Young's moduli for microspheres containing aCa-polyP-MP (1.74 MPa) and aCa-polyP-MP/ACC-P10-MP (2.38 MPa) were markedly higher compared to β-TCP-controls (0.63 mPa). Our results show that the combined

  19. Structure and Transformation of Amorphous Calcium Carbonate: A Solid-State 43Ca NMR and Computational Molecular Dynamics Investigation

    SciTech Connect

    Singer, Jared W.; Yazaydin, A. O.; Kirkpatrick, Robert J.; Bowers, Geoffrey M.

    2012-05-22

    Amorphous calcium carbonate (ACC) is a metastable precursor to crystalline CaCO{sub 3} phases that precipitates by aggregation of ion pairs and prenucleation clusters. We use {sup 43}Ca solid-state NMR spectroscopy to probe the local structure and transformation of ACC synthesized from seawater-like solutions with and without Mg{sup 2+} and computational molecular dynamics (MD) simulations to provide more detailed molecular-scale understanding of the ACC structure. The {sup 43}Ca NMR spectra of ACC collected immediately after synthesis consist of broad, featureless resonances with Gaussian line shapes (FWHH = 27.6 {+-} 1 ppm) that do not depend on Mg{sup 2+} or H{sub 2}O content. A correlation between {sup 43}Ca isotropic chemical shifts and mean Ca-O bond distances for crystalline hydrous and anhydrous calcium carbonate phases indicates indistinguishable maximum mean Ca-O bond lengths of {approx}2.45 {angstrom} for all our samples. This value is near the upper end of the published Ca-O bond distance range for biogenic and synthetic ACCs obtained by Ca-X-ray absorption spectroscopy. It is slightly smaller than the values from the structural model of Mgfree ACC by Goodwin et al. obtained from reverse Monte Carlo (RMC) modeling of X-ray scattering data and our own computational molecular dynamics (MD) simulation based on this model. An MD simulation starting with the atomic positions of the Goodwin et al. RMC model using the force field of Raiteri and Gale shows significant structural reorganization during the simulation and that the interconnected carbonate/water-rich channels in the Goodwin et al. model shrink in size over the 2 ns simulation time. The distribution of polyhedrally averaged Ca-O bond distances from the MD simulation is in good agreement with the {sup 43}Ca NMR peak shape, suggesting that local structural disorder dominates the experimental line width of ACC.

  20. Calcium carbonate overdose

    MedlinePlus

    Tums overdose; Calcium overdose ... Calcium carbonate can be dangerous in large amounts. ... Some products that contain calcium carbonate are certain: ... and mineral supplements Other products may also contain calcium ...

  1. Hydrogels from Amorphous Calcium Carbonate and Polyacrylic Acid: Bio-Inspired Materials for "Mineral Plastics".

    PubMed

    Sun, Shengtong; Mao, Li-Bo; Lei, Zhouyue; Yu, Shu-Hong; Cölfen, Helmut

    2016-09-19

    Given increasing environmental issues due to the large usage of non-biodegradable plastics based on petroleum, new plastic materials, which are economic, environmentally friendly, and recyclable are in high demand. One feasible strategy is the bio-inspired synthesis of mineral-based hybrid materials. Herein we report a facile route for an amorphous CaCO3 (ACC)-based hydrogel consisting of very small ACC nanoparticles physically cross-linked by poly(acrylic acid). The hydrogel is shapeable, stretchable, and self-healable. Upon drying, the hydrogel forms free-standing, rigid, and transparent objects with remarkable mechanical performance. By swelling in water, the material can completely recover the initial hydrogel state. As a matrix, thermochromism can also be easily introduced. The present hybrid hydrogel may represent a new class of plastic materials, the "mineral plastics". PMID:27444970

  2. [Calcium-oxygen modified amorphous and nanocrystalline carbon layers as biomaterials].

    PubMed

    Dorner-Reisel, A; Schürer, C; Nischan, C; Klemm, V; Irmer, G; Müller, E

    2002-01-01

    Undoped and Ca-O-modified diamond-like carbon coatings were deposited by a direct current discharge. Hardness and Young's modulus of Ca-O-modified DLCs were reduced in comparison with the undoped DLC, but the adherence of the Ca-O-modified films is improved. Ca-O-modified DLCs have a higher fraction of nano-crystalline regions with carbon in sp2 hybridisation. In addition, an increased oxygen content and CaCO3 was identified in Ca-O-modified DLCs. While mouse fibroblasts of the type L929 attach and grow on unmodified diamond-like carbon coatings synthesized by the decomposition of hydrocarbon, the addition of CaO-H2O into the precursor gas improves the coatings biological acceptance by the cells. PMID:12451874

  3. Strong stabilization of amorphous calcium carbonate emulsion by ovalbumin: gaining insight into the mechanism of 'polymer-induced liquid precursor' processes.

    PubMed

    Wolf, Stephan E; Leiterer, Jork; Pipich, Vitaliy; Barrea, Raul; Emmerling, Franziska; Tremel, Wolfgang

    2011-08-17

    The impact of the ovo proteins ovalbumin and lysozyme--present in the first stage of egg shell formation--on the homogeneous formation of the liquid amorphous calcium carbonate (LACC) precursor, was studied by a combination of complementing methods: in situ WAXS, SANS, XANES, TEM, and immunogold labeling. Lysozyme (pI = 9.3) destabilizes the LACC emulsion whereas the glycoprotein ovalbumin (pI = 4.7) extends the lifespan of the emulsified state remarkably. In the light of the presented data: (a) Ovalbumin is shown to behave commensurable to the 'polymer-induced liquid precursor' (PILP) process proposed by Gower et al. Ovalbumin can be assumed to take a key role during eggshell formation where it serves as an effective stabilization agent for transient precursors and prevents undirected mineralization of the eggshell. (b) It is further shown that the emulsified LACC carries a negative surface charge and is electrostatically stabilized. (c) We propose that the liquid amorphous calcium carbonate is affected by polymers by depletion stabilization and de-emulsification rather than 'induced' by acidic proteins and polymers during a so-called polymer-induced liquid-precursor process. The original PILP coating effect, first reported by Gower et al., appears to be a result of a de-emulsification process of a stabilized LACC phase. The behavior of the liquid amorphous carbonate phase and the polymer-induced liquid-precursor phase itself can be well described by colloid chemical terms: electrostatic and depletion stabilization and de-emulsification by depletion destabilization. PMID:21736300

  4. Strong stabilization of liquid amorphous calcium carbonate by ovalbumin: gaining insight into the mechanism of ‘polymer-induced liquid precursor’ processes

    PubMed Central

    Leiterer, Jork; Pipich, Vitaliy; Barrea, Raul; Tremel, Wolfgang

    2011-01-01

    The impact of the ovo-proteins ovalbumin and lysozyme—present in the first stage of egg shell formation—on the homogeneous formation of the liquid-amorphous calcium carbonate (LACC) precursor, was studied by a combination of complementing methods: in situ WAXS, SANS, XANES, TEM, and immunogold labeling. Lysozyme (pI = 9.3) destabilizes the LACC emulsion whereas the glycoprotein ovalbumin (pI = 4.7) extends the lifespan of the emulsified state remarkably. In the light of the presented data: (a) Ovalbumin is shown to behave commensurable to the ‘polymer-induced liquid precursor’ (PILP) process proposed by Gower et al. Ovalbumin can be assumed to take a key role during eggshell formation where it serves as an effective stabilization agent for transient precursors and prevents undirected mineralization of the eggshell. (b) It is further shown that the emulsified LACC carries a negative surface charge and is electrostatically stabilized. (c) We propose that the liquid amorphous calcium carbonate is affected by polymers by depletion stabilization and de-emulsification rather than ‘induced’ by acidic proteins and polymers during a polymer-induced liquid-precursor process. The original PILP coating effect, first reported by Gower et al., appears to be a result of a de-emulsification process of a stabilized LACC phase. The behavior of the liquid amorphous carbonate phase and the polymer-induced liquid-precursor phase itself can be well described by colloid chemical terms: electrostatic and depletion stabilization and de-emulsification by depletion destabilization. PMID:21736300

  5. Hydrogen bonding induced distortion of CO3 units and kinetic stabilization of amorphous calcium carbonate: results from 2D (13)C NMR spectroscopy.

    PubMed

    Sen, Sabyasachi; Kaseman, Derrick C; Colas, Bruno; Jacob, Dorrit E; Clark, Simon M

    2016-07-27

    Systematic correlation in alkaline-earth carbonate compounds between the deviation of the CO3 units from the perfect D3h symmetry and their (13)C nuclear magnetic resonance (NMR) chemical shift anisotropy (CSA) parameters is established. The (13)C NMR CSA parameters of amorphous calcium carbonate (ACC) are measured using two-dimensional (13)C phase adjusted spinning sidebands (PASS) NMR spectroscopy and are analyzed on the basis of this correlation. The results indicate a distortion of the CO3 units in ACC in the form of an in-plane displacement of the C atom away from the centroid of the O3 triangle, resulting from hydrogen bonding with the surrounding H2O molecules, without significant out-of-plane displacement. Similar distortion for all C atoms in the structure of ACC suggests a uniform spatial disposition of H2O molecules around the CO3 units forming a hydrogen-bonded amorphous network. This amorphous network is stabilized against crystallization by steric frustration, while additives such as Mg presumably provide further stabilization by increasing the energy of dehydration. PMID:27276013

  6. Phosphate-water interplay tunes amorphous calcium carbonate metastability: spontaneous phase separation and crystallization vs stabilization viewed by solid state NMR.

    PubMed

    Kababya, Shifi; Gal, Assaf; Kahil, Keren; Weiner, Steve; Addadi, Lia; Schmidt, Asher

    2015-01-21

    Organisms tune the metastability of amorphous calcium carbonates (ACC), often by incorporation of additives such as phosphate ions and water molecules, to serve diverse functions, such as modulating the availability of calcium reserves or constructing complex skeletal scaffolds. Although the effect of additive distribution on ACC was noted for several biogenic and synthetic systems, the molecular mechanisms by which additives govern ACC stability are not well understood. By precipitating ACC in the presence of different PO4(3-) concentrations and regulating the initial water content, we identify conditions yielding either kinetically locked or spontaneously transforming coprecipitates. Solid state NMR, supported by FTIR, XRD, and electron microscopy, define the interactions of phosphate and water within the initial amorphous matrix, showing that initially the coprecipitates are homogeneous molecular dispersions of structural water and phosphate in ACC, and a small fraction of P-rich phases. Monitoring the transformations of the homogeneous phase shows that PO4(3-) and waters are extracted first, and they phase separate, leading to solid-solid transformation of ACC to calcite; small part of ACC forms vaterite that subsequently converts to calcite. The simultaneous water-PO4(3-) extraction is the key for the subsequent water-mediated accumulation and crystallization of hydroxyapatite (HAp) and carbonated hydroxyapatite. The thermodynamic driving force for the transformations is calcite crystallization, yet it is gated by specific combinations of water-phosphate levels in the initial amorphous coprecipitates. The molecular details of the spontaneously transforming ACC and of the stabilized ACC modulated by phosphate and water at ambient conditions, provide insight into biogenic and biomimetic pathways. PMID:25523637

  7. Time-resolved evolution of short- and long-range order during the transformation of amorphous calcium carbonate to calcite in the sea urchin embryo

    NASA Astrophysics Data System (ADS)

    Tester, Chantel; Wu, Ching-Hsuan; Krejci, Minna; Mueller, Laura; Park, Alex; Lai, Barry; Chen, Si; Sun, Chengjun; Balasubramanian, Mahaling; Joester, Derk

    2013-03-01

    The biological use of amorphous mineral precursors is thought to be directly related to the ability to create single crystalline, yet composite materials with complex shapes that are beyond our synthetic capabilities. Despite considerable effort in recent years, it has not been possible to capture the mechanistic detail of the disorder-to-order transformation that is a key element of this process. This is largely due to lack of sensitivity, lack of temporal and spatial resolution, and artifacts of sample preparation. To overcome these challenges we use strontium as a probe for X-ray absorption spectroscopy (XAS). In pulse-chase experiments, sea urchin embryos incorporate Sr2 + from Sr-enriched seawater into small volumes of the developing endoskeleton. During the chase, the transformation of the newly deposited amorphous mineral is characterized by Sr-K α XAS of cryo-frozen whole embryos. We find that the initial mineral has short-range order resembling hydrated amorphous calcium carbonate. Within 3h, the short-range order of calcite is adopted, with long-range order developing over the next 20h. Pulse-chase experiments combined with heavy element labeling can be used in numerous mineralizing systems to study phase transformations during biological crystal growth.

  8. Raman Spectroscopy of Amorphous Carbon

    SciTech Connect

    Tallant, D.R.; Friedmann, T.A.; Missert, N.A.; Siegal, M.P.; Sullivan, J.P.

    1998-01-01

    Amorphous carbon is an elemental form of carbon with low hydrogen content, which may be deposited in thin films by the impact of high energy carbon atoms or ions. It is structurally distinct from the more well-known elemental forms of carbon, diamond and graphite. It is distinct in physical and chemical properties from the material known as diamond-like carbon, a form which is also amorphous but which has a higher hydrogen content, typically near 40 atomic percent. Amorphous carbon also has distinctive Raman spectra, whose patterns depend, through resonance enhancement effects, not only on deposition conditions but also on the wavelength selected for Raman excitation. This paper provides an overview of the Raman spectroscopy of amorphous carbon and describes how Raman spectral patterns correlate to film deposition conditions, physical properties and molecular level structure.

  9. Amorphous carbon for photovoltaics

    NASA Astrophysics Data System (ADS)

    Risplendi, Francesca; Grossman, Jeffrey C.

    2015-03-01

    All-carbon solar cells have attracted attention as candidates for innovative photovoltaic devices. Carbon-based materials such as graphene, carbon nanotubes (CNT) and amorphous carbon (aC) have the potential to present physical properties comparable to those of silicon-based materials with advantages such as low cost and higher thermal stability.In particular a-C structures are promising systems in which both sp2 and sp3 hybridization coordination are present in different proportions depending on the specific density, providing the possibility of tuning their optoelectronic properties and achieving comparable sunlight absorption to aSi. In this work we employ density functional theory to design suitable device architectures, such as bulk heterojunctions (BHJ) or pn junctions, consisting of a-C as the active layer material.Regarding BHJ, we study interfaces between aC and C nanostructures (such as CNT and fullerene) to relate their optoelectronic properties to the stoichiometry of aC. We demonstrate that the energy alignment between the a-C mobility edges and the occupied and unoccupied states of the CNT or C60 can be widely tuned by varying the aC density to obtain a type II interface.To employ aC in pn junctions we analyze the p- and n-type doping of a-C focusingon an evaluation of the Fermi level and work function dependence on doping.Our results highlight promising features of aC as the active layer material of thin-film solar cells.

  10. Superhydrophobic amorphous carbon/carbon nanotube nanocomposites

    NASA Astrophysics Data System (ADS)

    Han, Z. J.; Tay, B. K.; Shakerzadeh, M.; Ostrikov, K.

    2009-06-01

    Superhydrophobic amorphous carbon/carbon nanotube nanocomposites are fabricated by plasma immersion ion implantation with carbon nanotube forests as a template. The microstructure of the fabricated nanocomposites shows arrays of carbon nanotubes capped with amorphous carbon nanoparticles. Contact angle measurements show that both advancing and receding angles close to 180° can be achieved on the nanocomposites. The fabrication here does not require patterning of carbon nanotubes or deposition of conformal coatings with low surface energy, which are usually involved in conventional approaches for superhydrophobic surfaces. The relationship between the observed superhydrophobicity and the unique microstructure of the nanocomposites is discussed.

  11. Calcium carbonate with magnesium overdose

    MedlinePlus

    The combination of calcium carbonate and magnesium is commonly found in antacids. These medicines provide heartburn relief. Calcium carbonate with magnesium overdose occurs when someone takes more than the ...

  12. Impregnating Coal With Calcium Carbonate

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K.; Voecks, Gerald E.; Gavalas, George R.

    1991-01-01

    Relatively inexpensive process proposed for impregnating coal with calcium carbonate to increase rates of gasification and combustion of coal and to reduce emission of sulfur by trapping sulfur in calcium sulfide. Process involves aqueous-phase reactions between carbon dioxide (contained within pore network of coal) and calcium acetate. Coal impregnated with CO2 by exposing it to CO2 at high pressure.

  13. Review of casein phosphopeptides-amorphous calcium phosphate.

    PubMed

    Reema, Sharma Dhar; Lahiri, Prateek Kumar; Roy, Shantanu Sen

    2014-01-01

    Casein phosphopeptides-amorphous calcium phosphate (CPP-ACP) is a bioactive agent with a base of milk products, which has been formulated from two parts: casein phosphopeptides (CPP) and amorphous calcium phosphate (ACP). CPP was produced from milk protein casein and has a remarkable ability to stabilize calcium phosphate in solution and to substantially increase the level of calcium phosphate in dental plaque. CPP-ACP buffers the free calcium and phosphate ion activities, thereby helping to maintain a state of supersaturation with respect to tooth enamel, reducing demineralisation and promoting remineralisation. The free calcium and phosphate ions move out of the CPP, enter the enamel rods and reform onto apatite crystals. Laboratory, animal and human studies have shown that CPP-ACP inhibits cariogenic activity. CPP-ACP is useful in the treatment of white spot lesions, hypomineralised enamel, mild fluorosis, tooth sensitivity and erosion, and prevents plaque accumulation around brackets and other orthodontic appliances. CPP-ACP also facilitates a normal post-eruptive maturation process and is ideal for protecting primary teeth at a time when oral care is difficult. CPP-ACP has commercial potential as an additive to foods, soft drinks and chewing gum, as well as additive to toothpastes and mouthwashes to control dental caries. PMID:25028684

  14. Mechanisms of mineral membrane fouling growth modulated by pulsed modes of current during electrodialysis: evidences of water splitting implications in the appearance of the amorphous phases of magnesium hydroxide and calcium carbonate.

    PubMed

    Cifuentes-Araya, Nicolás; Astudillo-Castro, Carolina; Bazinet, Laurent

    2014-07-15

    Experiments revealed the fouling nature evolutions along different electrodialysis (ED) trials, and how it disappears when current pulsation acts repetitively on the interfaces of ion-exchange membranes (IEMs). Fouling was totally controlled on the diluate side of cation-exchange membrane (CEM) by the repetitive pulsation frequency of the higher on-duty ratios applied. They created steady water splitting proton-barriers that neutralized OH(-) leakage through the membrane, decreasing the interfacial pH, and fouling of the concentrate side. The anion-exchange membrane (AEM) on the diluate side was similarly protected, but it was fouled once water splitting OH(-) generation became either intense enough or excessively weak. Interestingly, amorphous magnesium hydroxide (AMH) stemmed on the CEM-diluate side from brucite under intense water splitting OH(-) generation, and/or strong OH(-) leakage electromigration through the membrane. Water dissociation and overlimiting current regimes triggered drastic water molecule removal from crystal lattices through an accelerated cascade water splitting reaction. Also, amorphous calcium carbonate (ACC) appeared on CEM under intense water splitting reaction, and disappeared once intense OH(-) leakage was allowed by the water splitting proton-barrier dissipation. Our findings have implications for membrane fouling control, as well as for the understanding of the growth behavior of CaCO3 and Mg(OH)2 species on electromembrane interfaces. PMID:24863787

  15. Amorphous Carbon-Boron Nitride Nanotube Hybrids

    NASA Technical Reports Server (NTRS)

    Kim, Jae Woo (Inventor); Siochi, Emilie J. (Inventor); Wise, Kristopher E. (Inventor); Lin, Yi (Inventor); Connell, John (Inventor)

    2016-01-01

    A method for joining or repairing boron nitride nanotubes (BNNTs). In joining BNNTs, the nanotube structure is modified with amorphous carbon deposited by controlled electron beam irradiation to form well bonded hybrid a-C/BNNT structures. In repairing BNNTs, the damaged site of the nanotube structure is modified with amorphous carbon deposited by controlled electron beam irradiation to form well bonded hybrid a-C/BNNT structures at the damage site.

  16. Synthesis of amorphous calcium phosphate using various types of cyclodextrins

    SciTech Connect

    Li Yanbao; Wiliana, Tjandra; Tam, Kam C. . E-mail: mkctam@ntu.edu.sg

    2007-05-03

    Amorphous calcium phosphate (ACP) was synthesised in aqueous solution at room temperature using cyclodextrins. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) and thermal analysis (DTA/TGA) were performed on the calcium phosphate precipitates obtained from solutions. We observed that only {beta}-CD could stabilise the amorphous phase in the mother solution because of the lower solubility of {beta}-CD in water and the ACP remained stable in aqueous solution for more than 24 h at room temperature. The ACP particle has an initial particle size of less than 40 nm, Ca/P molar ratio of 1.67 and {beta}-CD absorbed on its surface. The mechanism for the stabilisation of ACP is proposed.

  17. Gravimetric Determination of Calcium as Calcium Carbonate Hydrate.

    ERIC Educational Resources Information Center

    Henrickson, Charles H.; Robinson, Paul R.

    1979-01-01

    The gravimetric determination of calcium as calcium carbonate is described. This experiment is suitable for undergraduate quantitative analysis laboratories. It is less expensive than determination of chloride as silver chloride. (BB)

  18. Casein Phosphopeptide-Amorphous Calcium Phosphate Nanocomplexes: A Structural Model.

    PubMed

    Cross, Keith J; Huq, N Laila; Reynolds, Eric C

    2016-08-01

    Tryptic digestion of the calcium-sensitive caseins yields casein phosphopeptides (CPP) that contain clusters of phosphorylated seryl residues. The CPP stabilize calcium and phosphate ions through the formation of complexes. The calcium phosphate in these complexes is biologically available for intestinal absorption and remineralization of subsurface lesions in tooth enamel. We have studied the structure of the complexes formed by the CPP with calcium phosphate using a variety of nuclear magnetic resonance (NMR) techniques. Translational diffusion measurements indicated that the β-CN(1-25)-ACP nanocomplex has a hydrodynamic radius of 1.526 ± 0.044 nm at pH 6.0, which increases to 1.923 ± 0.082 nm at pH 9.0. (1)H NMR spectra were well resolved, and (3)JH(N)-H(α) measurements ranged from a low of 5.5 Hz to a high of 8.1 Hz. Total correlation spectroscopy and nuclear Overhauser effect spectroscopy spectra were acquired and sequentially assigned. Experiments described in this paper have allowed the development of a structural model of the β-CN(1-25)-amorphous calcium phosphate nanocomplex. PMID:27434168

  19. 21 CFR 184.1191 - Calcium carbonate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... three common methods of manufacture: (1) As a byproduct in the “Lime soda process”; (2) By precipitation of calcium carbonate from calcium hydroxide in the “Carbonation process”; or (3) By precipitation...

  20. 21 CFR 73.1070 - Calcium carbonate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Calcium carbonate. 73.1070 Section 73.1070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1070 Calcium carbonate. (a) Identity. (1) The color additive calcium carbonate is a fine,...

  1. 21 CFR 73.1070 - Calcium carbonate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Calcium carbonate. 73.1070 Section 73.1070 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1070 Calcium carbonate. (a) Identity. (1) The color additive calcium carbonate is a fine, white, synthetically prepared powder consisting essentially...

  2. 21 CFR 582.1191 - Calcium carbonate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium carbonate. 582.1191 Section 582.1191 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1191 Calcium carbonate. (a) Product. Calcium carbonate. (b) Conditions of use....

  3. 21 CFR 73.1070 - Calcium carbonate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Calcium carbonate. 73.1070 Section 73.1070 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1070 Calcium carbonate. (a) Identity. (1) The color additive calcium carbonate is a fine, white, synthetically prepared powder consisting essentially...

  4. 21 CFR 582.1191 - Calcium carbonate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Calcium carbonate. 582.1191 Section 582.1191 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1191 Calcium carbonate. (a) Product. Calcium carbonate. (b) Conditions of use....

  5. Characterization of calcium carbonate/chitosan composites

    SciTech Connect

    Gonsalves, K.E.; Zhang, S.

    1995-12-31

    The crystal growth of calcium carbonate on a chitosan substrate was achieved using a supersaturated calcium carbonate solution, by using various additives, polyacrylic acid (PAA). Polyacrylic acid modified the chitosan-film surface and promoted the nucleation of calcium carbonate crystals.

  6. Importance of FTIR Spectra Deconvolution for the Analysis of Amorphous Calcium Phosphates

    NASA Astrophysics Data System (ADS)

    Brangule, Agnese; Agris Gross, Karlis

    2015-03-01

    This work will consider Fourier transform infrared spectroscopy - diffuse reflectance infrared reflection (FTIR-DRIFT) for collecting the spectra and deconvolution to identify changes in bonding as a means of more powerful detection. Spectra were recorded from amorphous calcium phosphate synthesized by wet precipitation, and from bone. FTIR-DRIFT was used to study the chemical environments of PO4, CO3 and amide. Deconvolution of spectra separated overlapping bands in the ʋ4PO4, ʋ2CO3, ʋ3CO3 and amide region allowing a more detailed analysis of changes at the atomic level. Amorphous calcium phosphate dried at 80 oC, despite showing an X-ray diffraction amorphous structure, displayed carbonate in positions resembling a carbonated hydroxyapatite. Additional peaks were designated as A1 type, A2 type or B type. Deconvolution allowed the separation of CO3 positions in bone from amide peaks. FTIR-DRIFT spectrometry in combination with deconvolution offers an advanced tool for qualitative and quantitative determination of CO3, PO4 and HPO4 and shows promise to measure the degree of order.

  7. Hardness and microplasticity of nanocrystalline and amorphous calcium phosphate coatings

    NASA Astrophysics Data System (ADS)

    Ievlev, V. M.; Kostyuchenko, A. V.; Darinskii, B. M.; Barinov, S. M.

    2014-02-01

    The hardness of thin (1.0-4.0 μm) hydroxyapatite coatings with different structures (nanocrystalline, amorphous-crystalline, and amorphous) grown by rf magnetron sputtering on Ti and Si plates has been studied using the nanoindentation method. All the grown structures are characterized by the strain which has reversible and irreversible components. The hardness of nanocrystalline coatings (about 10 GPa) corresponds to the average hardness of hydroxyapatite single crystals. The structure of nanocrystalline coatings in the indentation zone and outside it has been investigated and changes in the structure under the indenter have been revealed using high-resolution transmission electron microscopy. From a comparison of the hardnesses of coatings with different structures and based on an analysis of the intragranular structure, it has been assumed that the plastic deformation occurs according to a dislocation-free mechanism. The plastic deformation is interpreted in terms of the cluster representation of the hydroxyapatite structure and amorphous calcium phosphates of the same elemental composition and cluster-boundary sliding during the deformation.

  8. Amorphous calcium phosphate and its application in dentistry

    PubMed Central

    2011-01-01

    Amorphous Calcium Phosphate (ACP) is an essential mineral phase formed in mineralized tissues and the first commercial product as artificial hydroxyapatite. ACP is unique among all forms of calcium phosphates in that it lacks long-range, periodic atomic scale order of crystalline calcium phosphates. The X-ray diffraction pattern is broad and diffuse with a maximum at 25 degree 2 theta, and no other different features compared with well-crystallized hydroxyapatite. Under electron microscopy, its morphological form is shown as small spheroidal particles in the scale of tenths nanometer. In aqueous media, ACP is easily transformed into crystalline phases such as octacalcium phosphate and apatite due to the growing of microcrystalline. It has been demonstrated that ACP has better osteoconductivity and biodegradability than tricalcium phosphate and hydroxyapatite in vivo. Moreover, it can increase alkaline phosphatase activities of mesoblasts, enhance cell proliferation and promote cell adhesion. The unique role of ACP during the formation of mineralized tissues makes it a promising candidate material for tissue repair and regeneration. ACP may also be a potential remineralizing agent in dental applications. Recently developed ACP-filled bioactive composites are believed to be effective anti-demineralizing/remineralizing agents for the preservation and repair of tooth structures. This review provides an overview of the development, structure, chemical composition, morphological characterization, phase transformation and biomedical application of ACP in dentistry. PMID:21740535

  9. The Electronic Structure of Amorphous Carbon Nanodots.

    PubMed

    Margraf, Johannes T; Strauss, Volker; Guldi, Dirk M; Clark, Timothy

    2015-06-18

    We have studied hydrogen-passivated amorphous carbon nanostructures with semiempirical molecular orbital theory in order to provide an understanding of the factors that affect their electronic properties. Amorphous structures were first constructed using periodic calculations in a melt/quench protocol. Pure periodic amorphous carbon structures and their counterparts doped with nitrogen and/or oxygen feature large electronic band gaps. Surprisingly, descriptors such as the elemental composition and the number of sp(3)-atoms only influence the electronic structure weakly. Instead, the exact topology of the sp(2)-network in terms of effective conjugation defines the band gap. Amorphous carbon nanodots of different structures and sizes were cut out of the periodic structures. Our calculations predict the occurrence of localized electronic surface states, which give rise to interesting effects such as amphoteric reactivity and predicted optical band gaps in the near-UV/visible range. Optical and electronic gaps display a dependence on particle size similar to that of inorganic colloidal quantum dots. PMID:25731776

  10. Electronic transport in amorphous carbon

    SciTech Connect

    Sullivan, J.P.; Friedmann, T.A.

    1997-12-01

    Electronic transport in a-C films has been the subject of considerable debate. In this study, combined stress relaxation and electrical transport studies were used to identify the transport mechanism in a-C films prepared by pulsed-laser deposition. The stress relaxation was modeled by a first-order kinetic reaction involving transformation of 4-fold coordinated carbon atoms to 3-fold coordinated carbon atoms, and the distribution of activation energies for this process was determined. The activation energies were found to range from about 1 eV to over 2 eV, and using these activation energies, the increase in 3-fold carbon concentration with time-temperature annealing was obtained. Conductivity measurements were also performed as a function of time-temperature annealing. It was found that the conductivity of a-C films is exponentially proportional to increases in 3-fold carbon concentration. This result can be explained by thermally activated hopping along carbon 3-fold chains combined with chain-to-chain tunneling. From the data, a typical chain length was estimated to consist of 13 carbon atoms. The heterogeneous nature of the conductivity may explain the spatially localized electron emission which is observed in a-C assuming a tunnel barrier emission model.

  11. Infrared emission from hydrogenated amorphous carbon and amorphous carbon grains in the interstellar medium

    NASA Technical Reports Server (NTRS)

    Duley, W. W.; Jones, A. P.; Taylor, S. D.; Williams, D. A.

    1993-01-01

    The correlations deduced by Boulanger et al. (1990) from IRAS maps of the Chamaeleon, Taurus and Ursa Major molecular cloud complexes are interpreted in terms of the evolutionary hydrogenated amorphous carbon model of interstellar dust. In particular, regions of relatively strong 12-micron emission may be regions where recently accreted carbon is being converted by ambient UV to small PAHs in situ. Regions of weak 12-micron emission are probably quiescent regions where carbon has been annealed to amorphous carbon. Observational consequences of these inferences are briefly described.

  12. Novel microwave synthesis of amorphous calcium phosphate nanospheres.

    PubMed

    Zhou, Huan; Bhaduri, Sarit

    2012-05-01

    Amorphous calcium phosphate (ACP) is an important precursor phase in tissue mineralization. It shows high solubility and excellent remineralization ability. Commercially viable techniques for producing ACP are high-cost/low-efficiency process. This article describes a novel microwave (MW)-assisted ACP synthesis route as an alternative to current ACP synthesis methods. An important feature of the process is the use of supersaturated biomimetic fluids (SBFs), which are based on Kokubo-like simulated body fluids. However, our present compositions are substantially different in that they no longer simulate the body fluid compositions. The effects of solution composition and processing parameters were studied. The mechanism of ACP synthesis under MW irradiation process is also discussed. The as-synthesized ACP nanospheres were characterized and showed good reactivity and biocompatibility. These as-synthesized nanoparticles can be potential candidates for biomedical applications and remineralization mechanism study. PMID:22331618

  13. Investigations on silicon/amorphous-carbon and silicon/nanocrystalline palladium/ amorphous-carbon interfaces.

    PubMed

    Roy, M; Sengupta, P; Tyagi, A K; Kale, G B

    2008-08-01

    Our previous work revealed that significant enhancement in sp3-carbon content of amorphous carbon films could be achieved when grown on nanocrystalline palladium interlayer as compared to those grown on bare silicon substrates. To find out why, the nature of interface formed in both the cases has been investigated using Electron Probe Micro Analysis (EPMA) technique. It has been found that a reactive interface in the form of silicon carbide and/silicon oxy-carbide is formed at the interface of silicon/amorphous-carbon films, while palladium remains primarily in its native form at the interface of nanocrystalline palladium/amorphous-carbon films. However, there can be traces of dissolved oxygen within the metallic layer as well. The study has been corroborated further from X-ray photoelectron spectroscopic studies. PMID:19049221

  14. Spinning up the polymorphs of calcium carbonate

    PubMed Central

    Boulos, Ramiz A.; Zhang, Fei; Tjandra, Edwin S.; Martin, Adam D.; Spagnoli, Dino; Raston, Colin L.

    2014-01-01

    Controlling the growth of the polymorphs of calcium carbonate is important in understanding the changing environmental conditions in the oceans. Aragonite is the main polymorph in the inner shells of marine organisms, and can be readily converted to calcite, which is the most stable polymorph of calcium carbonate. Both of these polymorphs are significantly more stable than vaterite, which is the other naturally occurring polymorph of calcium carbonate, and this is reflected in its limited distribution in nature. We have investigated the effect of high shear forces on the phase behaviour of calcium carbonate using a vortex fluidic device (VFD), with experimental parameters varied to explore calcium carbonate mineralisation. Variation of tilt angle, rotation speed and temperature allow for control over the size, shape and phase of the resulting calcium carbonate. PMID:24448077

  15. Binding of calcium and carbonate to polyacrylates.

    PubMed

    Tribello, Gareth A; Liew, CheeChin; Parrinello, Michele

    2009-05-21

    Polyacrylate molecules can be used to slow the growth of calcium carbonate. However, little is known about the mechanism by which the molecules impede the growth rate. A recent computational study (Bulo et al. Macromolecules 2007, 40, 3437) used metadynamics to investigate the binding of calcium to polyacrylate chains and has thrown some light on the coiling and precipitation of these polymers. We extend these simulations to examine the binding of calcium and carbonate to polyacrylate chains. We show that calcium complexed with both carbonate and polyacrylate is a very stable species. The free energies of calcium-carbonate-polyacrylate complexes, with different polymer configurations, are calculated, and differences in the free energy of the binding of carbonate are shown to be due to differences in the amount of steric hindrance about the calcium, which prevents the approach of the carbonate ion. PMID:19400592

  16. Rapid Annealing Of Amorphous Hydrogenated Carbon

    NASA Technical Reports Server (NTRS)

    Alterovitz, Samuel A.; Pouch, John J.; Warner, Joseph D.

    1989-01-01

    Report describes experiments to determine effects of rapid annealing on films of amorphous hydrogenated carbon. Study represents first efforts to provide information for applications of a-C:H films where rapid thermal processing required. Major finding, annealing causes abrupt increase in absorption and concomitant decrease in optical band gap. Most of change occurs during first 20 s, continues during longer annealing times. Extend of change increases with annealing temperature. Researchers hypothesize abrupt initial change caused by loss of hydrogen, while gradual subsequent change due to polymerization of remaining carbon into crystallites or sheets of graphite. Optical band gaps of unannealed specimens on silicon substrates lower than those of specimens on quartz substrates.

  17. Nanostructural characterization of amorphous diamondlike carbon films

    SciTech Connect

    SIEGAL,MICHAEL P.; TALLANT,DAVID R.; MARTINEZ-MIRANDA,L.J.; BARBOUR,J. CHARLES; SIMPSON,REGINA L.; OVERMYER,DONALD L.

    2000-01-27

    Nanostructural characterization of amorphous diamondlike carbon (a-C) films grown on silicon using pulsed-laser deposition (PLD) is correlated to both growth energetic and film thickness. Raman spectroscopy and x-ray reflectivity probe both the topological nature of 3- and 4-fold coordinated carbon atom bonding and the topographical clustering of their distributions within a given film. In general, increasing the energetic of PLD growth results in films becoming more ``diamondlike'', i.e. increasing mass density and decreasing optical absorbance. However, these same properties decrease appreciably with thickness. The topology of carbon atom bonding is different for material near the substrate interface compared to material within the bulk portion of an a-C film. A simple model balancing the energy of residual stress and the free energies of resulting carbon topologies is proposed to provide an explanation of the evolution of topographical bonding clusters in a growing a-C film.

  18. Amorphous calcium phosphate composites with improved mechanical properties

    PubMed Central

    O’Donnell, J.N.R.; Antonucci, J.M.; Skrtic, D.

    2008-01-01

    Hybridized zirconium amorphous calcium phosphate (ACP)-filled methacrylate composites make good calcium and phosphate releasing materials for anti-demineralizing/remineralizing applications with low mechanical demands. The objective of this study was to assess the effect of the particle size of the filler on the mechanical properties of these composites. Photo-curable resins were formulated from ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate and methacryloxyethyl phthalate. Camphorquinone and ethyl-4-N,N-dimethylaminobenzoate were utilized as components of the photoinitiator system. After 2 h of mechanical milling in isopropanol, an approximate 64 % reduction in the median particle diameter was observed [27.48 μm vs. 9.98 μm] for unmilled and milled wet ACP, respectively. Dry ACP showed a 43 % reduction in particle size from pre- to post-milling. As well as dry composites, those that had been immersed in aqueous media were evaluated for their Young’s Modulus, water sorption, biaxial tensile, three-point flexural and diametral tensile strength. Mechanically milling the filler increased the volume of fine particles in the composite specimens, resulting in a more homogeneous intra-composite distribution of ACP and a reduction in voids. In turn, less water diffused into the milled composites upon aqueous exposure, and they showed a marked improvement in biaxial flexure strength and a moderate improvement in flexural strength over composites with unmilled ACP. The demonstrated improvement in the mechanical stability of milled Zr-ACP composites may help in extending their dental applicability. PMID:18688290

  19. Multi-Functions of Carbonated Calcium Deficient Hydroxyapatite (CDHA)

    NASA Astrophysics Data System (ADS)

    Zhou, Huan

    Natural bone is a complex composite mainly constituted of inorganic minerals and organic collagen molecules. Calcium phosphate (CaP) based materials have been proposed as the predominant bone substitute for bone tissue engineering applications due to their chemical similarity to bone mineral. Amorphous carbonated calcium deficient hydroxyapatite (CDHA) is an important compound among CaP materials because of the amorphous crystallite structure. The presence of extra ions in its lattice structure not only influences cell attachment and proliferation of osteoblasts, but also helps in bone metabolism. Biomimetic coating approach is the most widely used approach to produce CDHA coatings to implant. It is a process using simulated body fluid (SBF) to deposit bone-like CDHA coating to various material surfaces. The CDHA formation mechanism, SBF compositions and reacting conditions of biomimetic coating have already been sufficiently studied and compared in the past 20 years. It is an attempt in this thesis to explore new applications of SBF in biomedical research, focusing on different biomaterial applications: 1) based on the low temperature reaction condition of SBF, bisphosphonate incorporated CDHA coatings were deposited onto Ti6Al4V surface for the treatment of osteoporosis; 2) amorphous calcium phosphate nanospheres with extra elements in the lattice structure were prepared by a novel microwave assisted approach, providing a new potential of CaP materials production; 3) CDHA particles formed in SBF can be used as great fillers with biopolymers for preparing biocomposites for biomedical applications; 4) based on the high activity of CDHA amorphous structure and the stabilization ability of ethanol, yttrium and europium doped calcium phosphates were prepared using CDHA as a sacrificing template. In the end, future work based on these observations in the thesis is addressed, including areas of drug delivery, biocomposite fabrication and preparation of functionalized

  20. 21 CFR 73.1070 - Calcium carbonate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Calcium carbonate. 73.1070 Section 73.1070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF... mixtures for coloring drugs. (b) Specifications. Calcium carbonate shall meet the specifications...

  1. 21 CFR 73.1070 - Calcium carbonate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Calcium carbonate. 73.1070 Section 73.1070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF... mixtures for coloring drugs. (b) Specifications. Calcium carbonate shall meet the specifications...

  2. 21 CFR 582.5191 - Calcium carbonate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium carbonate. 582.5191 Section 582.5191 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5191 Calcium carbonate....

  3. Degree of vinyl conversion in experimental amorphous calcium phosphate composites

    NASA Astrophysics Data System (ADS)

    Tarle, Z.; Knežević, A.; Matošević, D.; Škrtić, D.; Ristić, M.; Prskalo, K.; Musić, S.

    2009-04-01

    An experimental dental composite, based on amorphous calcium phosphate (ACP) with the potential to arrest caries development and regenerate mineral-deficient tooth structures has recently been developed. The aim of this study was to assess the degree of vinyl conversion (DVC) attained in experimental composites based on zirconia-modified ACP. Photo-activated resins were based on ethoxylated bisphenol A dimethacrylate (EBPADMA) [ETHM series with varying EBPADMA/triethylene glycol dimethacrylate (TEGDMA) molar ratios assigned 0.5-ETHM I, 0.85-ETHM II and 1.35-ETHM III], or 2,2-bis[p-(2'-hydroxy-3'-methacryloxypropoxy)phenyl]-propane (Bis-GMA) [BTHZ series]. To asses a possible effect of filler particle size on DVC, composites containing 60 mass % resin and 40 mass % of either milled ACP (mACP; median diameter d m = 0.9 μm) or coarse ACP (cACP; d m = 6.0 μm) were prepared, and irradiated with LED curing unit for 40 s. The DVC was calculated as the % change in the ratio of the integrated peak areas between the aliphatic and aromatic absorption bands determined by Fourier transform infrared spectroscopy (FTIR). The highest DVCs values were attained in mACP-BTHZ, cACP-BTHZ and mACP-ETHM III formulations. DVC of tested ACP composites (on average (76.76 ± 4.43)%) compares well with or exceeds DVCs values reported for the majority of commercial materials.

  4. Characterization of calcium phosphate cements modified by addition of amorphous calcium phosphate.

    PubMed

    Van den Vreken, Natasja M F; Pieters, Ilse Y; Declercq, Heidi A; Cornelissen, Maria J; Verbeeck, Ronald M H

    2010-02-01

    In this study the influence of amorphous calcium phosphate (ACP) on the setting of, and the formed apatite crystallite size in, a calcium phosphate cement (CPC) based on alpha-tricalcium phosphate (alpha-TCP) or tetracalcium phosphate (TTCP)/monocalcium phosphate monohydrate (MCPM) was investigated. Setting times at 22 degrees C were measured in air atmosphere; those at 37 degrees C were measured at 100% relative humidity. The phase composition of the set cements was investigated after 1 week using X-ray diffractometry and infrared spectroscopy and the morphology was investigated using scanning electron microscopy. The compressive strength (CS) of the set CPCs was measured after 1 day. Viability of MC3T3-E1 cells on the CPCs was analyzed after 7, 14 and 21 days of incubation using the CellTiter 96 Aqueous Non-Radioactive Cell Proliferation Assay. The alpha-TCP-based cement exhibited long setting times, a high CS and was converted to a calcium-deficient hydroxyapatite (CDHAp). The TTCP/MCPM-based CPC was only partly converted to CDHAp, produced acceptable setting times and had a low CS. Addition of ACP to these two CPCs resulted in cements that exhibited good setting times, CS suitable for non-load-bearing applications and a full conversion to nanocrystalline CDHAp. Moreover, the ACP containing CPCs demonstrated good cell viability, making them suitable candidates for bone substitute materials. PMID:19654057

  5. The effect of amorphous calcium phosphate on protein protection against thermal denaturation.

    PubMed

    Yang, Yuling; Wang, Guangchuan; Zhu, Genxing; Xu, Xurong; Pan, Haihua; Tang, Ruikang

    2015-05-21

    The hybrid nanoparticles of amorphous calcium phosphate (ACP)-catalase (CAT) developed by in situ biomineralization can create a stable semi-aqueous nanoscale environment for entrapped proteins against thermal denaturation. This finding indicates the importance of an amorphous mineral phase in the preservation of organic macromolecules. PMID:25913601

  6. Oxygenated amorphous carbon for resistive memory applications

    NASA Astrophysics Data System (ADS)

    Santini, Claudia A.; Sebastian, Abu; Marchiori, Chiara; Jonnalagadda, Vara Prasad; Dellmann, Laurent; Koelmans, Wabe W.; Rossell, Marta D.; Rossel, Christophe P.; Eleftheriou, Evangelos

    2015-10-01

    Carbon-based electronics is a promising alternative to traditional silicon-based electronics as it could enable faster, smaller and cheaper transistors, interconnects and memory devices. However, the development of carbon-based memory devices has been hampered either by the complex fabrication methods of crystalline carbon allotropes or by poor performance. Here we present an oxygenated amorphous carbon (a-COx) produced by physical vapour deposition that has several properties in common with graphite oxide. Moreover, its simple fabrication method ensures excellent reproducibility and tuning of its properties. Memory devices based on a-COx exhibit outstanding non-volatile resistive memory performance, such as switching times on the order of 10 ns and cycling endurance in excess of 104 times. A detailed investigation of the pristine, SET and RESET states indicates a switching mechanism based on the electrochemical redox reaction of carbon. These results suggest that a-COx could play a key role in non-volatile memory technology and carbon-based electronics.

  7. Amorphous silicon-carbon alloys and amorphous carbon from direct methane and ethylene activation by ECR

    SciTech Connect

    Conde, J.P.; Chu, V.; Giorgis, F.; Pirri, C.F.; Arekat, S.

    1997-07-01

    Hydrogenated amorphous silicon-carbon alloys are prepared using electron-cyclotron resonance (ECR) plasma-enhanced chemical vapor deposition. Hydrogen is introduced into the source resonance cavity as an excitation gas. Silane is introduced in the main chamber in the vicinity of the plasma stream, whereas the carbon source gases, methane or ethylene, are introduced either with the silane or with the hydrogen as excitation gases. The effect of the type of carbon-source gas, excitation gas mixture and silane-to-carbon source gas flow ratio on the deposition rate, bandgap, subgap density of states, spin density and hydrogen evolution are studied.

  8. Amorphous calcium phosphate is a major component of the forming fin bones of zebrafish: Indications for an amorphous precursor phase.

    PubMed

    Mahamid, Julia; Sharir, Amnon; Addadi, Lia; Weiner, Steve

    2008-09-01

    A fundamental question in biomineralization is the nature of the first-formed mineral phase. In vertebrate bone formation, this issue has been the subject of a long-standing controversy. We address this key issue using the continuously growing fin bony rays of the Tuebingen long-fin zebrafish as a model for bone mineralization. Employing high-resolution scanning and transmission electron microscopy imaging, electron diffraction, and elemental analysis, we demonstrate the presence of an abundant amorphous calcium phosphate phase in the newly formed fin bones. The extracted amorphous mineral particles crystallize with time, and mineral crystallinity increases during bone maturation. Based on these findings, we propose that this amorphous calcium phosphate phase may be a precursor phase that later transforms into the mature crystalline mineral. PMID:18753619

  9. Amorphous Silicon-Carbon Nanostructure Solar Cells

    NASA Astrophysics Data System (ADS)

    Schriver, Maria; Regan, Will; Loster, Matthias; Zettl, Alex

    2011-03-01

    Taking advantage of the ability to fabricate large area graphene and carbon nanotube networks (buckypaper), we produce Schottky junction solar cells using undoped hydrogenated amorphous silicon thin films and nanostructured carbon films. These films are useful as solar cell materials due their combination of optical transparency and conductance. In our cells, they behave both as a transparent conductor and as an active charge separating layer. We demonstrate a reliable photovoltaic effect in these devices with a high open circuit voltage of 390mV in buckypaper devices. We investigate the unique interface properties which result in an unusual J-V curve shape and optimize fabrication processes for improved solar conversion efficiency. These devices hold promise as a scalable solar cell made from earth abundant materials and without toxic and expensive doping processes.

  10. Coaxial carbon plasma gun deposition of amorphous carbon films

    NASA Technical Reports Server (NTRS)

    Sater, D. M.; Gulino, D. A.; Rutledge, S. K.

    1984-01-01

    A unique plasma gun employing coaxial carbon electrodes was used in an attempt to deposit thin films of amorphous diamond-like carbon. A number of different structural, compositional, and electrical characterization techniques were used to characterize these films. These included scanning electron microscopy, scanning transmission electron microscopy, X ray diffraction and absorption, spectrographic analysis, energy dispersive spectroscopy, and selected area electron diffraction. Optical absorption and electrical resistivity measurements were also performed. The films were determined to be primarily amorphous, with poor adhesion to fused silica substrates. Many inclusions of particulates were found to be present as well. Analysis of these particulates revealed the presence of trace impurities, such as Fe and Cu, which were also found in the graphite electrode material. The electrodes were the source of these impurities. No evidence of diamond-like crystallite structure was found in any of the film samples. Details of the apparatus, experimental procedure, and film characteristics are presented.

  11. Ab Initio Studies of Calcium Carbonate Hydration.

    PubMed

    Lopez-Berganza, Josue A; Diao, Yijue; Pamidighantam, Sudhakar; Espinosa-Marzal, Rosa M

    2015-11-25

    Ab initio simulations of large hydrated calcium carbonate clusters are challenging due to the existence of multiple local energy minima. Extensive conformational searches around hydrated calcium carbonate clusters (CaCO3·nH2O for n = 1-18) were performed to find low-energy hydration structures using an efficient combination of Monte Carlo searches, density-functional tight binding (DFTB+) method, and density-functional theory (DFT) at the B3LYP level, or Møller-Plesset perturbation theory at the MP2 level. This multilevel optimization yields several low-energy structures for hydrated calcium carbonate. Structural and energetics analysis of the hydration of these clusters revealed a first hydration shell composed of 12 water molecules. Bond-length and charge densities were also determined for different cluster sizes. The solvation of calcium carbonate in bulk water was investigated by placing the explicitly solvated CaCO3·nH2O clusters in a polarizable continuum model (PCM). The findings of this study provide new insights into the energetics and structure of hydrated calcium carbonate and contribute to the understanding of mechanisms where calcium carbonate formation or dissolution is of relevance. PMID:26505205

  12. Filtered pulsed carbon cathodic arc: Plasma and amorphous carbon properties

    NASA Astrophysics Data System (ADS)

    Liu, Dongping; Benstetter, Günther; Lodermeier, Edgar; Zhang, Jialiang; Liu, Yanhong; Vancea, Johann

    2004-06-01

    The carbon plasma ion energies produced by the filtered pulsed cathodic arc discharge method were measured as a function of filter inductance. The energy determination is based on the electro-optical time-of-flight method. The average ion energies of the pulsed ion beams were found to depend upon the rise time and duration of pulsed arc currents, which suggests that a gain of ion kinetic energy mainly arises from the electric plasma field from the ambipolar expansion of both electrons and ions, and an electron drag force because of the high expansion velocity of the electrons. The tetrahedral amorphous carbon (ta-C) films with a sp3 fraction of ˜70% were deposited on silicon substrates at the average ion energies of >6 eV in the highly ionized plasmas. The ta-C films were found to be covered with a few graphitelike atomic layers. The surface properties of ultrathin carbon films, such as nanoscale friction coefficients, surface layer thickness, and silicon contents were strongly dependent on the ion energies. The growth of amorphous carbon films was explained in terms of the thermal spike migration of surface carbon atoms. In terms of this model, the thermal spike provides the energy required to release surface atoms from their metastable positions and leads to the formation of the sp3 bonded carbon on a sp3 bonded matrix. The experimental results indicate that the low-energy (<3 eV) carbon ions have insufficient energies to cause the rearrangement reaction within the film and they form graphitelike structures at film surface.

  13. Au nanoparticles improve amorphous carbon to be gas sensors

    NASA Astrophysics Data System (ADS)

    Liu, Keng-Wen; Lee, Jian-Heng; Chou, Hsiung; Lin, Tzu-Ching; Lin, Si-Ting; Shih-Jye Sun Collaboration

    In order to make the amorphous carbon possess the gas sensing capability transferring some sp3 orbits to sp2 is necessary. It is proposed that the metallic materials having a large charge exchange with sp3 carbon orbits are being catalysts to transfer the carbon orbits. We found embedding gold nanoparticles to the amorphous carbon will induce many compact sp2 orbits around the nanoparticles, which make the amorphous carbon be the candidate material for the gas sensors. The orbits of amorphous carbon near the interface of Au nanoparticles can be changed from sp3 to compact sp2 to reduce the surface energy of Au nanoparticles. Meanwhile, our molecular dynamics simulation has confirmed the fact, when an Au nanoparticle is embedded in the amorphous carbon system the ratio of sp2 orbits increases dramatically. Similar results also have been confirmed from the Raman spectrum measurements. We controlled the carrier transport by changing the hopping barriers formed by amorphous carbon matrix between the Au nanoparticles to modify the resistance. These nanocomposites exhibit a superior sensitivity to NH3 at room temperature as well as good reproducibility and short response/recovery times, which could have potential applications in gas sensors. Dept. of Applied Physics,NUK, Kaohsiung, Taiwan.

  14. Novel technique for phosphorus recovery from aqueous solutions using amorphous calcium silicate hydrates (A-CSHs).

    PubMed

    Okano, Kenji; Uemoto, Masahide; Kagami, Jumpei; Miura, Keiichi; Aketo, Tsuyoshi; Toda, Masaya; Honda, Kohsuke; Ohtake, Hisao

    2013-05-01

    A novel technique for phosphorus (P) recovery from aqueous solutions was developed using amorphous calcium silicate hydrates (A-CSHs). A-CSHs, which have a high Ca/Si molar ratio of 2.0 or greater, could be synthesized using unlimitedly available, inexpensive materials such as siliceous shale and calcium hydroxide. A-CSHs showed high performance for P recovery from an anaerobic sludge digestion liquor (ASDL) and the synthetic model liquor (s-ASDL) containing 89 mg PO4-P/L. After 20 min mixing, 1.5 g/L A-CSHs could remove approximately 69 and 73% PO4-P from ASDL and s-ASDL, respectively. By contrast, autoclaved lightweight concrete particles, which contained crystalline calcium silicate hydrates as a principal component, removed only 10 and 6% PO4-P from ASDL and s-ASDL, respectively, under the same experimental conditions. When A-CSHs were washed with deionized water to remove free Ca(OH)2, P removability was significantly improved (up to 82%) despite the reduction in the amount of Ca(2+) released. Unlike in the case of Ca(OH)2, no significant carbonate inhibition was observed with P removal by A-CSHs. Moreover, P removed by A-CSHs showed better settleability, filterability, and dewaterability than P precipitated with conventional CaCl2 and Ca(OH)2. The present study demonstrated that A-CSHs have great potential as a novel, beneficial material for P recovery and recycling. PMID:23497975

  15. Properties of vacuum arc deposited amorphous hard carbon films

    SciTech Connect

    Anders, S.; Anders, A.; Raoux, S.

    1995-04-01

    Amorphous hard carbon films formed by vacuum arc deposition are hydrogen-free, dense, and very hard. The properties of amorphous hard carbon films depend strongly on the energy of the incident ions. A technique which is called Plasma Immersion Ion Implantation can be applied to vacuum arc deposition of amorphous hard carbon films to influence the ion energy. The authors have studied the influence of the ion energy on the elastic modulus determined by an ultrasonic method, and have measured the optical gap for films with the highest sp{sup 3} content they have obtained so far with this deposition technique. The results show an elastic modulus close to that of diamond, and an optical gap of 2.1 eV which is much greater than for amorphous hard carbon films deposited by other techniques.

  16. Calcination of calcium carbonate and blend therefor

    SciTech Connect

    Mallow, W.A.; Dziuk, J.J. Jr.

    1989-05-09

    This patent describes a method for the accelerated calcination of a calcium carbonate material. It comprises: heating the calcium carbonate material to a temperature and for a time sufficient to calcine the material to the degree desired while in the presence of a fused salt catalyst consisting of particles having a size above or below that of the calcium carbonate material; the catalyst comprising at least one fused salt having the formula M{sub 2}CO{sub 3}. CaCO{sub 3}-CaO-H{sub 2}O{sub {ital x}}, wherein M is an alkali metal selected from sodium or potassium and x is 0 to 1 and the salt is formed by fusing M{sub 2}CO{sub 3} and CaCO{sub 3} in a molar ratio of about 1:2 to 2:1 when the alkali metal is sodium and about 1:1 to 2:1 when the alkali metal is potassium. This patent also describes a blend adapted to be heated to form CaO. It comprises: a calcium carbonate material and a catalyst consisting of particles having a size above or below that of the calcium carbonate material; the catalyst comprising at least one fused salt having the formula M{sub 2}CO{sub 3}-CaCO{sub 3}CaO-H{sub 2}O{sub {ital x}}.

  17. Calcination of calcium carbonate and blend therefor

    SciTech Connect

    Mallow, William A.; Dziuk, Jr., Jerome J.

    1989-01-01

    A method for calcination of a calcium carbonate material comprising heating the calcium carbonate material to a temperature and for a time sufficient to calcine the material to the degree desired while in the presence of a catalyst; said catalyst comprising at least one fused salt having the formula MCO.sub.3.CaCO.sub.3.CaO.H.sub.2 O.sub.x, wherein M is an alkali metal and x is 0 to 1 and formed by fusing MCO.sub.3 and CaCO.sub.3 in a molar ratio of about 1:2 to 2:1, and a blend adapted to be heated to CaO comprising a calcium carbonate material and at least one such fused salt.

  18. Amorphization of Silicon Carbide by Carbon Displacement

    SciTech Connect

    Devanathan, Ram; Gao, Fei; Weber, William J.

    2004-05-10

    We have used molecular dynamics simulations to examine the possibility of amorphizing silicon carbide (SiC) by exclusively displacing C atoms. At a defect generation corresponding to 0.2 displacements per atom, the enthalpy surpasses the level of melt-quenched SiC, the density decreases by about 15%, and the radial distribution function shows a lack of long-range order. Prior to amorphization, the surviving defects are mainly C Frenkel pairs (67%), but Si Frenkel pairs (18%) and anti-site defects (15%) are also present. The results indicate that SiC can be amorphized by C sublattice displacements. Chemical short-range disorder, arising mainly from interstitial production, plays a significant role in the amorphization.

  19. Calcium

    MedlinePlus

    ... of calcium dietary supplements are carbonate and citrate. Calcium carbonate is inexpensive, but is absorbed best when taken ... antacid products, such as Tums® and Rolaids®, contain calcium carbonate. Each pill or chew provides 200–400 mg ...

  20. 21 CFR 582.5191 - Calcium carbonate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Calcium carbonate. 582.5191 Section 582.5191 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or...

  1. 21 CFR 582.5191 - Calcium carbonate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Calcium carbonate. 582.5191 Section 582.5191 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or...

  2. 21 CFR 582.5191 - Calcium carbonate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Calcium carbonate. 582.5191 Section 582.5191 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or...

  3. 21 CFR 582.5191 - Calcium carbonate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Calcium carbonate. 582.5191 Section 582.5191 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or...

  4. Mapping residual organics and carbonate at grain boundaries and the amorphous interphase in mouse incisor enamel.

    PubMed

    Gordon, Lyle M; Joester, Derk

    2015-01-01

    Dental enamel has evolved to resist the most grueling conditions of mechanical stress, fatigue, and wear. Adding insult to injury, it is exposed to the frequently corrosive environment of the oral cavity. While its hierarchical structure is unrivaled in its mechanical resilience, heterogeneity in the distribution of magnesium ions and the presence of Mg-substituted amorphous calcium phosphate (Mg-ACP) as an intergranular phase have recently been shown to increase the susceptibility of mouse enamel to acid attack. Herein we investigate the distribution of two important constituents of enamel, residual organic matter and inorganic carbonate. We find that organics, carbonate, and possibly water show distinct distribution patterns in the mouse enamel crystallites, at simple grain boundaries, and in the amorphous interphase at multiple grain boundaries. This has implications for the resistance to acid corrosion, mechanical properties, and the mechanism by which enamel crystals grow during amelogenesis. PMID:25852562

  5. Mapping residual organics and carbonate at grain boundaries and the amorphous interphase in mouse incisor enamel

    PubMed Central

    Gordon, Lyle M.; Joester, Derk

    2015-01-01

    Dental enamel has evolved to resist the most grueling conditions of mechanical stress, fatigue, and wear. Adding insult to injury, it is exposed to the frequently corrosive environment of the oral cavity. While its hierarchical structure is unrivaled in its mechanical resilience, heterogeneity in the distribution of magnesium ions and the presence of Mg-substituted amorphous calcium phosphate (Mg-ACP) as an intergranular phase have recently been shown to increase the susceptibility of mouse enamel to acid attack. Herein we investigate the distribution of two important constituents of enamel, residual organic matter and inorganic carbonate. We find that organics, carbonate, and possibly water show distinct distribution patterns in the mouse enamel crystallites, at simple grain boundaries, and in the amorphous interphase at multiple grain boundaries. This has implications for the resistance to acid corrosion, mechanical properties, and the mechanism by which enamel crystals grow during amelogenesis. PMID:25852562

  6. Fracture of Carbon Nanotube - Amorphous Carbon Composites: Molecular Modeling

    NASA Technical Reports Server (NTRS)

    Jensen, Benjamin D.; Wise, Kristopher E.; Odegard, Gregory M.

    2015-01-01

    Carbon nanotubes (CNTs) are promising candidates for use as reinforcements in next generation structural composite materials because of their extremely high specific stiffness and strength. They cannot, however, be viewed as simple replacements for carbon fibers because there are key differences between these materials in areas such as handling, processing, and matrix design. It is impossible to know for certain that CNT composites will represent a significant advance over carbon fiber composites before these various factors have been optimized, which is an extremely costly and time intensive process. This work attempts to place an upper bound on CNT composite mechanical properties by performing molecular dynamics simulations on idealized model systems with a reactive forcefield that permits modeling of both elastic deformations and fracture. Amorphous carbon (AC) was chosen for the matrix material in this work because of its structural simplicity and physical compatibility with the CNT fillers. It is also much stiffer and stronger than typical engineering polymer matrices. Three different arrangements of CNTs in the simulation cell have been investigated: a single-wall nanotube (SWNT) array, a multi-wall nanotube (MWNT) array, and a SWNT bundle system. The SWNT and MWNT array systems are clearly idealizations, but the SWNT bundle system is a step closer to real systems in which individual tubes aggregate into large assemblies. The effect of chemical crosslinking on composite properties is modeled by adding bonds between the CNTs and AC. The balance between weakening the CNTs and improving fiber-matrix load transfer is explored by systematically varying the extent of crosslinking. It is, of course, impossible to capture the full range of deformation and fracture processes that occur in real materials with even the largest atomistic molecular dynamics simulations. With this limitation in mind, the simulation results reported here provide a plausible upper limit on

  7. Angular magnetoresistance in semiconducting undoped amorphous carbon thin films

    NASA Astrophysics Data System (ADS)

    Sagar, Rizwan Ur Rehman; Saleemi, Awais Siddique; Zhang, Xiaozhong

    2015-05-01

    Thin films of undoped amorphous carbon thin film were fabricated by using Chemical Vapor Deposition and their structure was investigated by using High Resolution Transmission Electron Microscopy and Raman Spectroscopy. Angular magnetoresistance (MR) has been observed for the first time in these undoped amorphous carbon thin films in temperature range of 2 ˜ 40 K. The maximum magnitude of angular MR was in the range of 9.5% ˜ 1.5% in 2 ˜ 40 K. The origin of this angular MR was also discussed.

  8. Angular magnetoresistance in semiconducting undoped amorphous carbon thin films

    SciTech Connect

    Sagar, Rizwan Ur Rehman; Saleemi, Awais Siddique; Zhang, Xiaozhong

    2015-05-07

    Thin films of undoped amorphous carbon thin film were fabricated by using Chemical Vapor Deposition and their structure was investigated by using High Resolution Transmission Electron Microscopy and Raman Spectroscopy. Angular magnetoresistance (MR) has been observed for the first time in these undoped amorphous carbon thin films in temperature range of 2 ∼ 40 K. The maximum magnitude of angular MR was in the range of 9.5% ∼ 1.5% in 2 ∼ 40 K. The origin of this angular MR was also discussed.

  9. Egg-white-mediated crystallization of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Zheng, Liang; Hu, Yanli; Ma, Yongjun; Zhou, Yong; Nie, Fude; Liu, Xun; Pei, Chonghua

    2012-12-01

    In this paper, shape-controlled crystallization and self-assembly of CaCO3 hierarchical architectures has been successfully synthesized via the gas diffusion method in egg white solution. Stepwise growth and assembly of CaCO3 nanoparticles has been observed from transition of an amorphous CaCO3 to the crystallization and stabilization of platelet-like nanoparticles and eventually, the wool sphere-like CaCO3 hierarchical architectures assembling of nanoparticles. The proteins binding on nanoparticle surfaces proved to regulate the growth of nanoparticles and subsequent assembly into hierarchical superstructures via electrostatic and dipole interactions. The samples were characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and nano mechanical Tester. The measured average elastic modulus and the hardness of calcium carbonate hybrid materials were 5.32 GPa and 0.1886 GPa by the nano-indenter test, respectively.

  10. Two competitive nucleation mechanisms of calcium carbonate biomineralization in response to surface functionality in low calcium ion concentration solution

    PubMed Central

    Deng, Hua; Wang, Shuo; Wang, Xiumei; Du, Chang; Shen, Xingcan; Wang, Yingjun; Cui, Fuzhai

    2015-01-01

    Four self-assembled monolayer surfaces terminated with –COOH, –OH, –NH2 and –CH3 functional groups are used to direct the biomineralization processes of calcium carbonate (CaCO3) in low Ca2+ concentration, and the mechanism of nucleation and initial crystallization within 12 h was further explored. On −COOH surface, nucleation occurs mainly via ion aggregation mechanism while prenucleation ions clusters may be also involved. On −OH and −NH2 surfaces, however, nucleation forms via calcium carbonate clusters, which aggregate in solution and then are adsorbed onto surfaces following with nucleation of amorphous calcium carbonate (ACC). Furthermore, strongly negative-charged −COOH surface facilitates the direct formation of calcites, and the −OH and −NH2 surfaces determine the formation of vaterites with preferred crystalline orientations. Neither ACC nor crystalline CaCO3 is observed on −CH3 surface. Our findings present a valuable model to understand the CaCO3 biomineralization pathway in natural system where functional groups composition plays a determining role during calcium carbonate crystallization. PMID:26814639

  11. Two competitive nucleation mechanisms of calcium carbonate biomineralization in response to surface functionality in low calcium ion concentration solution.

    PubMed

    Deng, Hua; Wang, Shuo; Wang, Xiumei; Du, Chang; Shen, Xingcan; Wang, Yingjun; Cui, Fuzhai

    2015-09-01

    Four self-assembled monolayer surfaces terminated with -COOH, -OH, -NH2 and -CH3 functional groups are used to direct the biomineralization processes of calcium carbonate (CaCO3) in low Ca(2+) concentration, and the mechanism of nucleation and initial crystallization within 12 h was further explored. On -COOH surface, nucleation occurs mainly via ion aggregation mechanism while prenucleation ions clusters may be also involved. On -OH and -NH2 surfaces, however, nucleation forms via calcium carbonate clusters, which aggregate in solution and then are adsorbed onto surfaces following with nucleation of amorphous calcium carbonate (ACC). Furthermore, strongly negative-charged -COOH surface facilitates the direct formation of calcites, and the -OH and -NH2 surfaces determine the formation of vaterites with preferred crystalline orientations. Neither ACC nor crystalline CaCO3 is observed on -CH3 surface. Our findings present a valuable model to understand the CaCO3 biomineralization pathway in natural system where functional groups composition plays a determining role during calcium carbonate crystallization. PMID:26814639

  12. A shear localization mechanism for lubricity of amorphous carbon materials

    PubMed Central

    Ma, Tian-Bao; Wang, Lin-Feng; Hu, Yuan-Zhong; Li, Xin; Wang, Hui

    2014-01-01

    Amorphous carbon is one of the most lubricious materials known, but the mechanism is not well understood. It is counterintuitive that such a strong covalent solid could exhibit exceptional lubricity. A prevailing view is that lubricity of amorphous carbon results from chemical passivation of dangling bonds on surfaces. Here we show instead that lubricity arises from shear induced strain localization, which, instead of homogeneous deformation, dominates the shearing process. Shear localization is characterized by covalent bond reorientation, phase transformation and structural ordering preferentially in a localized region, namely tribolayer, resulting in shear weakening. We further demonstrate an anomalous pressure induced transition from stick-slip friction to continuous sliding with ultralow friction, due to gradual clustering and layering of graphitic sheets in the tribolayer. The proposed shear localization mechanism sheds light on the mechanism of superlubricity, and would enrich our understanding of lubrication mechanism of a wide variety of amorphous materials. PMID:24412998

  13. A shear localization mechanism for lubricity of amorphous carbon materials.

    PubMed

    Ma, Tian-Bao; Wang, Lin-Feng; Hu, Yuan-Zhong; Li, Xin; Wang, Hui

    2014-01-01

    Amorphous carbon is one of the most lubricious materials known, but the mechanism is not well understood. It is counterintuitive that such a strong covalent solid could exhibit exceptional lubricity. A prevailing view is that lubricity of amorphous carbon results from chemical passivation of dangling bonds on surfaces. Here we show instead that lubricity arises from shear induced strain localization, which, instead of homogeneous deformation, dominates the shearing process. Shear localization is characterized by covalent bond reorientation, phase transformation and structural ordering preferentially in a localized region, namely tribolayer, resulting in shear weakening. We further demonstrate an anomalous pressure induced transition from stick-slip friction to continuous sliding with ultralow friction, due to gradual clustering and layering of graphitic sheets in the tribolayer. The proposed shear localization mechanism sheds light on the mechanism of superlubricity, and would enrich our understanding of lubrication mechanism of a wide variety of amorphous materials. PMID:24412998

  14. A shear localization mechanism for lubricity of amorphous carbon materials

    NASA Astrophysics Data System (ADS)

    Ma, Tian-Bao; Wang, Lin-Feng; Hu, Yuan-Zhong; Li, Xin; Wang, Hui

    2014-01-01

    Amorphous carbon is one of the most lubricious materials known, but the mechanism is not well understood. It is counterintuitive that such a strong covalent solid could exhibit exceptional lubricity. A prevailing view is that lubricity of amorphous carbon results from chemical passivation of dangling bonds on surfaces. Here we show instead that lubricity arises from shear induced strain localization, which, instead of homogeneous deformation, dominates the shearing process. Shear localization is characterized by covalent bond reorientation, phase transformation and structural ordering preferentially in a localized region, namely tribolayer, resulting in shear weakening. We further demonstrate an anomalous pressure induced transition from stick-slip friction to continuous sliding with ultralow friction, due to gradual clustering and layering of graphitic sheets in the tribolayer. The proposed shear localization mechanism sheds light on the mechanism of superlubricity, and would enrich our understanding of lubrication mechanism of a wide variety of amorphous materials.

  15. Substrate/layer interface of amorphous-carbon hard coatings

    NASA Astrophysics Data System (ADS)

    Böhme, O.; Cebollada, A.; Yang, S.; Teer, D. G.; Albella, J. M.; Román, E.

    2000-08-01

    A combined study of the crystalline structure, the chemical interaction, and diffusion processes of the substrate/layer interface of amorphous-carbon hard coatings is presented. The structure of the coatings and their gradient layer interface to a chromium buffer layer has been investigated on two substrates [Si(100) and tool steel] using x-ray diffraction (XRD). Chemical interaction and diffusion processes at the interfaces and within the layers were analyzed by Auger electron spectroscopy and x-ray photoemission spectroscopy depth profiles. The chromium buffer layer revealed similar textured structure on both substrates. The subsequent gradient layer was determined (within XRD limits) to be amorphous and composed of an amorphous-carbon and chromium-carbide composite. The chromium carbide maintains the same stoichiometry (Cr3C2), regardless of the gradually changing chromium content. No large-scale interdiffusion was measured, either between or within the layers.

  16. Amorphous diamond: A high-pressure superhard carbon allotrope

    SciTech Connect

    Lin, Yu; Zhang, Li; Mao, Ho Kwang; Chow, Paul; Xiao, Yuming; Baldini, Maria; Shu, Jinfu; Mao, Wendy L.

    2011-01-01

    Compressing glassy carbon above 40 GPa, we have observed a new carbon allotrope with a fully sp³-bonded amorphous structure and diamondlike strength. Synchrotron x-ray Raman spectroscopy revealed a continuous pressure-induced sp²-to-sp³ bonding change, while x-ray diffraction confirmed the perseverance of noncrystallinity. The transition was reversible upon releasing pressure. Used as an indenter, the glassy carbon ball demonstrated exceptional strength by reaching 130 GPa with a confining pressure of 60 GPa. Such an extremely large stress difference of >70 GPa has never been observed in any material besides diamond, indicating the high hardness of this high-pressure carbon allotrope.

  17. Calcium carbonate crystal growth beneath Langmuir monolayers of acidic β-hairpin peptides.

    PubMed

    Gong, Haofei; Yang, Yi; Pluntke, Manuela; Marti, Othmar; Majer, Zsuzsa; Sewald, Norbert; Volkmer, Dirk

    2014-11-28

    Four amphiphilic peptides with designed hairpin structure were synthesized and their monolayers were employed as model systems to study biologically inspired calcium carbonate crystallization. Langmuir monolayers of hairpin peptides were investigated by surface pressure area isotherms, surface potential isotherms, Brewster angle microscopy (BAM), atomic force microscopy (AFM) and Fourier transform infrared (FTIR) spectroscopy. A β-hairpin conformation was found for all peptides at the air-water interface although their packing arrangements seem to be different. Crystallization of calcium carbonate under these peptide monolayers was investigated at different surface pressures and growth times both by in situ optical microscopy, BAM and ex situ investigations such as scanning electron microscopy (SEM) and transmission electron microscopy (TEM). An amorphous calcium carbonate precursor was found at the initial crystallization stage. The crystallization process occurred in three stages. It starts from the nucleation of amorphous particles being a kinetically controlled process. Crystal nuclei subsequently aggregate to large particles and vaterite crystals start to form inside the amorphous layer, with the monolayer fluidity exerting an important role. The third process includes the re-crystallization of vaterite to calcite, which is thermodynamically controlled by monolayer structural factors including the monolayer flexibility and packing arrangement of the polar headgroups. Thus, the kinetic factors, monolayer fluidity and flexibility as well as structure factors govern the crystal morphology and polymorph distribution simultaneously and synergistically. PMID:25292256

  18. Effect of Fluoride, Casein Phosphopeptide–Amorphous Calcium Phosphate and Casein Phosphopeptide–Amorphous Calcium Phosphate Fluoride on Enamel Surface Microhardness After Microabrasion: An in Vitro Study

    PubMed Central

    Ahmadi Zenouz, Ghazaleh; Ezoji, Fariba; Khafri, Soraya

    2015-01-01

    Objectives: This study aimed to assess the effect of applying casein phosphopeptide– amorphous calcium phosphate (CPP-ACP) paste, casein phosphopeptide–amorphous calcium phosphate fluoride (CPP-ACPF) paste and sodium fluoride gel on surface microhardness of enamel after microabrasion. Materials and Methods: Thirty freshly extracted human premolars were selected. All samples were subjected to hardness indentations made with the Vickers hardness machine and the average value was recorded as the initial surface microhardness. The specimens were then randomly divided into three groups (n=10) of CPP-ACPF, fluoride and CPPACP. The teeth were micro-abraded with Opalustre. Microhardness test was performed to assess the post-abrasion hardness. Three remineralization modalities were performed on samples of each group. The enamel surface microhardness measurements were performed. To compare the difference between groups, the rehardening and softening values were defined. One-way ANOVA and Tukey’s post hoc test at a significance level of 5% were used for statistical analysis. Results: The mean microhardness value (MMV) had a significant decrease after microabrasion from baseline. The MMV had a significant increase after remineralization in all groups. The MMV of CPP-ACPF group was significantly more than that of fluoride group (P=0.027). The rehardening value of fluoride group was significantly more than that of other groups (P<0.001). Conclusion: All the remineralizing agents were effective for rehardening the enamel after microabrasion. The CPP-ACP and CPP-ACPF pastes are effective, but to a lesser extent than neutral sodium fluoride gel in remineralizing enamel surface. Incorporation of fluoride to CPP-ACP formulation does not provide any additional remineralizing potential. PMID:27252753

  19. Electrochemical patterning of amorphous carbon on diamond

    NASA Technical Reports Server (NTRS)

    Marchywka, Mike; Pehrsson, Pehr E.; Binari, Steven C.; Moses, Daniel

    1993-01-01

    The ability to pattern ion-implantation damaged or other nondiamond carbon on a diamond substrate is useful for fabricating a variety of devices. We accomplished such patterning by an unmasked implantation into a diamond substrate followed by photolithography and a selective electrochemical etch. The use of a high resistivity medium coupled with applied biases over 50 V permitted etching without requiring contact between the substrate and an electrode. Many electrolytes gave etches that exhibit high selectivity for nondiamond carbon over both diamond and dielectrics such as photoresist. Optical, electrical, and Raman spectroscopic measurements elucidate the effects of the etch on the implanted diamond surface.

  20. Polymorphs calcium carbonate on temperature reaction

    SciTech Connect

    Chong, Kai-Yin; Chia, Chin-Hua; Zakaria, Sarani

    2014-09-03

    Calcium carbonate (CaCO{sub 3}) has three different crystal polymorphs, which are calcite, aragonite and vaterite. In this study, effect of reaction temperature on polymorphs and crystallite structure of CaCO{sub 3} was investigated. X-ray powder diffraction (XRD), fourier transform infrared (FTIR), and variable pressure scanning electron microscope (VPSEM) were used to characterize the obtained CaCO{sub 3} particles. The obtained results showed that CaCO{sub 3} with different crystal and particle structures can be formed by controlling the temperature during the synthesis process.

  1. Calcium and Oxygen Isotopic Composition of Calcium Carbonates

    NASA Astrophysics Data System (ADS)

    Niedermayr, Andrea; Eisenhauer, Anton; Böhm, Florian; Kisakürek, Basak; Balzer, Isabelle; Immenhauser, Adrian; Jürgen Köhler, Stephan; Dietzel, Martin

    2016-04-01

    Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h‑1 m‑2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in

  2. A facile magnesium-containing calcium carbonate biomaterial as potential bone graft.

    PubMed

    He, Fupo; Zhang, Jing; Tian, Xiumei; Wu, Shanghua; Chen, Xiaoming

    2015-12-01

    The calcium carbonate is the main composition of coral which has been widely used as bone graft in clinic. Herein, we readily prepared novel magnesium-containing calcium carbonate biomaterials (MCCs) under the low-temperature conditions based on the dissolution-recrystallization reaction between unstable amorphous calcium carbonate (ACC) and metastable vaterite-type calcium carbonate with water involved. The content of magnesium in MCCs was tailored by adjusting the proportion of ACC starting material that was prepared using magnesium as stabilizer. The phase composition of MCCs with various amounts of magnesium was composed of one, two or three kinds of calcium carbonates (calcite, aragonite, and/or magnesian calcite). The different MCCs differed in topography. The in vitro degradation of MCCs accelerated with increasing amount of introduced magnesium. The MCCs with a certain amount of magnesium not only acquired higher compressive strength, but also promoted in vitro cell proliferation and osteogenic differentiation. Taken together, the facile MCCs shed light on their potential as bone graft. PMID:26539810

  3. In-situ observation of the transformation of amorphous calcium phosphate to crystalline hydroxyapatite

    NASA Astrophysics Data System (ADS)

    Stammeier, Jessica; Hippler, Dorothee; Mavromatis, Vasileios; Sacher, Stephan; Dietzel, Martin

    2016-04-01

    Amorphous calcium phosphate (Ca3(PO4)2*nH2O; ACP) is often a precursor phase of the mineral (hydroxy-) apatite (Ca5(PO4)3(OH)) that can be formed in natural settings during both authigenic and biogenic mineral formation. Particularly, in the biomineralization process of fish tissue, ACP has shown to be an important transient phase. In solution ACP rapidly transforms into the crystalline phase. The transformation rate highly depends on the physico-chemical conditions of the solution: Ca & P availability, pH and temperature. In natural settings Ca can be provided by different sources: from (1) seawater, (2) porewater, or (3) diagenetically-altered carbonates, whereas local supersaturation of P can be induced by microbial activity. In this study, we performed phosphate precipitation experiments in order to monitor the transformation process of the ACP to crystalline hydroxyapatite (HAP) using in-situ Raman spectroscopy. During the experiments the temperature was kept constant at 20.0 ± 0.01 ° C and pH at 9 ± 0.1. 50 ml of 0.3 CaCl 2H2O was titrated at a rate of 5 ml/min to an equal volume of 0.2 M Na2HPO4. The pH was kept constant by titration of 1 M NaOH. During the experiment samples were taken from the solution and instantly filtered. The obtained solid samples were lyophilized and analyzed with XRD, ATR and SEM. The respective solution samples were analyzed using ion chromatography and ICP OES, coupling the spectroscopic data with detailed solution chemistry data. We observed transformation of ACP to HAP to occur within 14 hours, illustrated in a clear peak shift in Raman spectra from 950 cm‑1 to 960 cm‑1. The obtained results are discussed in the aspects of distribution of major elements during the formation of phosphates and/or the diagenetic alteration of carbonates to phosphates in geologic settings. Financial support by DFG-FG 736 and NAWI Graz is kindly acknowledged.

  4. Calcium and calcium isotope changes during carbon cycle perturbations at the end-Permian

    NASA Astrophysics Data System (ADS)

    Komar, N.; Zeebe, R. E.

    2016-01-01

    Negative carbon and calcium isotope excursions, as well as climate shifts, took place during the most severe mass extinction event in Earth's history, the end-Permian (˜252 Ma). Investigating the connection between carbon and calcium cycles during transient carbon cycle perturbation events, such as the end-Permian, may help resolve the intricacies between the coupled calcium-carbon cycles, as well as provide a tool for constraining the causes of mass extinction. Here we identify the deficiencies of a simplified calcium model employed in several previous studies, and we demonstrate the importance of a fully coupled carbon cycle model when investigating the dynamics of carbon and calcium cycling. Simulations with a modified version of the Long-term Ocean-atmosphere-Sediment CArbon cycle Reservoir model, which includes a fully coupled carbon-calcium cycle, indicate that increased weathering rates and ocean acidification (potentially caused by Siberian Trap volcanism) are not capable of producing trends observed in the record, as previously claimed. Our model results suggest that combined effects of carbon input via Siberian Trap volcanism (12,000 Pg C), the cessation of biological carbon export, and variable calcium isotope fractionation (due to a change in the seawater carbonate ion concentration) represents a more plausible scenario. This scenario successfully reconciles δ13C and δ44Ca trends observed in the sediment record, as well as the proposed warming of >6°C.

  5. Structural studies of hydrated samples of amorphous calcium phosphate and phosphoprotein nanoclusters.

    PubMed

    Lenton, Samuel; Nylander, Tommy; Holt, Carl; Sawyer, Lindsay; Härtlein, Michael; Müller, Harrald; Teixeira, Susana C M

    2016-07-01

    There are abundant examples of nanoclusters and inorganic microcrystals in biology. Their study under physiologically relevant conditions remains challenging due to their heterogeneity, instability, and the requirements of sample preparation. Advantages of using neutron diffraction and contrast matching to characterize biomaterials are highlighted in this article. We have applied these and complementary techniques to search for nanocrystals within clusters of calcium phosphate sequestered by bovine phosphopeptides, derived from osteopontin or casein. The neutron diffraction patterns show broad features that could be consistent with hexagonal hydroxyapatite crystallites smaller than 18.9 Å. Such nanocrystallites are, however, undetected by the complementary X-ray and FTIR data, collected on the same samples. The absence of a distinct diffraction pattern from the nanoclusters supports the generally accepted amorphous calcium phosphate structure of the mineral core. PMID:26780236

  6. A safer disposal of hazardous phosphate coating sludge by formation of an amorphous calcium phosphate matrix.

    PubMed

    Navarro-Blasco, I; Duran, A; Pérez-Nicolás, M; Fernández, J M; Sirera, R; Alvarez, J I

    2015-08-15

    Phosphate coating hazardous wastes originated from the automotive industry were efficiently encapsulated by an acid-base reaction between phosphates present in the sludge and calcium aluminate cement, yielding very inert and stable monolithic blocks of amorphous calcium phosphate (ACP). Two different compositions of industrial sludge were characterized and loaded in ratios ranging from 10 to 50 wt.%. Setting times and compressive strengths were recorded to establish the feasibility of this method to achieve a good handling and a safe landfilling of these samples. Short solidification periods were found and leaching tests showed an excellent retention for toxic metals (Zn, Ni, Cu, Cr and Mn) and for organic matter. Retentions over 99.9% for Zn and Mn were observed even for loadings as high as 50 wt.% of the wastes. The formation of ACP phase of low porosity and high stability accounted for the effective immobilization of the hazardous components of the wastes. PMID:26024992

  7. Arrangement techniques of proteins and cells using amorphous calcium phosphate nanofiber scaffolds

    NASA Astrophysics Data System (ADS)

    Nonoyama, Takayuki; Kinoshita, Takatoshi; Higuchi, Masahiro; Nagata, Kenji; Tanaka, Masayoshi; Kamada, Mari; Sato, Kimiyasu; Kato, Katsuya

    2012-12-01

    We demonstrate arrangement techniques of proteins and cells using an amorphous calcium phosphate (ACP) nanofiber scaffold. It is well known that protein andosteoblastic cell are preferably adsorbed onto ACP surface. The ACP nanofiber scaffold was prepared by calcium phosphate mineralization on a polypeptide monolayer-coated mica substrate, and ACP nanofibers were oriented unidirectionaly. In a protein system, the ACP nanofiber scaffold was soaked in a fluorescein isothiocyanate conjugated immunoglobulin G (IgG-FITC) aqueous solution. From fluorescence microscopic measurement, the adsorbed IgG-FITC was highly confined and arranged on the ACP nanofiber. In a cell system, a mouse osteoblast-like cell (MC3T3-E1) behavior on the ACP nanofiber scaffold was observed. The cell was elongated unidirectionaly, and its cytoskeletal shape showed high aspect ratio. These results are clearly different from an ACP bulk template or bare mica substrate, and the arrangement technique enable to fabricate a fine-tuned biomaterial template.

  8. Calcium and calcium isotope changes during carbon cycle perturbations at the end-Permian

    NASA Astrophysics Data System (ADS)

    Komar, Nemanja; Zeebe, Richard

    2016-04-01

    Negative carbon and calcium isotope excursions, as well as climate shifts, took place during the most severe mass extinction event in Earth's history, the end-Permian (˜252 Ma). Investigating the connection between carbon and calcium cycles during transient carbon cycle perturbation events, such as the end-Permian, may help resolve the intricacies between the coupled calcium-carbon cycles, as well as provide a tool for constraining the causes of mass extinction. Here, we identify the deficiencies of a simplified calcium model employed in several previous studies and we demonstrate the importance of a fully coupled carbon-cycle model when investigating the dynamics of carbon and calcium cycling. Simulations with a modified version of the LOSCAR model, which includes a fully coupled carbon-calcium cycle, indicate that increased weathering rates and ocean acidification (potentially caused by Siberian Trap volcanism) are not capable of producing trends observed in the record, as previously claimed. Our model results suggest that combined effects of carbon input via Siberian Trap volcanism (12,000 Pg C), the cessation of biological carbon export, and variable calcium isotope fractionation (due to a change in the seawater carbonate ion concentration) represents a more plausible scenario. This scenario successfully reconciles δ13C and δ44Ca trends observed in the sediment record, as well as the proposed warming of >6oC.

  9. Osteoblast response to zirconia-hybridized pyrophosphate-stabilized amorphous calcium phosphate

    PubMed Central

    Whited, Bryce M.; Skrtic, Drago; Love, Brian J.

    2006-01-01

    Calcium phosphate bioceramics, such as hydroxyapatite, have long been used as bone substitutes because of their proven biocompatibility and bone binding properties in vivo. Recently, a zirconia-hybridized pyrophosphate-stabilized amorphous calcium phosphate (Zr-ACP) has been synthesized, which is more soluble than hydroxyapatite and allows for controlled release of calcium and phosphate ions. These ions have been postulated to increase osteoblast differentiation and mineralization in vitro. The focus of this work is to elucidate the physicochemical properties of Zr-ACP and to measure cell response to Zr-ACP in vitro using a MC3T3-E1 mouse calvarial-derived osteoprogenitor cell line. Cells were cultured in osteogenic medium and mineral was added to culture at different stages in cell maturation. Culture in the presence of Zr-ACP showed significant increases in cell proliferation, alkaline phosphatase activity (ALP), and osteopontin (OPN) synthesis, whereas collagen synthesis was unaffected. In addition, calcium and phosphate ion concentrations and medium pH were found to transiently increase with the addition of Zr-ACP, and are hypothesized to be responsible for the osteogenic effect of Zr-ACP. PMID:16278876

  10. HRTEM study of Popigai impact diamond: heterogeneous diamond nanostructures in native amorphous carbon matrix

    NASA Astrophysics Data System (ADS)

    Kis, Viktoria K.; Shumilova, Tatyana; Masaitis, Victor

    2016-07-01

    High-resolution transmission electron microscopy was applied for the detailed nanostructural investigation of Popigai impact diamonds with the aim of revealing the nature of the amorphous carbon of the matrix. The successful application of two complementary specimen preparation methods, focused ion beam (FIB) milling and mechanical cleavage, allowed direct imaging of nanotwinned nanodiamond crystals embedded in a native amorphous carbon matrix for the first time. Based on its stability under the electron beam, native amorphous carbon can be easily distinguished from the amorphous carbon layer produced by FIB milling during specimen preparation. Electron energy loss spectroscopy of the native amorphous carbon revealed the dominance of sp 2-bonded carbon and the presence of a small amount of oxygen. The heterogeneous size distribution and twin density of the nanodiamond crystals and the structural properties of the native amorphous carbon are presumably related to non-graphitic (organic) carbon precursor material.

  11. Synthesis of amorphous carbon nanofibers using iron nanoparticles as catalysts

    NASA Astrophysics Data System (ADS)

    Ali, Mokhtar; Ramana, G. Venkata; Padya, Balaji; Srikanth, V. V. S. S.; Jain, P. K.

    2013-06-01

    Amongst various carbon nanomaterials, carbon nanofibers (CNFs) have lately attracted considerable interest as a promising reinforcement in polymer matrix composites. CNFs are often synthesized using copper nanoparticles as catalysts and by using chemical vapor deposition (CVD). In this work iron (Fe) nanoparticles are used as catalysts to synthesize amorphous carbon nanofibers. This owes significance since Fe nanoparticles often lead to tubes rather than fibers. Fe nanoparticles (size ˜30-60nm) are prepared by first mixing an appropriate quantity of potassium sodium tartrate tetrahydrate salt with iron (II) chloride dehydrate to obtain iron tartrate and then dried and heated in vacuum oven at about 250°C to remove tartrate. In a subsequent step, CNFs are obtained by using CVD. Acetylene was used as the carbon source in the CVD process. Scanning and transmission electron microscopy show the formation of nanofibers whose diameter is dependent on the size of Fe catalysts. Raman scattering from the fibers show that they are made up of carbon and are amorphous.

  12. Amorphous Diamond: A High-Pressure Superhard Carbon Allotrope

    SciTech Connect

    Lin, Yu; Zhang, Li; Mao, Ho-kwang; Chow, Paul; Xiao, Yuming; Baldini, Maria; Shu, Jinfu; Mao, Wendy L.

    2011-12-09

    Compressing glassy carbon above 40 GPa, we have observed a new carbon allotrope with a fully sp{sup 3}-bonded amorphous structure and diamondlike strength. Synchrotron x-ray Raman spectroscopy revealed a continuous pressure-induced sp{sup 2}-to-sp{sup 3} bonding change, while x-ray diffraction confirmed the perseverance of noncrystallinity. The transition was reversible upon releasing pressure. Used as an indenter, the glassy carbon ball demonstrated exceptional strength by reaching 130 GPa with a confining pressure of 60 GPa. Such an extremely large stress difference of >70 GPa has never been observed in any material besides diamond, indicating the high hardness of this high-pressure carbon allotrope.

  13. Energetics of water interactions with amorphous and nanocrystalline carbonates

    NASA Astrophysics Data System (ADS)

    Radha, A.; Navrotsky, A.

    2013-12-01

    Understanding carbonate surface-water interaction is important as it determines the reactivity, growth and dissolution of mineral surface. The stability and residence time of adsorbed water could influence the mobility of ions on mineral surface or hinder the surface reaction by blocking the surface active sites. The nature of water-carbonate interface has been characterized by several computational studies but not much experimentally measured data are available on such interaction energetics. We report the direct experimental measurement of enthalpies of water adsorption on amorphous and nanocrystalline Ca/Mg/Mn carbonates using a water vapor adsorption calorimetry. The simultaneous measurement of adsorption enthalpy as a function of amount of accurate dosed water vapor gives the actual interaction of water with carbonate surface. The distinct modes of water adsorption on different active sites on the surface would generate adsorption enthalpy curve with distinct energetic trends.

  14. Bonding topologies in diamondlike amorphous-carbon films

    SciTech Connect

    SIEGAL,MICHAEL P.; PROVENCIO,PAULA P.; TALLANT,DAVID R.; SIMPSON,REGINA L.; KLEINSORGE,B.; MILNE,W.I.

    2000-01-27

    The carbon ion energy used during filtered cathodic vacuum arc deposition determines the bonding topologies of amorphous-carbon (a-C) films. Regions of relatively low density occur near the substrate/film and film/surface interfaces and their thicknesses increase with increasing deposition energy. The ion subplantation growth results in mass density gradients in the bulk portion of a-C in the growth direction; density decreases with distance from the substrate for films grown using ion energies < 60 eV and increases for films grown using ion energies > 160 eV. Films grown between these energies are the most diamondlike with relatively uniform bulk density and the highest optical transparencies. Bonding topologies evolve with increasing growth energy consistent with the propagation of subplanted carbon ions inducing a partial transformation of 4-fold to 3-fold coordinated carbon atoms.

  15. Calcium carbonate and calcium sulfate in Martian meteorite EETA79001

    NASA Technical Reports Server (NTRS)

    Gooding, J. L.; Wentworth, S. J.

    1987-01-01

    Chips of glassy Lithology C of EETA79001 were studied by scanning electron microscopy and energy dispersive X-ray spectroscopy to determine the mineralogy and petrogenesis of the glass that was shown by others to contain trapped Mars-like gases. Calcium carbonite was identified as massive to acicular crystals for which Ca, C, and O were the major elements. Calcium sulfate was identified as prismatic-acicular crystals with Ca and S as the major elements.

  16. Synthesis, characterization, and in-vitro cytocompatibility of amorphous β-tri-calcium magnesium phosphate ceramics.

    PubMed

    Singh, Satish S; Roy, Abhijit; Lee, Boeun; Banerjee, Ipsita; Kumta, Prashant N

    2016-10-01

    Biphasic mixtures of crystalline β-tricalcium magnesium phosphate (β-TCMP) and an amorphous calcium magnesium phosphate have been synthesized and reported to support enhanced hMSC differentiation in comparison to β-tricalcium phosphate (β-TCP) due to the release of increased amounts of bioactive ions. In the current study, completely amorphous β-TCMP has been synthesized which is capable of releasing increased amounts of Mg(2+) and PO4(3-) ions, rather than a biphasic mixture as earlier reported. The amorphous phase formed was observed to crystallize between temperatures of 400-600°C. The scaffolds prepared with amorphous β-TCMP were capable of supporting enhanced hMSC proliferation and differentiation in comparison to commercially available β-TCP. However, a similar gene expression of mature osteoblast markers, OCN and COL-1, in comparison to biphasic β-TCMP was observed. To further study the role of Mg(2+) and PO4(3-) ions in regulating hMSC osteogenic differentiation, the capability of hMSCs to mineralize in growth media supplemented with Mg(2+) and PO4(3-) ions was studied. Interestingly, 5mM PO4(3-) supported mineralization while the addition of 5mM Mg(2+) to 5mM PO4(3-) inhibited mineralization. It was therefore concluded that the release of Ca(2+) ions from β-TCMP scaffolds also plays a role in regulating osteogenic differentiation on these scaffolds and it is noted that further work is required to more accurately determine the exact role of Mg(2+) in regulating hMSC osteogenic differentiation. PMID:27287163

  17. In situ molecular NMR picture of bioavailable calcium stabilized as amorphous CaCO₃ biomineral in crayfish gastroliths.

    PubMed

    Akiva-Tal, Anat; Kababya, Shifi; Balazs, Yael S; Glazer, Lilah; Berman, Amir; Sagi, Amir; Schmidt, Asher

    2011-09-01

    Bioavailable calcium is maintained by some crustaceans, in particular freshwater crayfish, by stabilizing amorphous calcium carbonate (ACC) within reservoir organs--gastroliths, readily providing the Ca(2+) needed to build a new exoskeleton. Despite the key scientific and biomedical importance of the in situ molecular-level picture of biogenic ACC and its stabilization in a bioavailable form, its description has eluded efforts to date. Herein, using multinuclear NMR, we accomplish in situ molecular-level characterization of ACC within intact gastroliths of the crayfish Cherax quadricarinatus. In addition to the known CaCO(3), chitin scaffold and inorganic phosphate (Pi), we identify within the gastrolith two primary metabolites, citrate and phosphoenolpyruvate (PEP) and quantify their abundance by applying solution NMR techniques to the gastrolith "soluble matrix." The long-standing question on the physico-chemical state of ACC stabilizing, P-bearing moieties within the gastrolith is answered directly by the application of solid state rotational-echo double-resonance (REDOR) and transferred-echo double-resonance (TEDOR) NMR to the intact gastroliths: Pi and PEP are found molecularly dispersed throughout the ACC as a solid solution. Citrate carboxylates are found < 5 Å from a phosphate (intermolecular CP distance), an interaction that must be mediated by Ca(2+). The high abundance and extensive interactions of these molecules with the ACC matrix identify them as the central constituents stabilizing the bioavailable form of calcium. This study further emphasizes that it is imperative to characterize the intact biogenic CaCO(3). Solid state NMR spectroscopy is shown to be a robust and accessible means of determining composition, internal structure, and molecular functionality in situ. PMID:21873244

  18. Europium-doped amorphous calcium phosphate porous nanospheres: preparation and application as luminescent drug carriers.

    PubMed

    Chen, Feng; Zhu, Ying-Jie; Zhang, Kui-Hua; Wu, Jin; Wang, Ke-Wei; Tang, Qi-Li; Mo, Xiu-Mei

    2011-01-01

    Calcium phosphate is the most important inorganic constituent of biological tissues, and synthetic calcium phosphate has been widely used as biomaterials. In this study, a facile method has been developed for the fabrication of amorphous calcium phosphate (ACP)/polylactide-block-monomethoxy(polyethyleneglycol) hybrid nanoparticles and ACP porous nanospheres. Europium-doping is performed to enable photoluminescence (PL) function of ACP porous nanospheres. A high specific surface area of the europium-doped ACP (Eu3+:ACP) porous nanospheres is achieved (126.7 m2/g). PL properties of Eu3+:ACP porous nanospheres are investigated, and the most intense peak at 612 nm is observed at 5 mol% Eu3+ doping. In vitro cytotoxicity experiments indicate that the as-prepared Eu3+:ACP porous nanospheres are biocompatible. In vitro drug release experiments indicate that the ibuprofen-loaded Eu3+:ACP porous nanospheres show a slow and sustained drug release in simulated body fluid. We have found that the cumulative amount of released drug has a linear relationship with the natural logarithm of release time (ln(t)). The Eu3+:ACP porous nanospheres are bioactive, and can transform to hydroxyapatite during drug release. The PL properties of drug-loaded nanocarriers before and after drug release are also investigated. PMID:21711603

  19. Europium-doped amorphous calcium phosphate porous nanospheres: preparation and application as luminescent drug carriers

    PubMed Central

    2011-01-01

    Calcium phosphate is the most important inorganic constituent of biological tissues, and synthetic calcium phosphate has been widely used as biomaterials. In this study, a facile method has been developed for the fabrication of amorphous calcium phosphate (ACP)/polylactide-block-monomethoxy(polyethyleneglycol) hybrid nanoparticles and ACP porous nanospheres. Europium-doping is performed to enable photoluminescence (PL) function of ACP porous nanospheres. A high specific surface area of the europium-doped ACP (Eu3+:ACP) porous nanospheres is achieved (126.7 m2/g). PL properties of Eu3+:ACP porous nanospheres are investigated, and the most intense peak at 612 nm is observed at 5 mol% Eu3+ doping. In vitro cytotoxicity experiments indicate that the as-prepared Eu3+:ACP porous nanospheres are biocompatible. In vitro drug release experiments indicate that the ibuprofen-loaded Eu3+:ACP porous nanospheres show a slow and sustained drug release in simulated body fluid. We have found that the cumulative amount of released drug has a linear relationship with the natural logarithm of release time (ln(t)). The Eu3+:ACP porous nanospheres are bioactive, and can transform to hydroxyapatite during drug release. The PL properties of drug-loaded nanocarriers before and after drug release are also investigated. PMID:21711603

  20. Amorphous calcium phosphate offers improved crack resistance: a design feature from nature?

    PubMed

    Saber-Samandari, Saeed; Gross, Karlis A

    2011-12-01

    Amorphous calcium phosphate (ACP) is found in biological organisms and coated implants, used in calcium phosphate cements, and has been recently confirmed as a precursor in mineralized tissue; however, nothing is known about crack initiation in ACP or its fracture toughness. The objective of this study was to determine the crack resistance of ACP to help understand its role in biological organisms and assist in the design of calcium-phosphate-based implants. ACP was manufactured by quenching droplets to form a bulk sample and individual splats. Testing of Berkovich and cube-corner indenter types revealed that the Berkovich indenter was more suitable, providing ease of crack detection. Nanoindentation was performed on polished ACP and hydroxyapatite (HAp), and cracks were identified with scanning electron microscopy. Additional nanoindentation was done on splats to assess the suitability for testing microarrays used in high throughput discovery of new bioceramics. ACP required about three times more force to initiate a crack compared to sintered HAp, but about nine times more than a single crystal. Crack initiation resistance decreased with increasing grain size. The fracture toughness of ACP was comparable to a single crystal, but higher for nanograined HAp. The crack initiation load can be potentially used for evaluating microsized samples. ACP prevents crack formation, but requires the presence of nanograins to provide a greater toughness. The implications of the higher crack initiation load in ACP are discussed for biological organisms and thermally processed biomaterials such as thermally sprayed and sintered HAp. PMID:21784179

  1. SECONDARY HYPERPARATHYROIDISM AFTER BARIATRIC SURGERY: TREATMENT IS WITH CALCIUM CARBONATE OR CALCIUM CITRATE?

    PubMed Central

    BARETTA, Giorgio Alfredo Pedroso; CAMBI, Maria Paula Carlini; RODRIGUES, Arieli Luz; MENDES, Silvana Aparecida

    2015-01-01

    Background : Bariatric surgery, especially Roux-en-Y gastric bypass, can cause serious nutritional complications arising from poor absorption of essential nutrients. Secondary hyperparathyroidism is one such complications that leads to increased parathyroid hormone levels due to a decrease in calcium and vitamin D, which may compromise bone health. Aim : To compare calcium carbonate and calcium citrate in the treatment of secondary hyperparathyroidism. Method : Patients were selected on the basis of their abnormal biochemical test and treatment was randomly done with citrate or calcium carbonate. Results : After 60 days of supplementation, biochemical tests were repeated, showing improvement in both groups. Conclusion : Supplementation with calcium (citrate or carbonate) and vitamin D is recommended after surgery for prevention of secondary hyperparathyroidism. PMID:26537273

  2. Phototransformation-Induced Aggregation of Functionalized Single-Walled Carbon Nanotubes: The Importance of Amorphous Carbon.

    PubMed

    Hou, Wen-Che; He, Chen-Jing; Wang, Yi-Sheng; Wang, David K; Zepp, Richard G

    2016-04-01

    Single-walled carbon nanotubes (SWCNTs) with proper functionalization are desirable for applications that require dispersion in aqueous and biological environments, and functionalized SWCNTs also serve as building blocks for conjugation with specific molecules in these applications. In this study, we examined the phototransformation of carboxylated SWCNTs and associated amorphous carbon impurities in the presence or absence of H2O2 under simulated sunlight conditions. We found that while carboxylated SWCNTs were rather unreactive with respect to direct solar photolysis, they photoreacted in the presence of H2O2, forming CO2 and strongly aggregated SWCNT products that precipitated. Photoreaction caused SWCNTs to lose oxygen-containing functionalities, and interestingly, the resulting photoproducts had spectral characteristics similar to those of parent carboxylated SWCNTs whose amorphous carbon was removed by base washing. These results indicated that photoreaction of the amorphous carbon was likely involved. The removal of amorphous carbon after indirect photoreaction was confirmed with thermogravimetric analysis (TGA). Further studies using carboxylated SWCNTs with and without base washing indicate that amorphous carbon reduced the extent of aggregation caused by photoreaction. The second-order rate constant for carboxylated SWCNTs reacting with (•)OH was estimated to be in the range of 1.7-3.8 × 10(9) MC(-1) s(-1). The modeled phototransformation half-lives fall in the range of 2.8-280 days in typical sunlit freshwaters. Our study indicates that photosensitized reactions involving (•)OH may be a transformation and removal pathway of functionalized SWCNTs in the aquatic environment, and that the residual amorphous carbon associated with SWCNTs plays a role in SWCNT stabilization. PMID:26928260

  3. Platelet adhesion on phosphorus-incorporated tetrahedral amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Liu, Aiping; Zhu, Jiaqi; Liu, Meng; Dai, Zhifei; Han, Xiao; Han, Jiecai

    2008-11-01

    The haemocompatibility of phosphorus-incorporated tetrahedral amorphous carbon (ta-C:P) films, synthesized by filtered cathodic vacuum arc technique with PH 3 as the dopant source, was assessed by in vitro platelet adhesion tests. Results based on scanning electron microscopy and contact angle measurements reveal that phosphorus incorporation improves the wettability and blood compatibility of ta-C film. Our studies may provide a novel approach for the design and synthesis of doped ta-C films to repel platelet adhesion and reduce thrombosis risk.

  4. Fortification of all-purpose wheat-flour tortillas with calcium lactate, calcium carbonate, or calcium citrate is acceptable.

    PubMed

    Romanchik-Cerpovicz, Joelle E; McKemie, Rebecca J

    2007-03-01

    Fortification helps provide adequate nutrients for individuals not meeting daily needs. Foods may be fortified with calcium to assist individuals with lactose intolerance and others preferring not to consume traditional forms of dairy. This study examined the quality of all-purpose wheat-flour tortillas fortified with calcium lactate, calcium carbonate, or calcium citrate. These tortillas were compared to similarly prepared nonfortified flour tortillas (control) and commercial nonfortified flour tortillas. Calcium-fortified tortillas contained 114 mg elemental calcium per standard serving (48 g tortilla), an 8.6-fold increase compared to nonfortified tortillas. Moisture contents and rollabilities of all tortillas were similar. Consumers (N=87) evaluated each tortilla in duplicate using a hedonic scale and reported liking the appearance, texture, flavor, aftertaste, and overall acceptability of all tortillas. However, the appearance of control tortillas was preferred over commercial tortillas (P<0.01), whereas the aftertaste of commercial tortillas or those fortified with calcium carbonate was preferred over the control (P<0.05). Despite these differences, consumers were equally willing to purchase both fortified and nonfortified tortillas, suggesting that appearance and aftertaste may not influence willingness to purchase. Overall, this study shows that fortification of flour tortillas with various forms of calcium is a feasible alternative calcium source. PMID:17324671

  5. The influence of aliphatic amines, diamines, and amino acids on the polymorph of calcium carbonate precipitated by the introduction of carbon dioxide gas into calcium hydroxide aqueous suspensions

    NASA Astrophysics Data System (ADS)

    Chuajiw, Wittaya; Takatori, Kazumasa; Igarashi, Teruki; Hara, Hiroki; Fukushima, Yoshiaki

    2014-01-01

    The influence of aliphatic organic additives including amines, diamines and amino acids, on the polymorph of calcium carbonate (CaCO3) precipitated from a calcium hydroxide (Ca(OH)2) suspensions and carbon dioxide gas (CO2) was studied by X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The amorphous calcium carbonate, vaterite, aragonite and calcite were observed for the precipitated samples with organic additives. While the precipitation without organic additive, only the stable phase; calcite was obtained. The observed crystal phases were related with the alkyl chain length in the aliphatic part of additives. These results suggested that hydrophobic interactions due to the van der Waals force between organic additives and surface of inorganic precipitates could not be ignored. We concluded that covering or adsorbing of these organic additives on the precipitates surfaces retarded the successive dissolution/recrystallisation process in the aqueous systems. The results revealed that not only the polar interaction from the hydrophilic functional groups, as the former reports proposed, but also the van der Waals interactions from the hydrophobic alkyl groups played the important role in the phase transformation of CaCO3.

  6. Raman spectroscopic studies of amorphous carbon and buckminsterfullerene

    SciTech Connect

    Sinha, K.

    1992-01-01

    Raman spectroscopic techniques have been applied to investigate a variety of carbon systems. Using resonance Raman spectroscopy as a probe for optical transitions in a system, a careful quantitative estimate of the Raman cross-section of graphite in the pre-resonance regime has been made. Raman and resonance Raman spectroscopy have been used to correlate the structural and electronic properties of amorphous carbon materials. The low optical gaps and e-2e spectroscopy measurements on evaporated carbon films suggests a structure close to graphite. Raman measurements, however, reveal a great amount of disorder in the material. This apparent contradiction has been resolved through the use of a phenomenological model for the electronic density of states for amorphous carbon systems. Raman spectroscopy has also been used to study the vibrational and the electronic properties of the recently discovered third allotrope of carbon, C[sub 60]. The vibrational modes of this molecule have been studied in great detail. The observed vibrational spectra confirms earlier work in this material. Furthermore, the mode frequencies have been found to be in reasonably good agreement with theoretical predictions. Resonance Raman studies of solid C[sub 60] and C[sub 60] dissolved in solvents has revealed, in the solid phase, the existence of optical transitions well below the symmetry allowed transitions for the isolated molecules. Loss of inversion symmetry in the solid state has been proposed to account for the resonance observed in the Raman excitation profile. Original Raman measurements on C[sub 60] revealed a strong peak at 1469 cm[sup [minus]1]. The peak was found to obey the correct selection rule for symmetric A[sub g] mode and was assigned to the [open quotes]pentagonal pinch[close quotes] mode of the molecule.

  7. Microstructure of amorphous aluminum hydroxide in belite-calcium sulfoaluminate cement

    SciTech Connect

    Song, Fei; Yu, Zhenglei; Yang, Fengling; Lu, Yinong Liu, Yunfei

    2015-05-15

    Belite-calcium sulfoaluminate (BCSA) cement is a promising low-CO{sub 2} alternative to ordinary Portland cement. Herein, aluminum hydroxide (AH{sub 3}), the main amorphous hydration product of BCSA cement, was investigated in detail. The microstructure of AH{sub 3} with various quantities of gypsum was investigated via scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The AH{sub 3} with various morphologies were observed and confirmed in the resulting pastes. Particular attention was paid to the fact that AH{sub 3} always contained a small amount of Ca according to the results of EDS analysis. The AH{sub 3} was then characterized via high resolution transmission electron microscopy (HRTEM). The results of HRTEM indicated that Ca arose from nanosized tricalcium aluminate hexahydrate which existed in the AH{sub 3}.

  8. ILLUMINATING THE ROLE OF AGGLOMERATES ON CRITICAL PHYSICOCHEMICAL PROPERTIES OF AMORPHOUS CALCIUM PHOSPHATE COMPOSITES

    PubMed Central

    O’Donnell, J.N.R.; Antonucci, J.M.; Skrtic, D.

    2009-01-01

    Water sorption (WS), mechanical strength, and ion release of polymeric composites formulated with 40 % as-made or milled amorphous calcium phosphate (ACP) are compared after 1, 2 and 3 months of aqueous exposure. Ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate and methacryloxyethyl phthalate comprised the resin. The WS (mass %) peaked at 3 months. WS of as-made ACP composites was significantly higher than WS of milled ACP composites and copolymers. Both composite groups experienced decreases in biaxial flexural strength (BFS) with water aging, with milled ACP composites retaining a significantly higher BFS throughout immersion. Ion release was moderately reduced in milled ACP composites, though they remained superior to as-made ACP composites due to significantly lower WS and higher BFS after prolonged aqueous exposure. PMID:19774100

  9. Calcium carbonate does not affect imatinib pharmacokinetics in healthy volunteers

    PubMed Central

    Tawbi, Hussein; Christner, Susan M.; Lin, Yan; Johnson, Matthew; Mowrey, Emily T.; Cherrin, Craig; Chu, Edward; Lee, James J.; Puhalla, Shannon; Stoller, Ronald; Appleman, Leonard R.; Miller, Brian M.; Beumer, Jan H.

    2013-01-01

    Purpose Imatinib mesylate (Gleevec®/Glivec®), has revolutionized the treatment of chronic myeloid leukemias (CML) and gastrointestinal stromal tumors (GIST), and there is evidence for an exposure response relationship. Calcium carbonate is increasingly used as a calcium supplement and in the setting of gastric upset associated with imatinib therapy. Calcium carbonate could conceivably elevate gastric pH and complex imatinib, thereby influencing imatinib absorption and exposure. We aimed to evaluate whether use of calcium carbonate has a significant effect on imatinib pharmacokinetics. Methods Eleven healthy subjects were enrolled in a 2-period, open-label, single-institution, randomized cross-over, fixed-schedule study. In one period, each subject received 400 mg of imatinib p.o.. In the other period, 4000 mg calcium carbonate (Tums Ultra®) was administered p.o. 15 min before 400 mg of imatinib. Plasma concentrations of imatinib and its active N-desmethyl metabolite CGP74588 were assayed by LC-MS; data were analyzed non-compartmentally, and compared after log transformation. Results Calcium carbonate administration did not significantly affect the imatinib area under the plasma concentration versus time curve (AUC) (41.2 μg/mL•h alone versus 40.8 μg/mL•h with calcium carbonate, P=0.99), maximum plasma concentration (Cmax) (2.35 μg/mL alone versus 2.39 μg/mL with calcium carbonate, P=0.89). Conclusions Our results indicate that the use of calcium carbonate does not significantly affect imatinib pharmacokinetics. PMID:24170263

  10. Behaviour of calcium carbonate in sea water

    USGS Publications Warehouse

    Cloud, P.E., Jr.

    1962-01-01

    Anomalies in the behaviour of calcium carbonate in natural solutions diminish when considered in context. Best values found by traditional oceanographie methods for the apparent solubility product constant K'CaCO3 in sea water at atmospheric pressure are consistent mineralogically-at 36 parts per thousand salinity and T-25??C, K'aragonlte is estimated as 1.12 ?? 10-6 and K'calcite as 0.61 ?? 10-6. At 30??C the corresponding values are 0.98 ?? 10-6 for aragonite and 0.53 ?? 10-6 for calcite. Because the K' computations do not compensate for ionic activity, however, they cannot give thermodynamically satisfactory results. It is of interest, therefore, that approximate methods and information now available permit the estimation from the same basic data of an activity product constant KCaCO3 close to that found in solutions to which Debye-Hu??ckel theory applies. Such methods indicate approximate Karagonite 7.8 ?? 10-9 for surface sea water at 29??C; Kcalcite would be proportionately lower. Field data and experimental results indicate that the mineralogy of precipitated CaCO3 depends primarily on degree of supersaturation, thus also on kinetic or biologic factors that facilitate or inhibit a high degree of supersaturation. The shallow, generally hypersaline bank waters west of Andros Island yield aragonitic sediments with O18 O16 ratios that imply precipitation mainly during the warmer months, when the combination of a high rate of evaporation, increasing salinity (and ionic strength), maximal temperatures and photosynthetic removal of CO2 result in high apparent supersaturation. The usual precipitate from solutions of low ionic strength is calcite, except where the aragonite level of supersaturation is reached as a result of diffusion phenomena (e.g. dripstones), gradual and marked evaporation, or biologic intervention. Published data also suggest the possibility of distinct chemical milieus for crystallographic variations in skeletal calcium carbonate. It appears

  11. Ability of Pit and Fissure Sealant-containing Amorphous Calcium Phosphate to inhibit Enamel Demineralization

    PubMed Central

    Owais, Arwa I; Kawaja, Wasan

    2016-01-01

    ABSTRACT Aim: To evaluate the effect of amorphous calcium phosphate (ACP)-containing pit and fissure sealant on inhibition of enamel demineralization in vitro. Materials and methods: Enamel specimens (n = 75) were prepared using freshly extracted noncarious human third molars. Box-shaped cavities (8 × 2 × 2 mm) on the buccal or lingual surfaces were prepared and restored with resin-based sealant (Concise™), ACP-containing sealant (Aegis®) or fluoride-containing sealant (Conseal-F™). The samples were acid challenged in a demineralizing solution of 50 mmol/l lactic acid at pH 5.0 for 4 days. The change in enamel microhardness (ASuH) was calculated. Data were analyzed using one-way analysis of variance (ANOVA) and Tukey’s post hoc test. Results: The mean SuH0 (±SD) (in Vicker’s unit) prior to the acid challenge was: Concise™ (318.83 ± 33.86), Aegis® (331.03 ± 21.52), Conseal-F™ (310.12 ± 34.31). Following the acid challenge, the values dropped in all groups and ASuH (±SD) values were 269.17 ± 47.49, 151.39 ± 23.96 and 175.79 ± 32.39 respectively. Conclusion: The ACP-containing pit and fissure sealant has the potential to inhibit enamel demineralization. How to cite this article: Zawaideh FI, Owais AI, Kawaja W. Ability of pit and fissure sealant-containing amorphous calcium phosphate to inhibit enamel demineralization. Int J Clin Pediatr Dent 2016;9(1):10-14. PMID:27274148

  12. RECOVERY OF CALCIUM CARBONATE AND SULFUR FROM FGD SCRUBBER WASTE

    EPA Science Inventory

    The report gives results of a demonstration of key process steps in the proprietary Kel-S process for recovering calcium carbonate and sulfur from lime/limestone flue gas desulfurization (FGD) scrubber waste. The steps are: reduction of the waste to calcium sulfide (using coal as...

  13. Seeded Growth Route to Noble Calcium Carbonate Nanocrystal.

    PubMed

    Islam, Aminul; Teo, Siow Hwa; Rahman, M Aminur; Taufiq-Yap, Yun Hin

    2015-01-01

    A solution-phase route has been considered as the most promising route to synthesize noble nanostructures. A majority of their synthesis approaches of calcium carbonate (CaCO3) are based on either using fungi or the CO2 bubbling methods. Here, we approached the preparation of nano-precipitated calcium carbonate single crystal from salmacis sphaeroides in the presence of zwitterionic or cationic biosurfactants without external source of CO2. The calcium carbonate crystals were rhombohedron structure and regularly shaped with side dimension ranging from 33-41 nm. The high degree of morphological control of CaCO3 nanocrystals suggested that surfactants are capable of strongly interacting with the CaCO3 surface and control the nucleation and growth direction of calcium carbonate nanocrystals. Finally, the mechanism of formation of nanocrystals in light of proposed routes was also discussed. PMID:26700479

  14. Seeded Growth Route to Noble Calcium Carbonate Nanocrystal

    PubMed Central

    Islam, Aminul; Teo, Siow Hwa; Rahman, M. Aminur; Taufiq-Yap, Yun Hin

    2015-01-01

    A solution-phase route has been considered as the most promising route to synthesize noble nanostructures. A majority of their synthesis approaches of calcium carbonate (CaCO3) are based on either using fungi or the CO2 bubbling methods. Here, we approached the preparation of nano-precipitated calcium carbonate single crystal from salmacis sphaeroides in the presence of zwitterionic or cationic biosurfactants without external source of CO2. The calcium carbonate crystals were rhombohedron structure and regularly shaped with side dimension ranging from 33–41 nm. The high degree of morphological control of CaCO3 nanocrystals suggested that surfactants are capable of strongly interacting with the CaCO3 surface and control the nucleation and growth direction of calcium carbonate nanocrystals. Finally, the mechanism of formation of nanocrystals in light of proposed routes was also discussed. PMID:26700479

  15. Selective Oxidation of Amorphous Carbon Layers without Damaging Embedded Single Wall Carbon Nanotube Bundles

    NASA Astrophysics Data System (ADS)

    Choi, Young Chul; Lim, Seong Chu

    2013-11-01

    Single wall carbon nanotubes (SWCNTs) were synthesized by arc discharge, and then purified by selective oxidation of amorphous carbon layers that were found to encase SWCNT bundles and catalyst metal particles. In order to remove selectively the amorphous carbon layers with SWCNTs being intact, we have systematically investigated the thermal treatment conditions; firstly, setting the temperature by measuring the activation energies of SWCNTs and amorphous carbon layers, and then, secondly, finding the optimal process time. As a consequence, the optimal temperature and time for the thermal treatment was found to be 460 °C and 20 min, respectively. The complete elimination of surrounding amorphous carbon layers makes it possible to efficiently disperse the SWCNT bundles, resulting in high absorbance of SWCNT-ink. The SWCNTs which were thermal-treated at optimized temperature (460 °C) and duration (20 min) showed much better crystallinity, dispersibility, and transparent conducting properties, compared with as-synthesized and the nanotubes thermal-treated at different experimental conditions.

  16. Amorphous calcium phosphate/urethane methacrylate resin composites. I. Physicochemical characterization

    PubMed Central

    Regnault, W.F.; Icenogle, T.B.; Antonucci, J.M.; Skrtic, D.

    2008-01-01

    Urethane dimethacrylate (UDMA), an oligomeric poly(ethylene glycol) extended UDMA (PEG-U) and a blend of UDMA/PEG-U were chosen as model systems for introducing both hydrophobic and hydrophilic segments and a range of compliances in their derived polymers. Experimental composites based on these three resins with amorphous calcium phosphate (ACP) as the filler phase were polymerized and evaluated for mechanical strength and ion release profiles in different aqueous media. Strength of all composites decreased upon immersion in saline (pH = 7.4). Both polymer matrix composition and the pH of the liquid environment strongly affected the ion release kinetics. In saline, the UDMA/PEG-U composite showed a sustained release for at least 350 h. The initially high ion release of the PEG-U composites decreased after 72 h, seemingly due to the mineral re-deposition at the composite surface. Internal conversion from ACP to poorly crystallized apatite could be observed by X-ray diffraction. In various lactic acid (LA) environments (initial pH = 5.1) ion release kinetics was much more complex. In LA medium without thymol and/or carboxymethylcellulose, as a result of unfavorable changes in the internal calcium/phosphate ion stoichiometry, the ion release rate greatly increased but without observable conversion of ACP to apatite. PMID:17619969

  17. Amorphous Calcium Phosphate-Based Bioactive Polymeric Composites for Mineralized Tissue Regeneration

    PubMed Central

    Skrtic, D.; Antonucci, J. M.; Eanes, E. D.

    2003-01-01

    Amorphous calcium phosphate (ACP), a postulated precursor in the formation of biological hydroxyapatite, has been evaluated as a filler phase in bioactive polymeric composites that utilize dental monomers to form the matrix phase on polymerization. In addition to excellent biocompatibility, these composites provided sustained release of calcium and phosphate ions into simulated saliva milieus. In an effort to enhance the physicochemical and mechanical properties and extend the utility of remineralizing ACP composites to a greater variety of dental applications, we have focused on: a) hybridizing ACP by introducing silica and/or zirconia, b) assessing the efficacy of potential coupling agents, c) investigating the effects of chemical structure and compositional variation of the resin matrices on the mechanical strength and ion-releasing properties of the composites, and d) improving the intrinsic adhesiveness of composites by using bifunctional monomers with an affinity for tooth structure in resin formulations. Si- and Zr-modified ACPs along with several monomer systems are found useful in formulating composites with improved mechanical and remineralizing properties. Structure-property studies have proven helpful in advancing our understanding of the remineralizing behavior of these bioactive composites. It is expected that this knowledge base will direct future research and lead to clinically valuable products, especially therapeutic materials appropriate for the healing or even regeneration of defective teeth and bone structures. PMID:27413603

  18. The use of amorphous calcium phosphate composites as bioactive basing materials

    PubMed Central

    Schumacher, Gary E.; Antonucci, Joseph M.; O’Donnell, Justin N.R.; Skrtic, Drago

    2008-01-01

    Background Amorphous calcium phosphate (ACP) polymeric composites release calcium and phosphate ions in aqueous environments, which may lead to the deposition of apatitic mineral in tooth structures. This study evaluates the strength of the composite/adhesive/dentin bond (SBS) for ACP basing-composites after various periods of water-aging. Methods Experimental composites were made using two resin matrices, with various ACPs or a commercial strontium ion-leachable glass. They applied successive coats of a dentin adhesive and basing composite to an acid-etched dentin surface and photopolymerized them. They added a commercial resin-based composite and light cured it. They determined the specimens’ SBS after they were aged in water for various periods at 37°C. Results The SBS of ACP composites was (18.3 ± 3.5) MPa, regardless of filler type, resin composition and water aging interval. After 24 hours of water aging, 92.6 percent of surfaces showed the adhesive failure. After two weeks of water aging, adhesive/cohesive failures were predominant in unmilled and milled ACP composites. Conclusions The SBS of ACP composites appears to be unaffected by filler type or immersion time for up to six months. The type of adhesive failure occurring with prolonged aqueous exposure is affected by filler type. Clinical Implications These materials may be effective remineralizing/antidemineralizing agents and may be clinically applicable as adhesives, protective liners and bases, orthodontic cements and pit-and-fissure sealants. PMID:17974645

  19. Antibacterial amorphous calcium phosphate nanocomposites with a quaternary ammonium dimethacrylate and silver nanoparticles

    PubMed Central

    Cheng, Lei; Weir, Michael D.; Xu, Hockin H. K.; Antonucci, Joseph M.; Kraigsley, Alison M.; Lin, Nancy J.; Lin-Gibson, Sheng; Zhou, Xuedong

    2012-01-01

    Objectives Calcium and phosphate ion-releasing resin composites are promising for remineralization. However, there has been no report on incorporating antibacterial agents to these composites. The objective of this study was to develop antibacterial and mechanically-strong nanocomposites incorporating a quaternary ammonium dimethacrylate (QADM), nanoparticles of silver (NAg), and nanoparticles of amorphous calcium phosphate (NACP). Methods The QADM, bis(2-methacryloyloxyethyl) dimethylammonium bromide (ionic dimethacrylate-1), was synthesized from 2-(N,N-dimethylamino)ethyl methacrylate and 2-bromoethyl methacrylate. Ng was synthesized by dissolving Ag 2-ethylhexanoate salt in 2-(tertbutylamino)ethyl methacrylate. Mechanical properties were measured in three-point flexure with bars of 2×2×25 mm (n = 6). Composite disks (diameter = 9 mm, thickness = 2 mm) were inoculated with Streptococcus mutans. The metabolic activity and lactic acid production of biofilms were measured (n = 6). Two commercial composites were used as controls. Results Flexural strength and elastic modulus of NACP+QADM, NACP+NAg, and NACP+QADM+NAg matched those of commercial composites with no antibacterial property (p > 0.1). The NACP+QADM+NAg composite decreased the titer counts of adherent S. mutans biofilms by an order of magnitude, compared to the commercial composites (p < 0.05). The metabolic activity and lactic acid production of biofilms on NACP+QADM+NAg composite were much less than those on commercial composites (p < 0.05). Combining QADM and NAg rendered the nanocomposite more strongly antibacterial than either agent alone (p < 0.05). Significance QADM and NAg were incorporated into calcium phosphate composite for the first time. NACP+QADM+NAg was strongly-antibacterial and greatly reduced the titer counts, metabolic activity, and acid production of S. mutans biofilms, while possessing mechanical properties similar to commercial composites. These nanocomposites are promising to have

  20. Carbon-enriched calcium carbide and its potential use

    SciTech Connect

    Ivakhnyuk, G.K.; Samonin, V.V.; Fedorov, N.F.; Vladimirov, V.A.; Stepanova, L.V.; Kas'yanova, O.M.

    1987-10-10

    The authors comparatively assess the feasibility of a variety of carbonaceous materials--lean coal, specialty coke, coal coke, semicoke, and coke residue from shale production--as raw materials for the production and carburization of calcium carbide and subsequently assess the value of the calcium carbide produced as a raw material in the production of graphite. They determine that calcium carbide enriched by their process is characterized by a high carbon content having the graphite structure and that the use of carburized calcium carbide allows for a significant increase in the output of graphite during low-temperature reaction of the carbide with magnesium chloride.

  1. Calcium carbonate scaling kinetics determined from radiotracer experiments with calcium-47

    SciTech Connect

    Turner, C.W.; Smith, D.W.

    1998-02-01

    The deposition of calcium carbonate is one of the principal modes of fouling of the heat-transfer surface of a fresh-water-cooled heat exchanger. The deposition rate of calcium carbonate on a heat-transfer surface has been measured using a calcium-47 radiotracer and compared to the measured rate of thermal fouling. The crystalline phase of calcium carbonate that precipitates depends on the degree of supersaturation at the heat-transfer surface, with aragonite precipitating at higher supersaturations and calcite precipitating at lower supersaturations. Whereas the mass deposition rates were constant with time, the thermal fouling rates decreased throughout the course of each experiment as a result of densification of the deposit. It is proposed that the densification was driven by the temperature gradient across the deposit together with the retrograde solubility of calcium carbonate. The temperature dependence of the deposition rate yielded an activation energy of 79 {+-} 4 kJ/mol for the precipitation of calcium carbonate on a heat-transfer surface.

  2. Creation and formation mechanism of new carbon phases constructed by amorphous carbon

    NASA Astrophysics Data System (ADS)

    Yao, Mingguang; Cui, Wen; Liu, Bingbing

    Our recent effort is focusing on the creation of new hard/superhard carbon phases constructed by disordered carbons or amorphous carbon clusters under high pressure. We showed that the pressure-induced amorphous hard carbon clusters from collapsed fullerenes can be used as building blocks (BBs) for constructing novel carbon structures. This new strategy has been verified by compressing a series of intercalated fullerides, pre-designed by selecting various dopants with special features. We demonstrate that the boundaries of the amorphous BBs are mediated by intercalated dopants and several new superhard materials have been prepared. We also found that the dopant-mediated BBs can be arranged in either ordered or disordered structures, both of which can be hard enough to indent the diamond anvils. The hardening mechanisms of the new phases have also been discussed. For the glassy carbon (GC) constructructed by disordered fullerene-like nanosized fragments, we also found that these disordered fragments can bond and the compressed GC transformed into a transparent superhard phase. Such pressure-induced transformation has been discovered to be driven by a novel mechanism (unpublished). By understanding the mechanisms we can clarify the controversial results on glassy carbon reported recently. The authors would like to thank the financial support from the National Natural Science Foundation of China (No. 11474121, 51320105007).

  3. Amorphous carbon thin films for optoelectric device application

    SciTech Connect

    Soga, T.; Jimbo, T.; Krishna, K.M.; Umeno, M.

    2000-01-30

    Thin films of amorphous carbon (a-C and a-C:H) have been deposited using different carbon precursor materials such as camphor--a natural source, graphite and CH{sub 4}/H{sub 2} mixture by different deposition methods, such as ion beam sputtering, pyrolysis, pulsed laser deposition and r.f. plasma CVD. The films are subjected to various standard characterization techniques in order to tailor the required structural and opto-electrical properties for device applications. The effects of deposition parameters and annealing temperatures on the properties of carbon thin films have been investigated. Both p- and n- type of carbon films have been obtained either through controlling the deposition parameters of a particular method or by doping. Solar cells of various configurations, such as n-C/p-Si, p-C/n-Si and n-C/p-C/p-Si, have been fabricated and their photoresponse characteristics are studied. An efficiency of 1.52% has been obtained, so far, for the cell of configuration n-C/p-C/p-Si. Effects of substrate temperature on the photovoltaic properties are also outlined in brief.

  4. Structure-property relations in amorphous carbon for photovoltaics

    NASA Astrophysics Data System (ADS)

    Risplendi, Francesca; Bernardi, Marco; Cicero, Giancarlo; Grossman, Jeffrey C.

    2014-07-01

    Carbon is emerging as a material with great potential for photovoltaics (PV). However, the amorphous form (a-C) has not been studied in detail as a PV material, even though it holds similarities with amorphous Silicon (a-Si) that is widely employed in efficient solar cells. In this work, we correlate the structure, bonding, stoichiometry, and hydrogen content of a-C with properties linked to PV performance such as the electronic structure and optical absorption. We employ first-principles molecular dynamics and density functional theory calculations to generate and analyze a set of a-C structures with a range of densities and hydrogen concentrations. We demonstrate that optical and electronic properties of interest in PV can be widely tuned by varying the density and hydrogen content. For example, sunlight absorption in a-C films can significantly exceed that of a same thickness of a-Si for a range of densities and H contents in a-C. Our results highlight promising features of a-C as the active layer material of thin-film solar cells.

  5. Structure-property relations in amorphous carbon for photovoltaics

    SciTech Connect

    Risplendi, Francesca; Cicero, Giancarlo; Bernardi, Marco; Grossman, Jeffrey C.

    2014-07-28

    Carbon is emerging as a material with great potential for photovoltaics (PV). However, the amorphous form (a-C) has not been studied in detail as a PV material, even though it holds similarities with amorphous Silicon (a-Si) that is widely employed in efficient solar cells. In this work, we correlate the structure, bonding, stoichiometry, and hydrogen content of a-C with properties linked to PV performance such as the electronic structure and optical absorption. We employ first-principles molecular dynamics and density functional theory calculations to generate and analyze a set of a-C structures with a range of densities and hydrogen concentrations. We demonstrate that optical and electronic properties of interest in PV can be widely tuned by varying the density and hydrogen content. For example, sunlight absorption in a-C films can significantly exceed that of a same thickness of a-Si for a range of densities and H contents in a-C. Our results highlight promising features of a-C as the active layer material of thin-film solar cells.

  6. Presence of Amorphous Carbon Nanoparticles in Food Caramels

    PubMed Central

    Sk, Md Palashuddin; Jaiswal, Amit; Paul, Anumita; Ghosh, Siddhartha Sankar; Chattopadhyay, Arun

    2012-01-01

    We report the finding of the presence of carbon nanoparticles (CNPs) in different carbohydrate based food caramels, viz. bread, jaggery, sugar caramel, corn flakes and biscuits, where the preparation involves heating of the starting material. The CNPs were amorphous in nature; the particles were spherical having sizes in the range of 4–30 nm, depending upon the source of extraction. The results also indicated that particles formed at higher temperature were smaller than those formed at lower temperature. Excitation tuneable photoluminescence was observed for all the samples with quantum yield (QY) 1.2, 0.55 and 0.63%, for CNPs from bread, jaggery and sugar caramels respectively. The present discovery suggests potential usefulness of CNPs for various biological applications, as the sources of extraction are regular food items, some of which have been consumed by humans for centuries, and thus they can be considered as safe. PMID:22540029

  7. Heat treatment of cathodic arc deposited amorphous hard carbon films

    SciTech Connect

    Anders, S.; Ager, J.W. III; Brown, I.G.

    1997-02-01

    Amorphous hard carbon films of varying sp{sup 2}/sp{sup 3} fractions have been deposited on Si using filtered cathodic are deposition with pulsed biasing. The films were heat treated in air up to 550 C. Raman investigation and nanoindentation were performed to study the modification of the films caused by the heat treatment. It was found that films containing a high sp{sup 3} fraction sustain their hardness for temperatures at least up to 400 C, their structure for temperatures up to 500 C, and show a low thickness loss during heat treatment. Films containing at low sp{sup 3} fraction graphitize during the heat treatment, show changes in structure and hardness, and a considerable thickness loss.

  8. Presence of Amorphous Carbon Nanoparticles in Food Caramels

    NASA Astrophysics Data System (ADS)

    Palashuddin, Sk; Jaiswal, Amit; Paul, Anumita; Ghosh, Siddhartha Sankar; Chattopadhyay, Arun

    2012-04-01

    We report the finding of the presence of carbon nanoparticles (CNPs) in different carbohydrate based food caramels, viz. bread, jaggery, sugar caramel, corn flakes and biscuits, where the preparation involves heating of the starting material. The CNPs were amorphous in nature; the particles were spherical having sizes in the range of 4-30 nm, depending upon the source of extraction. The results also indicated that particles formed at higher temperature were smaller than those formed at lower temperature. Excitation tuneable photoluminescence was observed for all the samples with quantum yield (QY) 1.2, 0.55 and 0.63%, for CNPs from bread, jaggery and sugar caramels respectively. The present discovery suggests potential usefulness of CNPs for various biological applications, as the sources of extraction are regular food items, some of which have been consumed by humans for centuries, and thus they can be considered as safe.

  9. Pulsed laser deposition of amorphous carbon/silver nanocomposites

    NASA Astrophysics Data System (ADS)

    Matenoglou, G.; Evangelakis, G. A.; Kosmidis, C.; Foulias, S.; Papadimitriou, D.; Patsalas, P.

    2007-07-01

    Metal/amorphous carbon (a-C:M) composite films are emerging as a category of very important engineering materials for surface protection. We implement pulsed laser deposition (PLD) to grow pure a-C and a-C:Ag nanocomposites. Our PLD process is assisted by a static electric field. We investigate the structural features of the a-C:Ag nanocomposites and the bonding configuration of the a-C matrix with respect to the electric field and the composition of the PLD target. For this study we use Auger electron spectroscopy (AES), electron energy loss spectroscopy (EELS) and X-ray diffraction (XRD). We show that the Ag mean grain size and the sp 2 content of the a-C matrix are increasing with increasing Ag content in the films.

  10. Presence of amorphous carbon nanoparticles in food caramels.

    PubMed

    Sk, Md Palashuddin; Jaiswal, Amit; Paul, Anumita; Ghosh, Siddhartha Sankar; Chattopadhyay, Arun

    2012-01-01

    We report the finding of the presence of carbon nanoparticles (CNPs) in different carbohydrate based food caramels, viz. bread, jaggery, sugar caramel, corn flakes and biscuits, where the preparation involves heating of the starting material. The CNPs were amorphous in nature; the particles were spherical having sizes in the range of 4-30 nm, depending upon the source of extraction. The results also indicated that particles formed at higher temperature were smaller than those formed at lower temperature. Excitation tuneable photoluminescence was observed for all the samples with quantum yield (QY) 1.2, 0.55 and 0.63%, for CNPs from bread, jaggery and sugar caramels respectively. The present discovery suggests potential usefulness of CNPs for various biological applications, as the sources of extraction are regular food items, some of which have been consumed by humans for centuries, and thus they can be considered as safe. PMID:22540029

  11. Dissolution kinetics of calcium carbonate in equatorial Pacific sediments

    SciTech Connect

    Berelson, W.M.; Hammond, D.E.; McManus, J.; Kilgore, T.E. )

    1994-06-01

    Calcium carbonate dissolution exerts a major influence on the carbonate chemistry of seawater and is an important factor in regulating atmospheric CO2 concentration. The authors use a numerical model, based on an estimate of k determined from benthic chamber flux measurements, the distribution of CO3 2-in the water column and percent of CaCO3 in the sediments, to derive the total alkalinity flux from Pacific Ocean sediments. The significance of this budget is discussed as are the following questions: what is the rate of calcium carbonate dissolution on the deep sea floor what controls carbonate dissolution, organic carbon rain rates, or bottom water carbonate ion concentration what is the equations that relates carbonate dissolution to degree of undersaturation and what is the associate rate constant 43 refs., 10 figs., 4 tabs.

  12. Casein Phosphopeptide-Amorphous Calcium Phosphate and Shear Bond Strength of Adhesives to Primary Teeth Enamel

    PubMed Central

    Farokh Gisovar, Elham; Hedayati, Nassim; Shadman, Niloofar; Shafiee, Leila

    2015-01-01

    Background: CPP-ACP (Phosphopeptide-Amorphous Calcium Phosphate) has an important role in caries prevention in pediatric patients. This study was done, because of the great use of CPP-ACP and the need for restoration for teeth treated with CPP-ACP as well as the importance of shear bond strength of adhesives in the success of restorations. Objectives: This study aimed to evaluate the effect of casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) on shear bond strength of dental adhesives to enamel of primary teeth molars. Materials and Methods: This in vitro study was conducted on 180 extracted primary molars. They were randomly divided into 6 groups and each group was divided into 2 subgroups (treated with CPP-ACP and untreated). In subgroups with CPP-ACP, enamel was treated with CPP-ACP paste 1 h/d for 5 days. Types of adhesives that were evaluated in this study were Tetric N-Bond, AdheSE, AdheSE One F, single Bond 2, SE Bond, and Adper Prompt L-Pop. Shear bond strength was tested with a universal testing machine and mode of failure was evaluated under stereomicroscope. Data were analyzed by T test, 2-way analysis of variance (ANOVA), Tukey and Fisher exact test using SPSS18. P < 0.05 was considered as significance level. Results: Shear bond strengths of different adhesive systems to enamel of primary teeth treated and untreated with CPP-ACP showed no significant difference (P > 0.05). Mode of failure in all groups regardless of CPP-ACP administration was mainly adhesive type. Our results indicated that CPP-ACP did not affect shear bond strength of studied adhesives to primary teeth enamel. Conclusions: To have a successful and durable composite restoration, having a high strength bonding is essential. Considering the wide use of CPP-ACP in preventing tooth decay and the role of adhesive shear bond strength (SBS) in success of composite restoration, we conducted the present study to evaluate the effect of CPP-ACP on the SBS of adhesives to primary teeth

  13. Calcium carbonate mineralization: X-ray microdiffraction probing of the interface of an evaporating drop on a superhydrophobic surface.

    PubMed

    Accardo, Angelo; Burghammer, Manfred; Di Cola, Emanuela; Reynolds, Michael; Di Fabrizio, Enzo; Riekel, Christian

    2011-07-01

    The liquid/air interface of calcium bicarbonate solution drops was probed by synchrotron radiation microbeam scattering. The drops were deposited on a nanopatterned superhydrophobic poly(methyl methacrylate) surface and raster-scanned during evaporation by small-angle and wide-angle X-ray scattering. The appearance of about 200-nm-size calcite crystallites at the interface could be spatially resolved at the onset of crystallization. Diffuse scattering from the interface is attributed to a dense nanoscale amorphous calcium carbonate phase. Calcite was found to be the major phase in the solid residue with vaterite as minor phase. PMID:21663321

  14. Research Update: Direct conversion of amorphous carbon into diamond at ambient pressures and temperatures in air

    SciTech Connect

    Narayan, Jagdish Bhaumik, Anagh

    2015-10-01

    We report on fundamental discovery of conversion of amorphous carbon into diamond by irradiating amorphous carbon films with nanosecond lasers at room-temperature in air at atmospheric pressure. We can create diamond in the form of nanodiamond (size range <100 nm) and microdiamond (>100 nm). Nanosecond laser pulses are used to melt amorphous diamondlike carbon and create a highly undercooled state, from which various forms of diamond can be formed upon cooling. The quenching from the super undercooled state results in nucleation of nanodiamond. It is found that microdiamonds grow out of highly undercooled state of carbon, with nanodiamond acting as seed crystals.

  15. Novel dental adhesives containing nanoparticles of silver and amorphous calcium phosphate

    PubMed Central

    Melo, Mary Anne S.; Cheng, Lei; Zhang, Ke; Weir, Michael D.; Rodrigues, Lidiany K. A.; Xu, Hockin H. K.

    2012-01-01

    Objectives Secondary caries is the main reason for restoration failure, and replacement of the failed restorations accounts for 50–70% of all restorations. Antibacterial adhesives could inhibit residual bacteria in tooth cavity and invading bacteria along the margins. Calcium (Ca) and phosphate (P) ion release could remineralize the lesions. The objectives of this study were to incorporate nanoparticles of silver (NAg) and nanoparticles of amorphous calcium phosphate (NACP) into adhesive for the first time, and to investigate the effects on dentin bond strength and plaque microcosm biofilms. Methods Scotchbond Multi-Purpose adhesive was used as control. NAg were added into primer and adhesive at 0.1% by mass. NACP were mixed into adhesive at 10%, 20%, 30% and 40%. Microcosm biofilms were grown on disks with primer covering the adhesive on a composite. Biofilm metabolic activity, colony-forming units (CFU) and lactic acid were measured. Results Human dentin shear bond strengths (n=10) ranged from 26 to 34 MPa; adding NAg and NACP into adhesive did not decrease the bond strength (p > 0.1). SEM examination revealed resin tags from well-filled dentinal tubules. Numerous NACP infiltrated into the dentinal tubules. While NACP had little antibacterial effect, NAg in bonding agents greatly reduced the biofilm viability and metabolic activity, compared to the control (p < 0.05). CFU for total microorganisms, total streptococci, and mutans streptococci on bonding agents with NAg were an order of magnitude less than those of the control. Lactic acid production by biofilms for groups containing NAg was 1/4 of that of the control. Significance Dental plaque microcosm biofilm viability and acid production were greatly reduced on bonding agents containing NAg and NACP, without compromising dentin bond strength. The novel method of incorporating dual agents (remineralizing agent NACP and antibacterial agent NAg) may have wide applicability to other dental bonding systems. PMID

  16. Mechanical and acid neutralizing properties and bacteria inhibition of amorphous calcium phosphate dental nanocomposite.

    PubMed

    Moreau, Jennifer L; Sun, Limin; Chow, Laurence C; Xu, Hockin H K

    2011-07-01

    Dental composites do not hinder bacteria colonization and plaque formation. Caries at the restoration margins is a frequent reason for replacement of existing restorations, which accounts for 50 to 70% of all restorations. The objectives of this study were to examine the filler level effect on nanocomposite containing nanoparticles of amorphous calcium phosphate (NACP) and investigate the load-bearing and acid-neutralizing properties and bacteria inhibition. NACP with 116-nm particle size were synthesized via a spray-drying technique and incorporated into a resin. Flexural strength of nanocomposite with 10 to 30% NACP fillers matched the strength of a commercial hybrid composite (p > 0.1). Nanocomposite with 40% NACP matched the strength of a microfill composite, which was 2-fold that of a resin-modified glass ionomer. Nanocomposite with 40% NACP neutralized a lactic acid solution of pH 4 by rapidly increasing the pH to 5.69 in 10 min. In contrast, the commercial controls had pH staying at near 4. Using Streptoccocus mutans, an agar disk-diffusion test showed no inhibition zone for commercial controls. In contrast, the inhibition zone was (2.5 ± 0.7) mm for nanocomposite with 40% NACP. Crystal violet staining showed that S. mutans coverage on nanocomposite was 1/4 that on commercial composite. In conclusion, novel calcium-phosphate nanocomposite matched the mechanical properties of commercial composite and rapidly neutralized lactic acid of pH 4. The nanocomposite appeared to moderately reduce the S. mutans growth, and further study is needed to obtain strong antimicrobial properties. The new nanocomposite may have potential to reduce secondary caries and restoration fracture, two main challenges facing tooth cavity restorations. PMID:21504057

  17. Array of amorphous calcium phosphate particles improves cellular activity on a hydrophobic surface.

    PubMed

    Kim, InAe; Kim, Hyun Jung; Kim, Hyun-Man

    2010-04-01

    Poor interaction between cells and surfaces, especially hydrophobic surfaces, results in delayed proliferation and increased apoptosis due to low cell adhesion signaling. To improve cell adhesion, hydrophilic array of amorphous calcium phosphate (ACP) was fabricated on a surface. A phosphate-buffered solution containing calcium ions was prepared at low temperature to prevent spontaneous precipitation. Then, the ion solution was heated to generate nuclei of ACP nanoparticles. The ACP nanoparticles adhered to the hydrophobic polystyrene surface forming an array composed of ACP particles. Multiple treatments of these nuclei with fresh CaP ion solutions increased the diameter and decreased the solubility of ACP particles enough to mediate cellular adhesion. The particle density in the array was dependent on the ion concentration of the CaP ion solutions. The ACP array improved a wide variety of activities when osteoblastic MC3T3-E1 cells were cultured on the ACP array fabricated on a hydrophobic bacteriological dish surface, compared to those cultured without the ACP array in vitro. The use of ACP array resulted in a lower apoptosis and also increased the spreading of cells to form stress fibers and focal contacts. Cells cultured on the ACP array proliferated more than cells cultured on a hydrophobic surface without the ACP array. The ACP array increased the expression of markers of differentiation in osteoblast. These results indicate that an array of ACP can be used as a coating material for enhancing biocompatibility in tissue engineering or biomaterials rather than modifying the surface with organic molecules. PMID:20119940

  18. Structure-Composition-Property Relationships in Polymeric Amorphous Calcium Phosphate-Based Dental Composites†

    PubMed Central

    O’Donnell, Justin N.R.; Schumacher, Gary E.; Antonucci, Joseph M.; Skrtic, Drago

    2009-01-01

    Our studies of amorphous calcium phosphate (ACP)-based materials over the last decade have yielded bioactive polymeric composites capable of protecting teeth from demineralization or even regenerating lost tooth mineral. The anti-cariogenic/re-mineralizing potential of these ACP composites originates from their propensity, when exposed to the oral environment, to release in a sustained manner sufficient levels of mineral-forming calcium and phosphate ions to promote formation of stable apatitic tooth mineral. However, the less than optimal ACP filler/resin matrix cohesion, excessive polymerization shrinkage and water sorption of these experimental materials can adversely affect their physicochemical and mechanical properties, and, ultimately, limit their lifespan. This study demonstrates the effects of chemical structure and composition of the methacrylate monomers used to form the matrix phase of composites on degree of vinyl conversion (DVC) and water sorption of both copolymers and composites and the release of mineral ions from the composites. Modification of ACP surface via introducing cations and/or polymers ab initio during filler synthesis failed to yield mechanically improved composites. However, moderate improvement in composite’s mechanical stability without compromising its remineralization potential was achieved by silanization and/or milling of ACP filler. Using ethoxylated bisphenol A dimethacrylate or urethane dimethacrylate as base monomers and adding moderate amounts of hydrophilic 2-hydroxyethyl methacrylate or its isomer ethyl-α-hydroxymethacrylate appears to be a promising route to maximize the remineralizing ability of the filler while maintaining high DVC. Exploration of the structure/composition/property relationships of ACP fillers and polymer matrices is complex but essential for achieving a better understanding of the fundamental mechanisms that govern dissolution/re-precipitation of bioactive ACP fillers, and, ultimately, the

  19. Biomineralization of calcium carbonates and their engineered applications: a review

    PubMed Central

    Dhami, Navdeep K.; Reddy, M. Sudhakara; Mukherjee, Abhijit

    2013-01-01

    Microbially induced calcium carbonate precipitation (MICCP) is a naturally occurring biological process in which microbes produce inorganic materials as part of their basic metabolic activities. This technology has been widely explored and promising with potential in various technical applications. In the present review, the detailed mechanism of production of calcium carbonate biominerals by ureolytic bacteria has been discussed along with role of bacteria and the sectors where these biominerals are being used. The applications of bacterially produced carbonate biominerals for improving the durability of buildings, remediation of environment (water and soil), sequestration of atmospheric CO2 filler material in rubbers and plastics etc. are discussed. The study also sheds light on benefits of bacterial biominerals over traditional agents and also the issues that lie in the path of successful commercialization of the technology of microbially induced calcium carbonate precipitation from lab to field scale. PMID:24194735

  20. Influence of some polysaccharides on the production of calcium carbonate filler particles

    NASA Astrophysics Data System (ADS)

    Kontrec, Jasminka; Kralj, Damir; Brečević, Ljerka; Falini, Giuseppe

    2008-10-01

    The influence of different water-soluble polysaccharides, dextrans (cationic, anionic and non-ionic) and soluble starch, on the precipitation of calcium carbonate, has been investigated in the model system in which calcium hydroxide and carbonic acid were reactants. In the absence of additives, the formation of metastable phases, vaterite and amorphous calcium carbonate is observed at the early stage of the process, and as a consequence of the solution-mediated transformation process calcite appears in the system as the only solid phase in equilibrium. In the presence of starch, vaterite is found in the final precipitate, with the content increasing with the increase of starch concentration, probably as a consequence of calcite nucleation and crystal growth inhibition. Non-ionic dextran causes the inhibition of vaterite nucleation, which results in the formation of calcite as a predominant solid phase throughout the precipitation process. The crystal size of the so-formed calcite reduces by increasing the relative molecular mass ( Mr) of neutral dextran. The presence of charged dextrans, either cationic or anionic, causes inhibition of the overall precipitation process: in the case of anionic dextran the inhibition seems to be the consequence of its reaction with Ca 2+ ions (supersaturation decrease), while cationic dextran most probably adsorbs electrostatically onto the negatively charged surfaces of calcite and vaterite.

  1. Incorporation of Chromate into Calcium Carbonate Structure during Coprecipitation

    SciTech Connect

    Hua, Bin; Deng, Baolin; Thornton, Edward C.; Yang, J.; Amonette, James E.

    2006-09-08

    To assess treatment technologies and establish regulatory framework for chromate-contaminated site remediation, it is imperative to know the exact chromium speciation in soil matrices. In an earlier study, Thornton and Amonette (1999) reported that some chromate in the bulk particles was not accessible to gaseous reductants or solution-phase extractants, based on XANES studies. We hypothesized that part of this non-extractable chromate may reside in the structure of minerals such as calcium carbonate. To test this hypothesis, a number of calcium carbonate precipitates were prepared in the presence of various concentrations of chromate during the precipitation, which could coprecipitate chromate, or by adding chromate after the precipitation was completed. Hydrochloric acid was used to dissolve calcium carbonate and therefore extract the coprecipitated and surface attached chromate. The results showed that the coprecipitated chromate was non-extractable by hot alkaline solution or phosphate buffer, but could be solubilized by HCl in proportional to the amount of calcium carbonate dissolved. The X-ray diffraction experiments revealed that the coprecipitation of chromate with calcium carbonate had an influence on its crystal structure: the higher the chromate concentration, the greater the ratio of vaterite to calcite.

  2. The Role of Carboxydothermus hydrogenoformans in the Conversion of Calcium Phosphate from Amorphous to Crystalline State

    PubMed Central

    Haddad, Mathieu; Vali, Hojatollah; Paquette, Jeanne; Guiot, Serge R.

    2014-01-01

    Two previously unknown modes of biomineralization observed in the presence of Carboxydothermus hydrogenoformans are presented. Following the addition of NaHCO3 and the formation of an amorphous calcium phosphate precipitate in a DSMZ medium inoculated with C. hydrogenoformans, two distinct crystalline solids were recovered after 15 and 30 days of incubation. The first of these solids occurred as micrometric clusters of blocky, angular crystals, which were associated with bacterial biofilm. The second solid occurred as 30–50 nm nanorods that were found scattered among the organic products of bacterial lysis. The biphasic mixture of solids was clearly dominated by the first phase. The X-ray diffractometry (XRD) peaks and Fourier transform infrared spectroscopy (FTIR) spectrum of this biphasic material consistently showed features characteristic of Mg-whitlockite. No organic content or protein could be identified by dissolving the solids. In both cases, the mode of biomineralization appears to be biologically induced rather than biologically controlled. Since Mg is known to be a strong inhibitor of the nucleation and growth of CaP, C. hydrogenoformans may act by providing sites that chelate Mg or form complexes with it, thus decreasing its activity as nucleation and crystal growth inhibitor. The synthesis of whitlockite and nano-HAP-like material by C. hydrogenoformans demonstrates the versatility of this organism also known for its ability to perform the water-gas shift reaction, and may have applications in bacterially mediated synthesis of CaP materials, as an environmentally friendly alternative process. PMID:24586811

  3. Atomic-scale compositional mapping reveals Mg-rich amorphous calcium phosphate in human dental enamel.

    PubMed

    La Fontaine, Alexandre; Zavgorodniy, Alexander; Liu, Howgwei; Zheng, Rongkun; Swain, Michael; Cairney, Julie

    2016-09-01

    Human dental enamel, the hardest tissue in the body, plays a vital role in protecting teeth from wear as a result of daily grinding and chewing as well as from chemical attack. It is well established that the mechanical strength and fatigue resistance of dental enamel are derived from its hierarchical structure, which consists of periodically arranged bundles of hydroxyapatite (HAP) nanowires. However, we do not yet have a full understanding of the in vivo HAP crystallization process that leads to this structure. Mg(2+) ions, which are present in many biological systems, regulate HAP crystallization by stabilizing its precursor, amorphous calcium phosphate (ACP), but their atomic-scale distribution within HAP is unknown. We use atom probe tomography to provide the first direct observations of an intergranular Mg-rich ACP phase between the HAP nanowires in mature human dental enamel. We also observe Mg-rich elongated precipitates and pockets of organic material among the HAP nanowires. These observations support the postclassical theory of amelogenesis (that is, enamel formation) and suggest that decay occurs via dissolution of the intergranular phase. This information is also useful for the development of more accurate models to describe the mechanical behavior of teeth. PMID:27617291

  4. Atomic-scale compositional mapping reveals Mg-rich amorphous calcium phosphate in human dental enamel

    PubMed Central

    La Fontaine, Alexandre; Zavgorodniy, Alexander; Liu, Howgwei; Zheng, Rongkun; Swain, Michael; Cairney, Julie

    2016-01-01

    Human dental enamel, the hardest tissue in the body, plays a vital role in protecting teeth from wear as a result of daily grinding and chewing as well as from chemical attack. It is well established that the mechanical strength and fatigue resistance of dental enamel are derived from its hierarchical structure, which consists of periodically arranged bundles of hydroxyapatite (HAP) nanowires. However, we do not yet have a full understanding of the in vivo HAP crystallization process that leads to this structure. Mg2+ ions, which are present in many biological systems, regulate HAP crystallization by stabilizing its precursor, amorphous calcium phosphate (ACP), but their atomic-scale distribution within HAP is unknown. We use atom probe tomography to provide the first direct observations of an intergranular Mg-rich ACP phase between the HAP nanowires in mature human dental enamel. We also observe Mg-rich elongated precipitates and pockets of organic material among the HAP nanowires. These observations support the postclassical theory of amelogenesis (that is, enamel formation) and suggest that decay occurs via dissolution of the intergranular phase. This information is also useful for the development of more accurate models to describe the mechanical behavior of teeth. PMID:27617291

  5. Axially aligned organic fibers and amorphous calcium phosphate form the claws of a terrestrial isopod (Crustacea).

    PubMed

    Vittori, Miloš; Srot, Vesna; Žagar, Kristina; Bussmann, Birgit; van Aken, Peter A; Čeh, Miran; Štrus, Jasna

    2016-08-01

    Skeletal elements that are exposed to heavy mechanical loads may provide important insights into the evolutionary solutions to mechanical challenges. We analyzed the microscopic architecture of dactylus claws in the woodlice Porcellio scaber and correlated these observations with analyses of the claws' mineral composition with energy dispersive X-ray spectrometry (EDX), electron energy loss spectroscopy (EELS) and selected area electron diffraction (SAED). Extraordinarily, amorphous calcium phosphate is the predominant mineral in the claw endocuticle. Unlike the strongly calcified exocuticle of the dactylus base, the claw exocuticle is devoid of mineral and is highly brominated. The architecture of the dactylus claw cuticle is drastically different from that of other parts of the exoskeleton. In contrast to the quasi-isotropic structure with chitin-protein fibers oriented in multiple directions, characteristic of the arthropod exoskeleton, the chitin-protein fibers and mineral components in the endocuticle of P. scaber claws are exclusively axially oriented. Taken together, these characteristics suggest that the claw cuticle is highly structurally anisotropic and fracture resistant and can be explained as adaptations to predominant axial loading of the thin, elongated claws. The nanoscale architecture of the isopod claw may inspire technological solutions in the design of durable machine elements subjected to heavy loading and wear. PMID:27320700

  6. Analysis of anticaries potential of pit and fissures sealants containing amorphous calcium phosphate using synchrotron microtomography.

    PubMed

    Delben, A C B; Cannon, M; Vieira, A E M; Basso, M D; Danelon, M; Santo, M R E; Stock, S R; Xiao, X; De Carlo, F

    2015-01-01

    The aim of this study was to analyze the anticaries potential of pit and fissure sealants containing amorphous calcium phosphate (ACP) by synchrotron microtomography. Bovine enamel blocks (4×4 mm; n=50) were selected through surface hardness (Knoop) analysis. Slabs were obtained through cross-sections taken 1 mm from the border of the enamel. Five indentations, spaced 100 μm apart, were made 300 μm from the border. Ten specimens were prepared for each tested material (Ultraseal XT plus TM, Aegis, Embrace, Vitremer and Experimental Sealant). The materials were randomly attached to the sectioned surfaces of the enamel blocks and fixed with sticky wax. The specimens were submitted to pH cycling. After that, the surface hardness (SH1) was determined, and the blocks were submitted to synchrotron microcomputed tomography analysis to calculate the mineral concentration (ΔgHAp cm(-3)) at different areas of the enamel. The comparison between the SH1 and ΔgHAp cm(-3) showed a correlation for all groups (r=0.840; p<0.001). The fluoride groups presented positive values of ΔgHAp cm(-3), indicating a mineral gain that was observed mainly in the outer part of the enamel. The ACP showed mineral loss in the outer enamel compared with fluoride groups, although it inhibited the demineralization in the deeper areas of enamel. The combination of two remineralizing agents (fluoride and ACP) was highly effective in preventing demineralization. PMID:25268042

  7. Conversion of amorphous calcium phosphate into hydroxyapatite investigated by EXAFS spectroscopy

    NASA Astrophysics Data System (ADS)

    Harries, J. E.; Hukins, D. W. L.; Holt, C.; Hasnain, S. S.

    1987-10-01

    Amorphous calcium phosphate (ACP) was precipitated from solution at pH 10. Some samples were allowed to transform to poorly crystalline hydroxyapatite (HAP), at this pH, for periods up to 120 h. All samples were stabilised by freeze-drying and characterised by extended X-ray absorption fine structure (EXAFS) spectroscopy as well as by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. EXAFS spectra, recorded above the K absorption edge of Ca, were interpreted using a model developed previously to explain the features of the EXAFS spectrum of fully crystalline HAP. Eight shells of atoms surrounding Ca out to 0.57 nm were required to explain the appearance of poorly crystalline HAP. In contrast, only the innermost three of these shells were required to interpret the spectrum of the initial ACP. Moreover, these three shells had almost identical radii and Debye-Waller factors as in the poorly crystalline HAP and so the process of crystallisation involves only the development of longer-range order without changing the immediate environment of Ca.

  8. Sputtering deposition and characterization of ultrathin amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Lu, Wei

    1999-11-01

    This dissertation focuses on experimental investigations of ultrathin, ultrasmooth amorphous carbon (a-C) films deposited on Si(100) substrates by radio frequency (RF) sputtering and characterization of the nanomechanical and nanotribological properties and thermal stability of the films. Ultrathin a-C films of thickness 5--100 nm and typical root-mean-square roughness of 0.15--1 nm were deposited on ultrasmooth Si(100) substrates using pure argon as the sputtering gas. A low-pressure RF argon discharge model was used to analyze the plasma parameters in the film growth environment. These plasma parameters correlate the deposition conditions with the film growth processes. Atomic force microscopy (AFM) and surface force microscopy (SFM) were used to characterize the nanomechanical and nanotribological properties of the a-C films. X-ray photoelectron spectroscopy (XPS) was used to investigate the compositions and microstructures of the films. Sputter-etching measurements of the a-C films by energetic argon ion bombardment were used to study the surface binding energy of carbon atoms in a-C films deposited under different conditions. The dependence of film properties on deposition conditions was studied, and relations between nanomechanical and nanotribological properties were discussed in terms of a modified deformation index. The deformation and nanotribology mechanisms of the a-C films were compared with those of other films, such as TiC and Cr films (both 100 nm thick), and bulk Si(100). Reactive RF sputtering of nitrogenated amorphous carbon (a-CNx) films was investigated by introducing nitrogen into the a-C films during film growth by using an argon-nitrogen gas mixture as the sputtering gas. The alloying effect of nitrogen on the film growth and properties, such as hardness and surface energy, was studied and interpreted in terms of the changes in the plasma environment induced due to differences in the composition of the sputtering gas mixture. The thermal

  9. In-depth modifications of implanted amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Freire, F. L.; Achete, C. A.; Franceschini, D. F.; Mariotto, G.

    1994-12-01

    Amorphous carbon films (a-C:H) and nitrogen incorporated carbon films [a-C:H(N)] deposited by a self-bias glow discharge have been implanted with 70 keV nitrogen ions at fluences of 0.6, 1 and 2×1017 N/cm2. The in-depth modifications caused by ion implantation were determined by means of nuclear techniques, such as Rutherford Backscattering Spectrometry (RBS), Nuclear Reaction Analysis (NRA) and Elastic Recoil Detection Analysis (ERDA), as well as by Auger Electron Spectroscopy (AES) and Raman scattering. ERDA profiles show that nitrogen implantation causes hydrogen depletion, the amount of which depends on the film composition and on the ion fluence. In a-C:H(N) films nitrogen loss was also measured. The induced structural modifications in both a-C:H and a-C:H(N) films were followed by both AES, using factor analysis, and microprobe Raman spectroscopy. They turn out to be related to the energy deposited by the incident ions. Our results indicate that the ion-beam bombardment causes in both a-C:H and a-C:H(N) films an increase of either the degree of disorder or the ratio between sp2/sp3 bonds across the hydrogen-depleted layer, which depends on the ion fluence.

  10. Automatic photometric titrations of calcium and magnesium in carbonate rocks

    USGS Publications Warehouse

    Shapiro, L.; Brannock, W.W.

    1955-01-01

    Rapid nonsubjective methods have been developed for the determination of calcium and magnesium in carbonate rocks. From a single solution of the sample, calcium is titrated directly, and magnesium is titrated after a rapid removal of R2O3 and precipitation of calcium as the tungstate. A concentrated and a dilute solution of disodium ethylenediamine tetraacetate are used as titrants. The concentrated solution is added almost to the end point, then the weak solution is added in an automatic titrator to determine the end point precisely.

  11. Hydrogen induced redox mechanism in amorphous carbon resistive random access memory

    PubMed Central

    2014-01-01

    We investigated the bipolar resistive switching characteristics of the resistive random access memory (RRAM) device with amorphous carbon layer. Applying a forming voltage, the amorphous carbon layer was carbonized to form a conjugation double bond conductive filament. We proposed a hydrogen redox model to clarify the resistive switch mechanism of high/low resistance states (HRS/LRS) in carbon RRAM. The electrical conduction mechanism of LRS is attributed to conductive sp2 carbon filament with conjugation double bonds by dehydrogenation, while the electrical conduction of HRS resulted from the formation of insulating sp3-type carbon filament through hydrogenation process. PMID:24475979

  12. In Situ Electrical Study on Primary Hydrogen Spillover from Nanocatalysts to Amorphous Carbon Support

    SciTech Connect

    Lin, C.; Yang, Z.; Xu, T.; Zhao, Y.

    2008-01-01

    Primary hydrogen spillover has been studied using a unique electrical method. We observed that at ambient temperature, when a discontinuous nanogranular Pd film is on the top of an amorphous carbon film, the electrical conductance of the carbon film decreases in pressurized hydrogen. In comparison, in the absence of this Pd layer, the conductance of the carbon film remains unchanged in pressurized hydrogen. The observed decrease in the current in the Pd/carbon structure is ascribed to the hydrogenation of the dangling carbon bonds and sp{sup 2}-sp{sup 3} transition in the amorphous carbon by the primary spillover hydrogen atoms from Pd nanoclusters.

  13. Ion chromatography detection of fluoride in calcium carbonate.

    PubMed

    Lefler, Jamie E; Ivey, Michelle M

    2011-09-01

    Fluoride in aquatic systems is increasing due to anthropogenic pollution, but little is known about how this fluoride affects organisms that live in and around aquatic habitats. Fluoride can bioaccumulate in structures comprised of calcium carbonate, such as shells and skeletons of both freshwater and saltwater species as diverse as snails, corals, and coccolithophorid algae. In this article, ion chromatography (IC) techniques are developed to detect and quantify fluoride in a matrix of calcium carbonate. Solid samples are dissolved in hydrochloric acid, pretreated to remove the majority of the chloride ions, and then analyzed using IC. With these methods, the 3σ limit of detection is 0.2 mg of fluoride/kg of calcium carbonate. PMID:21859530

  14. Gas desorption during friction of amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Rusanov, A.; Fontaine, J.; Martin, J.-M.; Mogne, T. L.; Nevshupa, R.

    2008-03-01

    Gas desorption induced by friction of solids, i.e. tribodesorption, is one of the numerous physical and chemical phenomena, which arise during friction as result of thermal and structural activation of material in a friction zone. Tribodesorption of carbon oxides, hydrocarbons, and water vapours may lead to significant deterioration of ultra high vacuum conditions in modern technological equipment in electronic, optoelectronic industries. Therefore, knowledge of tribodesorption is crucial for the performance and lifetime of vacuum tribosystems. Diamond-like carbon (DLC) coatings are interesting materials for vacuum tribological systems due to their high wear resistance and low friction. Highly hydrogenated amorphous carbon (a-C:H) films are known to exhibit extremely low friction coefficient under high vacuum or inert environment, known as 'superlubricity' or 'superlow friction'. However, the superlow friction period is not always stable and then tends to spontaneous transition to high friction. It is supposed that hydrogen supply from the bulk to the surface is crucial for establishing and maintaining superlow friction. Thus, tribodesorption can serve also as a new technique to determine the role of gases in superlow friction mechanisms. Desorption of various a-C:H films, deposited by PECVD, ion-beam deposition and deposition using diode system, has been studied by means of ultra-high vacuum tribometer equipped with a mass spectrometer. It was found that in superlow friction period desorption rate was below the detection limit in the 0-85 mass range. However, transition from superlow friction to high friction was accompanied by desorption of various gases, mainly of H2 and CH4. During friction transition, surfaces were heavily damaged. In experiments with DLC films with low hydrogen content tribodesorption was significant during the whole experiment, while low friction was not observed. From estimation of maximum surface temperature during sliding contact it was

  15. Precipitation of calcium carbonate from a calcium acetate and ammonium carbamate batch system

    NASA Astrophysics Data System (ADS)

    Prah, J.; Maček, J.; Dražič, G.

    2011-06-01

    In this paper, we report a novel approach for preparing precipitated calcium carbonate using solutions of ammonium carbamate and calcium acetate as the sources of calcium and carbon dioxide, respectively. Two different concentrations of the starting solutions at three different temperatures (15, 25 and 50 °C) were used for the reaction. The influence of temperature and concentration on the polymorphism and the resulting morphology of calcium carbonate are discussed. The most important parameter for controlling a particular crystal structure and precipitate morphology were the concentrations of the initial solutions. When initial solutions with lower concentrations were used, the crystal form of the precipitate changed with time. Regardless the different polymorphism at different temperatures, after one day only the calcite form was detected in all samples, regardless of at which temperature the samples were prepared. At higher concentrations, pure vaterite or a mixture of vaterite and calcite were present at the beginning of the experiment. After one day, pure vaterite was found in the samples that were prepared at 15 and 25 °C. If calcium carbonate precipitated at 50 °C, the XRD results showed a mixture of calcite and vaterite regardless of the time at which the sample was taken. The morphology of calcium carbonate particles prepared at various conditions changed from calcite cubes to spherical particles of vaterite and aragonite needles. When a low starting concentration was used, the morphology at the initial stage was strongly affected by the temperature at which the experiments were conducted. However, after one day only, cubes were present in all cases at low initial concentrations. In contrast, at high concentrations spherical particles precipitated at all three temperatures at the beginning of the reaction. Spherical particles were made up from smaller particles. Over time, the size of the particles was diminishing due to their disintegration into

  16. Antibacterial activity and ion release of bonding agent containing amorphous calcium phosphate nanoparticles

    PubMed Central

    Chen, Chen; Weir, Michael D.; Cheng, Lei; Lin, Nancy; Lin-Gibson, Sheng; Chow, Laurence C.; Zhou, Xuedong; Xu, Hockin H. K.

    2015-01-01

    Objectives Recurrent caries at the margins is a primary reason for restoration failure. The objectives of this study were to develop bonding agent with the double benefits of antibacterial and remineralizing capabilities, to investigate the effects of NACP filler level and solution pH on Ca and P ion release from adhesive, and to examine the antibacterial and dentin bond properties. Methods Nanoparticles of amorphous calcium phosphate (NACP) and a quaternary ammonium monomer (dimethylaminododecyl methacrylate, DMADDM) were synthesized. Scotchbond Multi-Purpose (SBMP) primer and adhesive served as control. DMADDM was incorporated into primer and adhesive at 5% by mass. NACP was incorporated into adhesive at filler mass fractions of 10%, 20%, 30% and 40%. A dental plaque microcosm biofilm model was used to test the antibacterial bonding agents. Calcium (Ca) and phosphate (P) ion releases from the cured adhesive samples were measured vs. filler level and solution pH of 7, 5.5 and 4. Results Adding 5% DMADDM and 10–40% NACP into bonding agent, and water-aging for 28 days, did not affect dentin bond strength, compared to SBMP control at 1 day (p > 0.1). Adding DMADDM into bonding agent substantially decreased the biofilm metabolic activity and lactic acid production. Total microorganisms, total streptococci, and mutans streptococci were greatly reduced for bonding agents containing DMADDM. Increasing NACP filler level from 10% to 40% in adhesive increased the Ca and P ion release by an order of magnitude. Decreasing solution pH from 7 to 4 increased the ion release from adhesive by 6–10 folds. Significance Bonding agents containing antibacterial DMADDM and remineralizer NACP were formulated to have Ca and P ion release, which increased with NACP filler level from 10% to 40% in adhesive. NACP adhesive was “smart” and dramatically increased the ion release at cariogenic pH 4, when these ions would be most-needed to inhibit caries. Therefore, bonding agent

  17. A Chemical Template for Synthesis of Molecular Sheets of Calcium Carbonate

    PubMed Central

    Rianasari, Ina; Benyettou, Farah; Sharma, Sudhir Kumar; Blanton, Thomas; Kirmizialtin, Serdal; Jagannathan, Ramesh

    2016-01-01

    Inspired by the discovery of graphene and its unique properties, we focused our research to develop a scheme to create nacre like lamellar structures of molecular sheets of CaCO3 interleaved with an organic material, namely carbon. We developed a facile, chemical template technique, using a formulation of poly(acrylic) acid (PAA) and calcium acetate to create lamellar stacks of single crystal sheets of CaCO3, with a nominal thickness of 17 Å, the same as a unit-cell dimension for calcite (c–axis = 17.062 Å), interleaved with amorphous carbon with a nominal thickness of 8 Å. The strong binding affinity between carboxylate anions and calcium cations in the formulation was used as a molecular template to guide CaCO3 crystallization. Computational modeling of the FTIR spectra showed good agreement with experimental data and confirmed that calcium ions are bridged between polymer chains, resulting in a net-like polymer structure. The process readily lends itself to explore the feasibility of creating molecular sheets of other important inorganic materials and potentially find applications in many fields such as super capacitors and “low k di-electric” systems. PMID:27145699

  18. A Chemical Template for Synthesis of Molecular Sheets of Calcium Carbonate.

    PubMed

    Rianasari, Ina; Benyettou, Farah; Sharma, Sudhir Kumar; Blanton, Thomas; Kirmizialtin, Serdal; Jagannathan, Ramesh

    2016-01-01

    Inspired by the discovery of graphene and its unique properties, we focused our research to develop a scheme to create nacre like lamellar structures of molecular sheets of CaCO3 interleaved with an organic material, namely carbon. We developed a facile, chemical template technique, using a formulation of poly(acrylic) acid (PAA) and calcium acetate to create lamellar stacks of single crystal sheets of CaCO3, with a nominal thickness of 17 Å, the same as a unit-cell dimension for calcite (c-axis = 17.062 Å), interleaved with amorphous carbon with a nominal thickness of 8 Å. The strong binding affinity between carboxylate anions and calcium cations in the formulation was used as a molecular template to guide CaCO3 crystallization. Computational modeling of the FTIR spectra showed good agreement with experimental data and confirmed that calcium ions are bridged between polymer chains, resulting in a net-like polymer structure. The process readily lends itself to explore the feasibility of creating molecular sheets of other important inorganic materials and potentially find applications in many fields such as super capacitors and "low k di-electric" systems. PMID:27145699

  19. A Chemical Template for Synthesis of Molecular Sheets of Calcium Carbonate

    NASA Astrophysics Data System (ADS)

    Rianasari, Ina; Benyettou, Farah; Sharma, Sudhir Kumar; Blanton, Thomas; Kirmizialtin, Serdal; Jagannathan, Ramesh

    2016-05-01

    Inspired by the discovery of graphene and its unique properties, we focused our research to develop a scheme to create nacre like lamellar structures of molecular sheets of CaCO3 interleaved with an organic material, namely carbon. We developed a facile, chemical template technique, using a formulation of poly(acrylic) acid (PAA) and calcium acetate to create lamellar stacks of single crystal sheets of CaCO3, with a nominal thickness of 17 Å, the same as a unit-cell dimension for calcite (c–axis = 17.062 Å), interleaved with amorphous carbon with a nominal thickness of 8 Å. The strong binding affinity between carboxylate anions and calcium cations in the formulation was used as a molecular template to guide CaCO3 crystallization. Computational modeling of the FTIR spectra showed good agreement with experimental data and confirmed that calcium ions are bridged between polymer chains, resulting in a net-like polymer structure. The process readily lends itself to explore the feasibility of creating molecular sheets of other important inorganic materials and potentially find applications in many fields such as super capacitors and “low k di-electric” systems.

  20. Calcium supplements

    MedlinePlus

    ... TYPES OF CALCIUM SUPPLEMENTS Forms of calcium include: Calcium carbonate: Over-the-counter (OTC) antacid products, such as Tums and Rolaids, contain calcium carbonate. These sources of calcium do not cost much. ...

  1. Distribution of calcium carbonate in desert soils: A model

    SciTech Connect

    Mayer, L.; McFadden, L.D.; Harden, J.W.

    1988-04-01

    A model that describes the distribution of calcium carbonate in desert soils as a function of dust flux, time, climate, and other soil-forming factors shows which factors most strongly influence the accumulation of carbonate and can be used to evaluate carbonate-based soil age estimates or paleoclimatic reconstructions. Models for late Holocene soils have produced carbonate distributions that are very similar to those of well-dated soils in New Mexico and southern California. These results suggest that (1) present climate is a fair representation of late Holocene climate, (2) carbonate dust flux can be approximated by its Holocene rate, and (3) changes in climate and/or dust flux at the end of the Pleistocene effected profound and complex changes in soil carbonate distributions. Both higher carbonate dust flux and greater effective precipitation are required during the latest Pleistocene-early Holocene to explain carbonate distributions in latest Pleistocene soils. 21 refs., 4 figs., 1 tab.

  2. Electromagnetic Wave Absorbing Properties of Amorphous Carbon Nanotubes

    PubMed Central

    Zhao, Tingkai; Hou, Cuilin; Zhang, Hongyan; Zhu, Ruoxing; She, Shengfei; Wang, Jungao; Li, Tiehu; Liu, Zhifu; Wei, Bingqing

    2014-01-01

    Amorphous carbon nanotubes (ACNTs) with diameters in the range of 7–50 nm were used as absorber materials for electromagnetic waves. The electromagnetic wave absorbing composite films were prepared by a dip-coating method using a uniform mixture of rare earth lanthanum nitrate doped ACNTs and polyvinyl chloride (PVC). The microstructures of ACNTs and ACNT/PVC composites were characterized using transmission electron microscope and X-ray diffraction, and their electromagnetic wave absorbing properties were measured using a vector-network analyzer. The experimental results indicated that the electromagnetic wave absorbing properties of ACNTs are superior to multi-walled CNTs, and greatly improved by doping 6 wt% lanthanum nitrate. The reflection loss (R) value of a lanthanum nitrate doped ACNT/PVC composite was −25.02 dB at 14.44 GHz, and the frequency bandwidth corresponding to the reflector loss at −10 dB was up to 5.8 GHz within the frequency range of 2–18 GHz. PMID:25007783

  3. Glutamate detection by amino functionalized tetrahedral amorphous carbon surfaces.

    PubMed

    Kaivosoja, Emilia; Tujunen, Noora; Jokinen, Ville; Protopopova, Vera; Heinilehto, Santtu; Koskinen, Jari; Laurila, Tomi

    2015-08-15

    In this paper, a novel amperometric glutamate biosensor with glutamate oxidase (GlOx) immobilized directly on NH2 functionalized, platinum doped tetrahedral amorphous carbon (ta-C) film, has been successfully developed. First, we demonstrate that direct GlOx immobilization is more effective on amino-groups than on carboxyl- or hydroxyl-groups. Second, we show that anodizing and plasma treatments increase the amount of nitrogen and the proportion of protonated amino groups relative to amino groups on the aminosilane coating, which subsequently results in an increased amount of active GlOx on the surface. This effect, however, is found to be unstable due to unstable electrostatic interactions between GlOx and NH3(+). We demonstrate the detection of glutamate in the concentration range of 10µM-1mM using the NH2 functionalized Pt doped ta-C surface. The biosensor showed high sensitivity (2.9nA μM(-1)cm(-2)), low detection limit (10μM) and good storage stability. The electrode response to glutamate was linear in the concentrations ranging from 10µM to 500µM. In conclusion, the study shows that GlOx immobilization is most effective on aminosilane treated ta-C surface without any pre-treatments and the fabricated sensor structure is able to detect glutamate in the micromolar range. PMID:25966399

  4. Controlled epitaxial graphene growth within removable amorphous carbon corrals

    SciTech Connect

    Palmer, James; Hu, Yike; Hankinson, John; Guo, Zelei; Heer, Walt A. de; Kunc, Jan; Berger, Claire

    2014-07-14

    We address the question of control of the silicon carbide (SiC) steps and terraces under epitaxial graphene on SiC and demonstrate amorphous carbon (aC) corrals as an ideal method to pin SiC surface steps. aC is compatible with graphene growth, structurally stable at high temperatures, and can be removed after graphene growth. For this, aC is first evaporated and patterned on SiC, then annealed in the graphene growth furnace. There at temperatures above 1200 °C, mobile SiC steps accumulate at the aC corral that provide effective step flow barriers. Aligned step free regions are thereby formed for subsequent graphene growth at temperatures above 1330 °C. Atomic force microscopy imaging supports the formation of step-free terraces on SiC with the step morphology aligned to the aC corrals. Raman spectroscopy indicates the presence of good graphene sheets on the step-free terraces.

  5. Controlled epitaxial graphene growth within removable amorphous carbon corrals

    NASA Astrophysics Data System (ADS)

    Palmer, James; Kunc, Jan; Hu, Yike; Hankinson, John; Guo, Zelei; Berger, Claire; de Heer, Walt A.

    2014-07-01

    We address the question of control of the silicon carbide (SiC) steps and terraces under epitaxial graphene on SiC and demonstrate amorphous carbon (aC) corrals as an ideal method to pin SiC surface steps. aC is compatible with graphene growth, structurally stable at high temperatures, and can be removed after graphene growth. For this, aC is first evaporated and patterned on SiC, then annealed in the graphene growth furnace. There at temperatures above 1200 °C, mobile SiC steps accumulate at the aC corral that provide effective step flow barriers. Aligned step free regions are thereby formed for subsequent graphene growth at temperatures above 1330 °C. Atomic force microscopy imaging supports the formation of step-free terraces on SiC with the step morphology aligned to the aC corrals. Raman spectroscopy indicates the presence of good graphene sheets on the step-free terraces.

  6. Mechanical and acid neutralizing properties and bacteria inhibition of amorphous calcium phosphate dental nanocomposite

    PubMed Central

    Moreau, Jennifer L.; Sun, Limin; Chow, Laurence C.; Xu, Hockin H. K.

    2012-01-01

    Dental composites do not hinder bacteria colonization and plaque formation. Caries at the restoration margins is a frequent reason for replacement of existing restorations, which accounts for 50 to 70% of all restorations. The objectives of this study were to examine the filler level effect on nanocomposite containing nanoparticles of amorphous calcium phosphate (NACP) and investigate the load-bearing and acid-neutralizing properties and bacteria inhibition. NACP with 116-nm particle size were synthesized via a spray-drying technique and incorporated into a resin. Flexural strength of nanocomposite with 10 to 30% NACP fillers matched the strength of a commercial hybrid composite (p > 0.1). Nanocomposite with 40% NACP matched the strength of a microfill composite, which was 2-fold that of a resin-modified glass ionomer. Nanocomposite with 40% NACP neutralized a lactic acid solution of pH 4 by rapidly increasing the pH to 5.69 in 10 min. In contrast, the commercial controls had pH staying at near 4. Using Streptoccocus mutans, an agar disk-diffusion test showed no inhibition zone for commercial controls. In contrast, the inhibition zone was (2.5 ± 0.7) mm for nanocomposite with 40% NACP. Crystal violet staining showed that S. mutans coverage on nanocomposite was 1/4 that on commercial composite. In conclusion, novel calcium–phosphate nanocomposite matched the mechanical properties of commercial composite and rapidly neutralized lactic acid of pH 4. The nanocomposite appeared to moderately reduce the S. mutans growth, and further study is needed to obtain strong antimicrobial properties. The new nanocomposite may have potential to reduce secondary caries and restoration fracture, two main challenges facing tooth cavity restorations. PMID:21504057

  7. Protective effect of casein phosphopeptide-amorphous calcium phosphate on enamel erosion: Atomic force microscopy studies.

    PubMed

    Ceci, Matteo; Mirando, Maria; Beltrami, Riccardo; Chiesa, Marco; Poggio, Claudio

    2015-01-01

    The aim of this study was to investigate the in vitro effect of a casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) paste (GC Tooth Mousse- TM, GC Corporation, Tokyo, Japan) on preventing enamel erosion, by using Atomic Force Microscopy (AFM). 30 human incisors, were equally assigned to 6 groups: intact enamel, enamel + soft drink, enamel + TM, enamel + TM + soft drink, enamel + soft drink + TM, enamel + soft drink + TM + soft drink. Specimens were observed through atomic force microscopy (AFM). The most common topographical parameters were determined, such as the surface roughness (Rrms ). The use of soft drink on intact enamel has roughened the surface of the sample. The application of the CPP-ACP paste on non-treated enamel made the surface smoother. A significant decrease in roughness was seen after remineralization with CPP-ACP paste. Significant differences were recorded when comparing softened enamel with softened enamel remineralized with CPP-ACP paste. Comparing eroded enamel with demineralized/remineralized specimens, the application of a CPP-ACP paste leads to a significant reduction in roughness values. AFM images of enamel surface treated with CPP-ACP resulted in less morphological changes of the tooth substrate when compared with the only eroded enamel surface morphology; thus, indicating that CPP-ACP paste promoted remineralization. Specimens' surface roughness remained similar regardless that the protective agent is used before or after exposure to coke or between two demineralizing cycles. The results confirmed the effectiveness of the CPP-ACP paste on preventing enamel erosion produced by soft drinks. PMID:25917931

  8. ADHESION OF AMORPHOUS CALCIUM PHOSPHATE COMPOSITES BONDED TO DENTIN: A STUDY IN FAILURE MODALITY

    PubMed Central

    O’Donnell, J.N.R.; Schumacher, G.E.; Antonucci, J.M.; Skrtic, D.

    2009-01-01

    Aims As a bioactive filler capable of remineralizing tooth structures, the main disadvantage of as-made amorphous calcium phosphate (am-ACP) are its large agglomerates. The objective of this study was to mill ACP, and compare the adhesive strength to dentin, work to fracture, and failure modes of both groups to glass-filled composites and one commercial compomer after 24 h, 1 week, 1, 3 and 6 months of exposure to simulated saliva solution (SLS). Flat dentin surfaces were acid-etched, primed, and photopolymerized. Composites were applied, photo-cured, and debonded in shear. The resin used in each composite was identical: ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate and methacryloxyethyl phthalate. Fillers consisted of am-ACP and milled ACP (m-ACP), and a strontium-containing glass (Sr-glass) at respective mass fractions of (40, 60, and 75) %. Findings 90 % of the fracture surfaces in this study showed adhesive failure, with most of these occurring at the dentin/primer interface. 52 % of failures after 24 h immersion occurred at the primer/composite interface. After six months of SLS exposure, 80 % of specimens failed at the dentin/primer interface, with a 42 % overall reduction in bond strength. Conclusions Milled ACP composites showed initial mechanical advantages over am-ACP composites and the compomer, and produced a higher incidence of a failure mode consistent with stronger adhesion. Evidence is provided which suggests that milled ACP composites may offer enhanced potential in clinical bonding applications. PMID:19107798

  9. AMORPHOUS CALCIUM PHOSPHATE COMPOSITES AND THEIR EFFECT ON COMPOSITE-ADHESIVE-DENTIN BONDING

    PubMed Central

    Antonucci, J.M.; O’Donnell, J.N.R.; Schumacher, G.E.; Skrtic, D.

    2009-01-01

    This study evaluates the bond strength and related properties of photo-polymerizable, remineralizing amorphous calcium phosphate (ACP) polymeric composite-adhesive systems to dentin after various periods of aqueous aging at 37 °C. An experimental ACP base and lining composite was made from a photo-activated resin comprising 2,2-bis[p-(2’-hydroxy-3’-methacryloxypropoxy)phenyl]propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), 2-hydroxyethyl methacrylate (HEMA) and zirconyl dimethacrylate (ZrDMA); designated BTHZ. An experimental orthodontic composite was formulated from a photo-activated resin comprising ethoxylated bisphenol A dimethacrylate (EBPADMA), TEGDMA, HEMA and methacryloxyethyl phthalate (MEP); designated ETHM. In both composite series three fillers were compared: 1) freshly precipitated zirconium-modified ACP freshly precipitated (as-prepared Zr-ACP), 2) milled Zr-ACP and 3) an ion-leachable fluoride glass. In addition to the shear bond strength (SBS), work to fracture and failure modes of the orthodontic composites were determined. The SBS of the base and lining ACP composites appeared unaffected by filler type or immersion time. In the orthodontic ACP composite series, milled ACP composites showed initial mechanical advantages over as-prepared ACP composites, and produced higher incidence of a failure mode consistent with stronger adhesion. After six months of aqueous exposure, 80 % of specimens failed at the dentin-primer interface, with a 42 % overall reduction in bond strength. BTHZ and ETHM based ACP composites are potentially effective anti-demineralizing-remineralizing agents with possible clinical utility as protective base-liners and orthodontic cements, respectively. The analysis of the bond strength and failure modalities suggests that milled ACP composites may offer greater potential in clinical applications. PMID:19696914

  10. In vitro remineralization of enamel by polymeric amorphous calcium phosphate composite: Quantitative micro-radiographic study

    PubMed Central

    Langhorst, S.E.; O'Donnell, J.N.R.; Skrtic, D.

    2009-01-01

    Objective: This study explores the efficacy of an experimental orthodontic amorphous calcium phosphate (ACP) composite to remineralize in vitro subsurface enamel lesions microradiographically similar to those seen in early caries. Methods: Lesions were artificially created in extracted human molars. Single tooth sections a minimum of 120 μm thick were cut and individually placed in holders exposing only the carious enamel surface. The exposed surfaces were either left untreated (control) or coated with a 1 mm thick layer of the experimental ACP composite (mass fraction 40 % zirconiahybridized ACP and 60 % photo-activated resin), or a commercial fluoride-releasing orthodontic cement. The composite-coated sections were then photo-cured and microradiographic images were taken of all three groups of specimens before the treatment. Specimens were then cyclically immersed in demineralizing and remineralizing solutions for one month at 37 °C to simulate the pH changes occurring in the oral environment. Microradiographs of all specimens were taken before and after treatment. Results: Quantitative digital image analysis of matched areas from the contact microradiographs taken before and after treatment indicated higher mineral recovery with ACP composites compared to the commercial orthodontic F-releasing cement (14.4 % vs. 4.3 %, respectively), while the control specimens showed an average of 55.4 % further demineralization. Significance: Experimental ACP composite efficiently established mineral ion transfer throughout the body of the lesions and restored the mineral lost due to acid attack. It can be considered a useful adjuvant for the control of caries in orthodontic applications. PMID:19215975

  11. Random vs realistic amorphous carbon models for high resolution microscopy and electron diffraction

    SciTech Connect

    Ricolleau, C. Alloyeau, D.; Le Bouar, Y.; Amara, H.; Landon-Cardinal, O.

    2013-12-07

    Amorphous carbon and amorphous materials in general are of particular importance for high resolution electron microscopy, either for bulk materials, generally covered with an amorphous layer when prepared by ion milling techniques, or for nanoscale objects deposited on amorphous substrates. In order to quantify the information of the high resolution images at the atomic scale, a structural modeling of the sample is necessary prior to the calculation of the electron wave function propagation. It is thus essential to be able to reproduce the carbon structure as close as possible to the real one. The approach we propose here is to simulate a realistic carbon from an energetic model based on the tight-binding approximation in order to reproduce the important structural properties of amorphous carbon. At first, we compare this carbon with the carbon obtained by randomly generating the carbon atom positions. In both cases, we discuss the limit thickness of the phase object approximation. In a second step, we show the influence of both carbons models on (i) the contrast of Cu, Ag, and Au single atoms deposited on carbon and (ii) the determination of the long-range order parameter in CoPt bimetallic nanoalloys.

  12. Tribological studies of amorphous hydrogenated carbon films in a vacuum, spacelike environment

    NASA Technical Reports Server (NTRS)

    Miyoshi, Kazuhisa

    1991-01-01

    Recent work on the adhesion and friction properties of plasma-deposited amorphous hydrogenated carbon films and their dependence on preparation conditions are reviewed. The results of the study indicate that plasma deposition enables one to deposit a variety of amorphous hydrogenated carbon (a-C:H) exhibiting diamondlike friction behavior. The plasma-deposited a-C:H films can be effectively used as hard lubricating films on ceramic materials such as silicon nitride in vacuum.

  13. CALCIUM CARBONATE DISSOLUTION RATE IN LIMESTONE CONTRACTORS

    EPA Science Inventory

    The rate of carbonate mineral dissolution from limestone was studied using a rotating disk apparatus and samples of limestone of varied composition. he purpose of this study was to determine the effect of limestone composition on the kinetics of carbonate mineral dissolution. he ...

  14. CALCIUM CARBONATE DISSOLUTION RATE IN LIMESTONE CONTACTORS

    EPA Science Inventory

    The rate of carbonate mineral dissolution from limestone was studied using a rotating disk apparatus and samples of limestone of varied composition. The purpose of this study was to determine the effect of limestone composition on the kinetics of carbonate mineral dissolution. Th...

  15. Calcium carbonate polymorph control using droplet-based microfluidics.

    PubMed

    Yashina, Alexandra; Meldrum, Fiona; Demello, Andrew

    2012-06-01

    Calcium carbonate (CaCO(3)) is one of the most abundant minerals and of high importance in many areas of science including global CO(2) exchange, industrial water treatment energy storage, and the formation of shells and skeletons. Industrially, calcium carbonate is also used in the production of cement, glasses, paints, plastics, rubbers, ceramics, and steel, as well as being a key material in oil refining and iron ore purification. CaCO(3) displays a complex polymorphic behaviour which, despite numerous experiments, remains poorly characterised. In this paper, we report the use of a segmented-flow microfluidic reactor for the controlled precipitation of calcium carbonate and compare the resulting crystal properties with those obtained using both continuous flow microfluidic reactors and conventional bulk methods. Through combination of equal volumes of equimolar aqueous solutions of calcium chloride and sodium carbonate on the picoliter scale, it was possible to achieve excellent definition of both crystal size and size distribution. Furthermore, highly reproducible control over crystal polymorph could be realised, such that pure calcite, pure vaterite, or a mixture of calcite and vaterite could be precipitated depending on the reaction conditions and droplet-volumes employed. In contrast, the crystals precipitated in the continuous flow and bulk systems comprised of a mixture of calcite and vaterite and exhibited a broad distribution of sizes for all reaction conditions investigated. PMID:22655005

  16. Insights into the fracture mechanisms and strength of amorphous and nanocomposite carbon.

    PubMed

    Fyta, M G; Remediakis, I N; Kelires, P C; Papaconstantopoulos, D A

    2006-05-12

    Tight-binding molecular dynamics simulations shed light into the fracture mechanisms and the ideal strength of tetrahedral amorphous carbon and of nanocomposite carbon containing diamond crystallites, two of the hardest materials. It is found that fracture in the nanocomposites, under tensile or shear load, occurs intergrain and so their ideal strength is similar to the pure amorphous phase. The onset of fracture takes place at weakly bonded sites in the amorphous matrix. On the other hand, the nanodiamond inclusions significantly enhance the elastic moduli, which approach those of diamond. PMID:16712372

  17. Drug loading into porous calcium carbonate microparticles by solvent evaporation.

    PubMed

    Preisig, Daniel; Haid, David; Varum, Felipe J O; Bravo, Roberto; Alles, Rainer; Huwyler, Jörg; Puchkov, Maxim

    2014-08-01

    Drug loading into porous carriers may improve drug release of poorly water-soluble drugs. However, the widely used impregnation method based on adsorption lacks reproducibility and efficiency for certain compounds. The aim of this study was to evaluate a drug-loading method based on solvent evaporation and crystallization, and to investigate the underlying drug-loading mechanisms. Functionalized calcium carbonate (FCC) microparticles and four drugs with different solubility and permeability properties were selected as model substances to investigate drug loading. Ibuprofen, nifedipine, losartan potassium, and metronidazole benzoate were dissolved in acetone or methanol. After dispersion of FCC, the solvent was removed under reduced pressure. For each model drug, a series of drug loads were produced ranging from 25% to 50% (w/w) in steps of 5% (w/w). Loading efficiency was qualitatively analyzed by scanning electron microscopy (SEM) using the presence of agglomerates and drug crystals as indicators of poor loading efficiency. The particles were further characterized by mercury porosimetry, specific surface area measurements, differential scanning calorimetry, and USP2 dissolution. Drug concentration was determined by HPLC. FCC-drug mixtures containing equivalent drug fractions but without specific loading strategy served as reference samples. SEM analysis revealed high efficiency of pore filling up to a drug load of 40% (w/w). Above this, agglomerates and separate crystals were significantly increased, indicating that the maximum capacity of drug loading was reached. Intraparticle porosity and specific surface area were decreased after drug loading because of pore filling and crystallization on the pore surface. HPLC quantification of drugs taken up by FCC showed only minor drug loss. Dissolution rate of FCC loaded with metronidazole benzoate and nifedipine was faster than the corresponding FCC-drug mixtures, mainly due to surface enlargement, because only small

  18. 40 CFR 415.300 - Applicability; description of the calcium carbonate production subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... calcium carbonate production subcategory. 415.300 Section 415.300 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Calcium Carbonate Production Subcategory § 415.300 Applicability; description of the calcium carbonate production subcategory. The provisions of this subpart are applicable to...

  19. In situ X-ray pair distribution function analysis of accelerated carbonation of a synthetic calcium-silicate-hydrate gel

    SciTech Connect

    Morandeau, Antoine E.; White, Claire E.

    2015-04-21

    Calcium–silicate–hydrate (C–S–H) gel is the main binder component in hydrated ordinary Portland cement (OPC) paste, and is known to play a crucial role in the carbonation of cementitious materials, especially for more sustainable alternatives containing supplementary cementitious materials. However, the exact atomic structural changes that occur during carbonation of C–S–H gel remain unknown. Here, we investigate the local atomic structural changes that occur during carbonation of a synthetic calcium–silicate–hydrate gel exposed to pure CO₂ vapour, using in situ X-ray total scattering measurements and subsequent pair distribution function (PDF) analysis. By analysing both the reciprocal and real-space scattering data as the C–S–H carbonation reaction progresses, all phases present during the reaction (crystalline and non-crystalline) have been identified and quantified, with the results revealing the emergence of several polymorphs of crystalline calcium carbonate (vaterite and calcite) in addition to the decalcified C–S–H gel. Furthermore, the results point toward residual calcium being present in the amorphous decalcified gel, potentially in the form of an amorphous calcium carbonate phase. As a result of the quantification process, the reaction kinetics for the evolution of the individual phases have been obtained, revealing new information on the rate of growth/dissolution for each phase associated with C–S–H gel carbonation. Moreover, the investigation reveals that the use of real space diffraction data in the form of PDFs enables more accurate determination of the phases that develop during complex reaction processes such as C–S–H gel carbonation in comparison to the conventional reciprocal space Rietveld analysis approach.

  20. Electrodeposition and characterization of Pd nanoparticles doped amorphous hydrogenated carbon films

    NASA Astrophysics Data System (ADS)

    Yu, Yuanlie; Zhang, Junyan

    2009-11-01

    Palladium (0) nanoparticles incorporated hydrogenated amorphous carbon (Pd/a-C:H) films were synthesized on single crystal silicon (100) substrates by electrochemical deposition route using methanol and camphor as carbon source, and Pd nanoparticles as dopant. The characterization results indicate that Pd nanocrystalline particles with diameter in the range of 1-5 nm dispersed in the amorphous carbon matrix. Compared with pure a-C:H films, the introduction of Pd nanoparticles didn't change the structure of carbon films. At the end, the growth mechanism of the Pd/a-C:H composite films was discussed.

  1. Superconductivity and unusual magnetic behavior in amorphous carbon

    NASA Astrophysics Data System (ADS)

    Felner, Israel

    2014-03-01

    Traces of superconductivity (SC) at elevated temperatures (up to 65 K) were observed by magnetic measurements in three different inhomogeneous sulfur doped amorphous carbon (a-C) systems: (a) in commercial and (b) synthesized powders and (c) in a-C thin films. (a) Studies performed on a commercial (a-C) powder, which contains 0.21% sulfur, revealed traces of non-percolated superconducting phases below T c = 65 K. The SC volume fraction is enhanced by the sulfur doping. (b) The a-C powder obtained by pyrolytic decomposition of sucrose did not show any sign of SC above 5 K. This powder was mixed with sulfur and synthesized at 400 °C (a-CS). The inhomogeneous products obtained show traces of SC phases at T c = 17 and 42 K. (c) Non-superconducting composite a-C-W thin films were grown by electron-beam induced deposition. SC emerged at T c = 34.4 K only after heat treatment with sulfur. Other parts of the pyrolytic a-CS powder show unusual magnetic features. (i) Pronounced irreversible peaks around 55-75 K appear in the first zero-field-cooled (ZFC) sweep only. Their origin is not known. (ii) Unexpectedly, these peaks are totally suppressed in the second ZFC runs measured a few minutes later. (iii) Around the peak position the field-cooled (FC) curves cross the ZFC plots (ZFC > FC). These peculiar magnetic observations are also ascribed to an a-CS powder prepared from the commercial a-C powder and are connected to each other. All SC and magnetic phenomena observed are intrinsic properties of the sulfur doped a-C materials. It is proposed that the a-CS systems behave similarly to well-known high T c curates and/or pnictides in which SC emerges from magnetic states.

  2. Single walled carbon nanotube network—Tetrahedral amorphous carbon composite film

    NASA Astrophysics Data System (ADS)

    Iyer, Ajai; Kaskela, Antti; Johansson, Leena-Sisko; Liu, Xuwen; Kauppinen, Esko I.; Koskinen, Jari

    2015-06-01

    Single walled carbon nanotube network (SWCNTN) was coated by tetrahedral amorphous carbon (ta-C) using a pulsed Filtered Cathodic Vacuum Arc system to form a SWCNTN—ta-C composite film. The effects of SWCNTN areal coverage density and ta-C coating thickness on the composite film properties were investigated. X-Ray photoelectron spectroscopy measurements prove the presence of high quality sp3 bonded ta-C coating on the SWCNTN. Raman spectroscopy suggests that the single wall carbon nanotubes (SWCNTs) forming the network survived encapsulation in the ta-C coating. Nano-mechanical testing suggests that the ta-C coated SWCNTN has superior wear performance compared to uncoated SWCNTN.

  3. Single walled carbon nanotube network—Tetrahedral amorphous carbon composite film

    SciTech Connect

    Iyer, Ajai Liu, Xuwen; Koskinen, Jari; Kaskela, Antti; Kauppinen, Esko I.; Johansson, Leena-Sisko

    2015-06-14

    Single walled carbon nanotube network (SWCNTN) was coated by tetrahedral amorphous carbon (ta-C) using a pulsed Filtered Cathodic Vacuum Arc system to form a SWCNTN—ta-C composite film. The effects of SWCNTN areal coverage density and ta-C coating thickness on the composite film properties were investigated. X-Ray photoelectron spectroscopy measurements prove the presence of high quality sp{sup 3} bonded ta-C coating on the SWCNTN. Raman spectroscopy suggests that the single wall carbon nanotubes (SWCNTs) forming the network survived encapsulation in the ta-C coating. Nano-mechanical testing suggests that the ta-C coated SWCNTN has superior wear performance compared to uncoated SWCNTN.

  4. Physico-chemical studies of amorphous carbon nanotubes synthesized at low temperature

    SciTech Connect

    Tan, Kim Han; Ahmad, Roslina; Leo, Bey Fen; Yew, Ming Chian; Ang, Bee Chin; Johan, Mohd Rafie

    2012-08-15

    Highlights: ► Amorphous carbon nanotubes are successfully produced via a simple method at low temperature. ► Nanotubes in straight morphologies with open ends. ► Acid treatment increases the extent of amorphous for nanotubes. ► Amorphous nanotubes exhibit phenomena of π plasmon absorbance and possess higher bandgap. -- Abstract: This work provides better understanding on the nature of amorphous carbon nanotubes, which are synthesized via a simple chemical route. Amorphous carbon nanotubes (α-CNTs) are successfully synthesized by heating a mixture of ferrocene and ammonium chloride at temperature as low as 200 °C and are treated with hydrochloric acid. Transmission and field emission scanning electron microscopy techniques are performed to examine the morphology and dimension of the samples. X-ray diffraction tests confirm the amorphous structure of the nanotubes. The Fourier transform infrared spectroscopy and Raman studies indicate that the treated α-CNTs consist of many defective walls and are more amorphous compared with the untreated α-CNTs. Ultraviolet–visible absorption studies reveal that the untreated and treated α-CNTs exhibit plasmon absorbance with high bandgaps of 4 eV and 4.35 eV, respectively.

  5. CALCULATING THE PH OF CALCIUM CARBONATE SATURATION

    EPA Science Inventory

    Two new expressions for the pH of saturation (pH subs) were derived. One is a simplified equation developed from an aqueous carbonate equilibrium system in which correction for ionic strength was considered. The other is a more accurate quadratic formula that involves computerize...

  6. Structural evolutions in polymer-derived carbon-rich amorphous silicon carbide.

    PubMed

    Wang, Kewei; Ma, Baisheng; Li, Xuqin; Wang, Yiguang; An, Linan

    2015-01-29

    The detailed structural evolutions in polycarbosilane-derived carbon-rich amorphous SiC were investigated semiquantitatively by combining experimental and analytical methods. It is revealed that the material is comprised of a Si-containing matrix phase and a free-carbon phase. The matrix phase is amorphous, comprised of SiC4 tetrahedra, SiCxOx-4 tetrahedra, and Si-C-C-Si/Si-C-H defects. With increasing pyrolysis temperature, the amorphous matrix becomes more ordered, accompanied by a transition from SiC2O2 to SiCO3. The transition was completed at 1250 °C, where the matrix phase started to crystallize by forming a small amount of β-SiC. The free-carbon phase was comprised of carbon nanoclusters and C-dangling bonds. Increasing pyrolysis temperature led to the transition of the free carbon from amorphous carbon to nanocrystalline graphite. The size of the carbon clusters decreased first and then increased, while the C-dangling bond content decreased continuously. The growth of carbon clusters was attributed to Ostwald ripening and described using a two-dimensional grain growth model. The calculated activation energy suggested that the decrease in C-dangling bonds is directly related to the lateral growth of the carbon clusters. PMID:25490064

  7. Ion beam deposition of amorphous carbon films with diamond like properties

    NASA Technical Reports Server (NTRS)

    Angus, John C.; Mirtich, Michael J.; Wintucky, Edwin G.

    1982-01-01

    Carbon films were deposited on silicon, quartz, and potassium bromide substrates from an ion beam. Growth rates were approximately 0.3 micron/hour. The films were featureless and amorphous and contained only carbon and hydrogen in significant amounts. The density and carbon/hydrogen ratio indicate the film is a hydrogen deficient polymer. One possible structure, consistent with the data, is a random network of methylene linkages and tetrahedrally coordinated carbon atoms.

  8. Tuning calcium carbonate growth through physical confinement and templating with amyloid-like polypeptide aggregates

    NASA Astrophysics Data System (ADS)

    Colaco, Martin Francis

    The creation of useful composite materials requires precise control of the interface between the components in order to tune the overall shape and material properties. Despite the current research into nanotechnology, our ability to create materials with nanoscale precision is nascent. However, nature has a paradigm for the creation of finely structured composites under mild conditions called biomineralization. Through control of protein template assembly, solution conditions, and physical confinement, organisms are able to create useful optical and structural materials, such as bones, teeth, and mollusk shells. The objective of this thesis is to elucidate the importance of these various controls in synthetic systems to further our ability to create nanostructured materials. We begin by examining the formation of self-assembled monolayers (SAMs) of organosilanes on silica oxides. The formation of functionalized surfaces can help control the mineralization of amorphous or crystalline calcium carbonate. Long-chained organosilanes organize on surfaces to form dense, solid-like films, with the terminal groups determining the hydrophobicity and stereochemistry of the film. Our work has shown that uniform hydrophobic and hydrophilic films can be formed by using cleaned silica over glass or mica and through a vapor phase reaction over a liquid one. Additionally, we showed that mixed SAMs with phase-separated domains could be created through the selection of organosilanes and reaction conditions. We have built on these functionalized surfaces through the use of microfabrication and a gas permeable polymer to create three-dimensionally confined microcrystallizers. Other researchers have shown that one-dimensional confinement with a multi-functional surface (patterned with a small nucleating ordered region in a disordered SAM) can stabilize the creation of an amorphous calcium carbonate film before a single, large, micropatterned crystal is grown. Our work has determined

  9. Deposition of calcium carbonate films by a polymer-induced liquid-precursor (PILP) process

    NASA Astrophysics Data System (ADS)

    Gower, Laurie B.; Odom, Damian J.

    2000-03-01

    A polypeptide additive has been used to transform the solution crystallization of calcium carbonate to a solidification process of a liquid-phase mineral precursor. In situ observations reveal that polyaspartate induces liquid-liquid phase separation of droplets of a mineral precursor. The droplets deposit on the substrate and coalesce to form a coating, which then solidifies into calcitic tablets and films. Transition bars form during the amorphous to crystalline transition, leading to sectorization of calcite tablets, and the defect textures and crystal morphologies are atypical of solution grown crystals. The formation of nonequilibrium crystal morphologies using an acidic polypeptide may have implications in the field of biomineralization, and the environmentally friendly aspects of this polymer-induced liquid-precursor (PILP) process may offer new techniques for aqueous-based processing of ceramic films, coatings, and particulates.

  10. Mechanical properties of amorphous hard carbon films prepared by cathodic arc deposition

    SciTech Connect

    Anders, S.; Anders, A.; Brown, I.G.

    1995-04-01

    Cathodic arc deposition combined with macroparticle filtering of the plasma is an efficient and versatile method for the deposition of amorphous hard carbon films of high quality. The film properties can be tailored over a broad range by varying the energy of the carbon ions incident upon the substrate and upon the growing film by applying a pulsed bias technique. By varying the bias voltage during the deposition process specific properties of the interface, bulk film and top surface layer can be obtained. We report on nanoindentation and transmission electron microscopy studies as well as stress measurements of cathodic-arc amorphous hard carbon films deposited with varied bias voltage. The investigations were performed on multilayers consisting of alternating hard and soft amorphous carbon.

  11. Zinc recovery from spent ZnO catalyst by carbon in the presence of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Hsu, Hua-Ching; Lin, Chun-I.; Chen, Hsi-Kuei

    2004-02-01

    Zinc recovery from the spent zinc oxide catalyst by carbon in the presence of calcium carbonate was studied using an X-ray diffractometer (XRD), an atomic absorption spectrometer (AAS), and a scanning electron microscope (SEM). The spent zinc oxide catalyst was determined to be composed of 87.5 wt pct zinc oxide and 3.1 wt pct zinc sulfide. The results of X-ray diffractometry revealed that calcium carbonate decomposed to calcium oxide and carbon dioxide; zinc oxide and zinc sulfide were reduced to zinc vapor and carbon monoxide evolving from solid sample; and sulfur content was scavenged as calcium sulfide remained in the solid. Steps involved in this reaction system were summarized to explain the overall reaction. The experimental results of atomic absorption spectrometry showed that the initial rate of zinc recovery and final zinc recovery can be increased by increasing either the sample height, the reaction temperature or the initial bulk density. Furthermore, they were found to increase with decrease in either the argon flow rate, the molar ratio of Zntotal/C, the molar ratio of Zntotal/CaCO3, the grain size of the spent catalyst, the agglomerate size of carbon, or the agglomerate size of calcium carbonate. Empirical expressions of the initial rate of zinc recovery and final zinc recovery have been determined.

  12. Large-deformation and high-strength amorphous porous carbon nanospheres

    NASA Astrophysics Data System (ADS)

    Yang, Weizhu; Mao, Shimin; Yang, Jia; Shang, Tao; Song, Hongguang; Mabon, James; Swiech, Wacek; Vance, John R.; Yue, Zhufeng; Dillon, Shen J.; Xu, Hangxun; Xu, Baoxing

    2016-04-01

    Carbon is one of the most important materials extensively used in industry and our daily life. Crystalline carbon materials such as carbon nanotubes and graphene possess ultrahigh strength and toughness. In contrast, amorphous carbon is known to be very brittle and can sustain little compressive deformation. Inspired by biological shells and honeycomb-like cellular structures in nature, we introduce a class of hybrid structural designs and demonstrate that amorphous porous carbon nanospheres with a thin outer shell can simultaneously achieve high strength and sustain large deformation. The amorphous carbon nanospheres were synthesized via a low-cost, scalable and structure-controllable ultrasonic spray pyrolysis approach using energetic carbon precursors. In situ compression experiments on individual nanospheres show that the amorphous carbon nanospheres with an optimized structure can sustain beyond 50% compressive strain. Both experiments and finite element analyses reveal that the buckling deformation of the outer spherical shell dominates the improvement of strength while the collapse of inner nanoscale pores driven by twisting, rotation, buckling and bending of pore walls contributes to the large deformation.

  13. Large-deformation and high-strength amorphous porous carbon nanospheres

    PubMed Central

    Yang, Weizhu; Mao, Shimin; Yang, Jia; Shang, Tao; Song, Hongguang; Mabon, James; Swiech, Wacek; Vance, John R.; Yue, Zhufeng; Dillon, Shen J.; Xu, Hangxun; Xu, Baoxing

    2016-01-01

    Carbon is one of the most important materials extensively used in industry and our daily life. Crystalline carbon materials such as carbon nanotubes and graphene possess ultrahigh strength and toughness. In contrast, amorphous carbon is known to be very brittle and can sustain little compressive deformation. Inspired by biological shells and honeycomb-like cellular structures in nature, we introduce a class of hybrid structural designs and demonstrate that amorphous porous carbon nanospheres with a thin outer shell can simultaneously achieve high strength and sustain large deformation. The amorphous carbon nanospheres were synthesized via a low-cost, scalable and structure-controllable ultrasonic spray pyrolysis approach using energetic carbon precursors. In situ compression experiments on individual nanospheres show that the amorphous carbon nanospheres with an optimized structure can sustain beyond 50% compressive strain. Both experiments and finite element analyses reveal that the buckling deformation of the outer spherical shell dominates the improvement of strength while the collapse of inner nanoscale pores driven by twisting, rotation, buckling and bending of pore walls contributes to the large deformation. PMID:27072412

  14. Properties of Amorphous Carbon Microspheres Synthesised by Palm Oil-CVD Method

    SciTech Connect

    Zobir, S. A. M.; Zainal, Z.; Sarijo, S. H.; Rusop, M.

    2011-03-30

    Amorphous carbon microspheres were synthesized using a dual-furnace chemical vapour deposition method at 800-1000 deg. C. Palm oil-based cooking oil (PO) and zinc nitrate solution was used as a carbon source and catalyst precursor, respectively with PO to zinc nitrate ratio of 30:20 (v/v) and a silicon wafer as the sample target. Regular microsphere shape of the amorphous carbons was obtained and a uniform microsphere structure improved as the carbonization temperature increased from 800 to 1000 deg. C. At 800 deg. C, no regular microspheres were formed but more uniform structure is observed at 900 deg. C. Generally the microspheres size is uniform when the heating temperature was increased to 1000 deg. C, but the presence of mixed sizes can still be observed. X-ray diffraction patterns show the presence of oxide of carbon, ZnO phase together with Zn oxalate phase. Raman spectra show two broad peaks characteristic to amorphous carbon at 1344 and 1582 cm{sup -1} for the D and G bands, respectively. These bands become more prominent as the preparation temperature increased from 800 to 1000 deg. C. This is in agreement with the formation of amorphous carbon microspheres as shown by the FESEM study and other Zn-based phases as a result of the oxidation process of the palm oil as the carbon source and the zinc nitrate as the catalyst precursor, respectively.

  15. Large-deformation and high-strength amorphous porous carbon nanospheres.

    PubMed

    Yang, Weizhu; Mao, Shimin; Yang, Jia; Shang, Tao; Song, Hongguang; Mabon, James; Swiech, Wacek; Vance, John R; Yue, Zhufeng; Dillon, Shen J; Xu, Hangxun; Xu, Baoxing

    2016-01-01

    Carbon is one of the most important materials extensively used in industry and our daily life. Crystalline carbon materials such as carbon nanotubes and graphene possess ultrahigh strength and toughness. In contrast, amorphous carbon is known to be very brittle and can sustain little compressive deformation. Inspired by biological shells and honeycomb-like cellular structures in nature, we introduce a class of hybrid structural designs and demonstrate that amorphous porous carbon nanospheres with a thin outer shell can simultaneously achieve high strength and sustain large deformation. The amorphous carbon nanospheres were synthesized via a low-cost, scalable and structure-controllable ultrasonic spray pyrolysis approach using energetic carbon precursors. In situ compression experiments on individual nanospheres show that the amorphous carbon nanospheres with an optimized structure can sustain beyond 50% compressive strain. Both experiments and finite element analyses reveal that the buckling deformation of the outer spherical shell dominates the improvement of strength while the collapse of inner nanoscale pores driven by twisting, rotation, buckling and bending of pore walls contributes to the large deformation. PMID:27072412

  16. Methotrexate intercalated calcium carbonate nanostructures: Synthesis, phase transformation and bioassay study.

    PubMed

    Dai, Chao-Fan; Wang, Wei-Yuan; Wang, Lin; Zhou, Lei; Li, Shu-Ping; Li, Xiao-Dong

    2016-12-01

    The formation and stabilization of amorphous calcium carbonate (ACC) is an active area of research owing to the presence of stable ACC in various biogenic minerals. In this paper, the synthesis of calcium carbonate (CaCO3) under the participation of methotrexate (MTX) via a facile gas diffusion route was reported. The results indicated that the addition of MTX can result in the phase transformation of CaCO3, and then two kinds of hybrids, i.e., MTX-vaterite and stable MTX-ACC came into being. Interestingly, the functional agent MTX served as both the target anticancer drug loaded and effective complexation agents to modify and control the morphology of final samples. The examination of MTX-ACC biodegradation process revealed that the collapse of MTX-ACC nanoparticles was due to the synergistic effect of drug release and the phase transformation. Finally, our study also proved that MTX-ACC exhibited the most excellent suppressing function on the viability of cancer cells, especially after long-time duration. PMID:27612750

  17. Calcium carbonate scale control, effect of material and inhibitors.

    PubMed

    Macadam, J; Parsons, S A

    2004-01-01

    This paper focuses on developing a reproducible method for reducing calcium carbonate scale formation on heated surfaces where scaling can cause serious problems. It is known that calcium carbonate precipitation is sensitive to impurity ions, such as iron and zinc, even at trace concentration levels. In this paper two sets of experiments are reported. The first experiments were undertaken to investigate the effect of zinc, copper and iron dosing on CaCO3 nucleation and precipitation. Results from the experiments showed that the most effective inhibitor of CaCO3 precipitation was zinc and the effect was linked to dose levels and temperature. Copper and iron had little effect on precipitation in the dose range investigated. The second trial was undertaken to translate the precipitation data to scale formation. These tests were undertaken at 70 degrees C. 5 mg x L(-1) zinc dose reduced the scale formation by 35%. The effect of iron on calcium carbonate scaling rate was not significant. The physical nature of the material on which the scale is formed also influences the scaling. The scaling experiment was also used to investigate the effect of different surface material (stainless steel, copper and aluminium) on CaCO3 scale formation. Copper surface scaled the most. PMID:14982176

  18. Synthesis of nano precipitated calcium carbonate by using a carbonation process through a closed loop reactor

    NASA Astrophysics Data System (ADS)

    Thriveni, Thenepalli; Ahn, Ji Whan; Ramakrishna, Chilakala; Ahn, Young Jun; Han, Choon

    2016-01-01

    Nano calcium carbonate particles have a wide range of industrial applications due to their beneficial properties such as high porosity and high surface area to volume ratio and due to their strengthening the mechanical properties of plastics and paper. Consequently, significant research has been done to deliver a new approach for the synthesis of precipitated nano calcium carbonate by using a carbonation process through a closed loop reactor. Both the experimental and the instrumental parameters, i.e. the CO2 flow rate, the concentration of the starting materials (Ca(OH)2 and CaO), the pH, the orifice diameter, etc., were investigated. The carbonation efficiency was increased due to the diffusion process involved in the loop reactor. The particle size was affected by the CO2 flow rate, reaction time, and orifice diameter. Finally, precipitated nano calcite calcium carbonate (50 to 100 nm) was synthesized by optimizing all the experimental and the instrumental parameters. The synthesized precipitated nano calcium carbonate was characterized by using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy. This study has proved that the carbonation efficiency can be enhanced for a short time by using a loop reactor and that the carbonation process was more energy efficient and cost effective than other conventional methods.

  19. Randomized crossover study comparing the phosphate-binding efficacy of calcium ketoglutarate versus calcium carbonate in patients on chronic hemodialysis.

    PubMed

    Bro, S; Rasmussen, R A; Handberg, J; Olgaard, K; Feldt-Rasmussen, B

    1998-02-01

    The objective of the study was to evaluate the phosphate-binding efficacy, side effects, and cost of therapy of calcium ketoglutarate granulate as compared with calcium carbonate tablets in patients on chronic hemodialysis. The study design used was a randomized, crossover open trial, and the main outcome measurements were plasma ionized calcium levels, plasma phosphate levels, plasma intact parathyroid hormone (PTH) levels, requirements for supplemental aluminum-aminoacetate therapy, patient tolerance, and cost of therapy. Nineteen patients on chronic hemodialysis were treated with a dialysate calcium concentration of 1.25 mmol/L and a fixed alfacalcidol dose for at least 2 months. All had previously tolerated therapy with calcium carbonate. Of the 19 patients included, 10 completed both treatment arms. After 12 weeks of therapy, the mean (+/-SEM) plasma ionized calcium level was significantly lower in the ketoglutarate arm compared with the calcium carbonate arm (4.8+/-0.1 mg/dL v 5.2+/-0.1 mg/dL; P = 0.004), whereas the mean plasma phosphate (4.5+/-0.3 mg/dL v 5.1+/-0.1 mg/dL) and PTH levels (266+/-125 pg/mL v 301+/-148 pg/mL) did not differ significantly between the two treatment arms. Supplemental aluminum-aminoacetate was not required during calcium ketoglutarate treatment, while two patients needed this supplement when treated with calcium carbonate. Five of 17 (29%) patients were withdrawn from calcium ketoglutarate therapy within 1 to 2 weeks due to intolerance (anorexia, vomiting, diarrhea, general uneasiness), whereas the remaining 12 patients did not experience any side effects at all. The five patients with calcium ketoglutarate intolerance all had pre-existing gastrointestinal symptoms; four of them had received treatment with cimetidine or omeprazol before inclusion into the study. Calculations based on median doses after 12 weeks showed that the cost of the therapy in Denmark was 10 times higher for calcium ketoglutarate compared with calcium

  20. Effect of some organic solvent-water mixtures composition on precipitated calcium carbonate in carbonation process

    NASA Astrophysics Data System (ADS)

    Konopacka-Łyskawa, Donata; Kościelska, Barbara; Karczewski, Jakub

    2015-05-01

    Precipitated calcium carbonate particles were obtained during carbonation of calcium hydroxide slurry with carbon dioxide. Aqueous solutions of isopropyl alcohol, n-butanol and glycerol were used as solvents. Concentration of organic additives in the reactive mixture was from 0% to 20% (vol). Precipitation process were performed in a stirred tank reactor equipped with gas distributor. Multimodal courses of particles size distribution were determined for produced CaCO3 particles. Calcium carbonate as calcite was precipitated in all experiments. The mean Sauter diameter of CaCO3 particles decreased when the concentration of all used organic additives increased. The amount of small particle fraction in the product increased with the increasing concentration of organic solvents. Similar physical properties of used liquid phase resulted in the similar characteristics of obtained particles.

  1. Cogrinding significance for calcium carbonate-calcium phosphate mixed cement. II. Effect on cement properties.

    PubMed

    Tadier, Solène; Bolay, Nadine Le; Fullana, Sophie Girod; Cazalbou, Sophie; Charvillat, Cédric; Labarrère, Michel; Boitel, Daniel; Rey, Christian; Combes, Christèle

    2011-11-01

    In the present study, we aim to evaluate the contribution of the cogrinding process in controlling calcium carbonate-dicalcium phosphate dihydrate cement properties. We set a method designed to evaluate phase separation, usually occurring during paste extrusion, which is quantitative, reliable, and discriminating and points out the determining role of cogrinding to limit filter-pressing. We show that solid-phase cogrinding leads to synergistic positive effects on cement injectability, mechanical properties, and radio-opacity. It allows maintaining a low (<0.4 kg) and constant load during the extrusion of paste, and the paste's composition remains constant and close to that of the initial paste. Analogous behavior was observed when adding a third component into the solid phase, especially SrCO(3) as a contrasting agent. Moreover, the cement's mechanical properties can be enhanced by lowering the L/S ratio because of the lower plastic limit. Finally, unloaded or Sr-loaded cements show uniform and increased optical density because of the enhanced homogeneity of dry component distribution. Interestingly, this study reveals that cogrinding improves and controls essential cement properties and involves processing parameters that could be easily scaled up. This constitutes a decisive advantage for the development of calcium carbonate-calcium phosphate mixed cements and, more generally, of injectable multicomponent bone cements that meet a surgeon's requirements. PMID:21953727

  2. Amorphous carbon for structured step bunching during graphene growth on SiC

    NASA Astrophysics Data System (ADS)

    Palmer, James; Kunc, Jan; Hu, Yike; Hankinson, John; Guo, Zelei; Berger, Claire; de Heer, Walt

    2014-03-01

    Structured growth of high quality graphene is necessary for technological development of carbon based materials. Specifically, control of the bunching and placement of surface steps under epitaxial graphene on SiC is an important consideration for graphene device production. We demonstrate lithographically patterned evaporated amorphous carbon as a method to pin SiC surface steps. Evaporated amorphous carbon is an ideal step-flow barrier on SiC due to its chemical compatibility with graphene growth and its structural stability at high temperatures, as well as its patternability. The amorphous carbon is deposited in vacuum on SiC prior to graphene growth. In the graphene furnace at temperatures above 1200°C, mobile SiC steps accumulate at these amorphous carbon barriers, forming an aligned step free region for graphene growth at temperatures above 1330°C. AFM imaging and Raman spectroscopy support the formation of quality step-free graphene sheets grown on SiC with the step morphology aligned to the carbon grid.

  3. Fractional absorption of active absorbable algal calcium (AAACa) and calcium carbonate measured by a dual stable-isotope method

    Technology Transfer Automated Retrieval System (TEKTRAN)

    With the use of stable isotopes, this study aimed to compare the bioavailability of active absorbable algal calcium (AAACa), obtained from oyster shell powder heated to a high temperature, with an additional heated seaweed component (Heated Algal Ingredient, HAI), with that of calcium carbonate. In ...

  4. Growth of metal-free carbon nanotubes on glass substrate with an amorphous carbon catalyst layer.

    PubMed

    Seo, Jae Keun; Choi, Won Seok; Kim, Hee Dong; Lee, Jae-Hyeoung; Choi, Eun Chang; Kim, Hyung Jin; Hong, Byungyou

    2011-12-01

    We have investigated the direct growth of metal-free carbon nanotubes (CNTs) on glass substrates with microwave-plasma enhanced chemical vapor deposition (MPECVD). Amorphous carbon (a-C) films were used as a catalyst layer to grow metal-free CNTs. The a-C films were deposited on Corning glass substrates using RF magnetron sputtering with the use of a carbon target (99.99%) at room temperature. They were pretreated with hydrogen plasma using a microwave PECVD at 600 degrees C. Then, CNTs were prepared using microwave PECVD with a mixture of methane (CH4) and hydrogen (H2) gases. The CNTs were grown at different substrate temperatures (400 degrees C, 500 degrees C, and 600 degrees C) for 30 minutes. Other conditions were fixed. The growth trends of CNTs against substrate temperature were observed by field emission scanning electron microscopy (FE-SEM). The structure of a-C catalyst layer and grown CNTs were measured by Raman spectroscopy. High-resolution transmission electron microscopy (HR-TEM) images showed that the CNTs had bamboo-like multi-walled structures. Energy dispersive spectroscopy (EDS) measurements confirmed that the CNTs consisted of only carbon. PMID:22409050

  5. In vitro cytocompatibility assessment of amorphous carbon structures using neuroblastoma and Schwann cells.

    PubMed

    Jain, Shilpee; Sharma, Ashutosh; Basu, Bikramjit

    2013-05-01

    The development of scaffolds for neural tissue engineering application requires an understanding of cell adhesion, proliferation, and migration of neuronal cells. Considering the potential application of carbon as scaffold materials and the lack of understanding of compatibility of amorphous carbon with neuronal cells, the carbon-based materials in the forms of carbon films and continuous electrospun carbon nanofibers having average diameter of ~200 nm are being investigated with or without ultraviolet (UV) and oxy-plasma (OP) treatments for cytocompatibility property using mouse Neuroblastoma (N2a) and rat Schwann cells (RT4-D6P2T). The use of Raman spectroscopy in combination with Fourier transform infrared (FTIR) and X-ray diffraction establishes the amorphous nature and surface-bonding characteristics of the studied carbon materials. Although both UV and OP treatments make carbon surfaces more hydrophilic, the cell viability of N2a cells is statistically more significant on OP treated fibers/films compared to UV fiber/film substrates after 4 days in culture. The electrospun carbon fibrous substrate provides the physical guidance to the cultured Schwann cells. Overall, the experimental results of this study demonstrate that the electrospun amorphous carbon nanofibrous scaffolds can be used as a suitable biomaterial substrate for supporting cell adhesion and proliferation of neuronal cells in the context of their applications as artificial nerve implants. PMID:23359403

  6. A comparative study of calcium absorption following a single serving administration of calcium carbonate powder versus calcium citrate tablets in healthy premenopausal women

    PubMed Central

    Wang, Haiyuan; Bua, Peter; Capodice, Jillian

    2014-01-01

    Background Calcium is an essential mineral often taken as a daily, long-term nutritional supplement. Data suggests that once-daily dosing is important with regard to long-term compliance of both drugs and nutritional supplements. Objective This study was undertaken to compare the bioavailability of a single serving of two calcium supplements in healthy, premenopausal women. Design A two-period, crossover bioavailability study of a single serving of calcium citrate tablets (two tablets=500 mg calcium) versus a single serving of calcium carbonate powder (one packet of powder=1,000 mg calcium) was performed in healthy women aged between 25 and 45. All subjects were on a calcium-restricted diet 7 days prior to testing and fasted for 12 h before being evaluated at 0, 1, 2, and 4 h after oral administration of the test agents. Blood measurements for total and ionized calcium and parathyroid hormone were performed and adverse events were monitored. Results Twenty-three women were evaluable with a mean age of 33.2±8.71. Results showed that administration of a single serving of a calcium carbonate powder resulted in greater absorption in total and ionized calcium versus a single serving of calcium citrate tablets at 4 h (4.25±0.21 vs. 4.16±0.16, p=0.001). There were minimal side effects and no reported serious adverse events. Conclusions This study shows that a single serving of a calcium carbonate powder is more bioavailable than a single serving of calcium citrate tablets. This may be beneficial for long-term compliance. PMID:24772062

  7. Precipitation of calcium carbonate and calcium phosphate under diffusion controlled mixing

    SciTech Connect

    Tsigabu Gebrehiwet; James R. Henriksen; Luanjing Guo; Don T. Fox; Hai Huang; Lee Tu; Yoshiko Fujita; Robert W. Smith; George Redden

    2014-07-01

    Multi-component mineral precipitation in porous, subsurface environments is challenging to simulate or engineer when in situ reactant mixing is controlled by diffusion. In contrast to well-mixed systems, the conditions that favor mineral precipitation in porous media are distributed along chemical gradients, which evolve spatially due to concurrent mineral precipitation and modification of solute transport in the media. The resulting physical and chemical characteristics of a mixing/precipitation zone are a consequence of coupling between transport and chemical processes, and the distinctive properties of individual chemical systems. We examined the spatial distribution of precipitates formed in “double diffusion” columns for two chemical systems, calcium carbonate and calcium phosphate. Polyacrylamide hydrogel was used as a low permeability, high porosity medium to maximize diffusive mixing and minimize pressure- and density-driven flow between reactant solutions. In the calcium phosphate system, multiple, visually dense and narrow bands of precipitates were observed that were reminiscent of previously reported Liesegang patterns. In the calcium carbonate system, wider precipitation zones characterized by more sparse distributions of precipitates and a more open channel structure were observed. In both cases, formation of precipitates inhibited, but did not necessarily eliminate, continued transport and mixing of the reactants. A reactive transport model with fully implicit coupling between diffusion, chemical speciation and precipitation kinetics, but where explicit details of nucleation processes were neglected, was able to qualitatively simulate properties of the precipitation zones. The results help to illustrate how changes in the physical properties of a precipitation zone depend on coupling between diffusion-controlled reactant mixing and chemistry-specific details of precipitation kinetics.

  8. Strain-Specific Ureolytic Microbial Calcium Carbonate Precipitation

    PubMed Central

    Hammes, Frederik; Boon, Nico; de Villiers, Johan; Verstraete, Willy; Siciliano, Steven Douglas

    2003-01-01

    During a study of ureolytic microbial calcium carbonate (CaCO3) precipitation by bacterial isolates collected from different environmental samples, morphological differences were observed in the large CaCO3 crystal aggregates precipitated within bacterial colonies grown on agar. Based on these differences, 12 isolates were selected for further study. We hypothesized that the striking differences in crystal morphology were the result of different microbial species or, alternatively, differences in the functional attributes of the isolates selected. Sequencing of 16S rRNA genes showed that all of the isolates were phylogenetically closely related to the Bacillus sphaericus group. Urease gene diversity among the isolates was examined by using a novel application of PCR-denaturing gradient gel electrophoresis (DGGE). This approach revealed significant differences between the isolates. Moreover, for several isolates, multiple bands appeared on the DGGE gels, suggesting the apparent presence of different urease genes in these isolates. The substrate affinities (Km) and maximum hydrolysis rates (Vmax) of crude enzyme extracts differed considerably for the different strains. For certain isolates, the urease activity increased up to 10-fold in the presence of 30 mM calcium, and apparently this contributed to the characteristic crystal formation by these isolates. We show that strain-specific calcification occurred during ureolytic microbial carbonate precipitation. The specificity was mainly due to differences in urease expression and the response to calcium. PMID:12902285

  9. Effect of calcium on adsorption capacity of powdered activated carbon.

    PubMed

    Li, Gang; Shang, Junteng; Wang, Ying; Li, Yansheng; Gao, Hong

    2013-12-01

    We investigated the effect of calcium ion on the adsorption of humic acid (HA) (as a target pollutant) by powered activated carbon. The HA adsorption isotherms at different pH and kinetics of two different solutions including HA alone and HA doped Ca(2+), were performed. It was showed that the adsorption capacity of powdered activated carbon (PAC) for HA was markedly enhanced when Ca(2+) was doped into HA. Also, HA and Ca(2+) taken as nitrate were tested on the uptake of each other respectively and it was showed that the adsorbed amounts of both of them were significantly promoted when HA and calcium co-existed. Furthermore, the adsorbed amount of HA slightly decreased with the increasing of Ca(2+) concentration, whereas the amount of calcium increased with the increasing of HA concentration, but all above the amounts without addition. Finally, the change of pH before and after adsorption process is studied. In the two different solutions including HA alone and HA doped Ca(2+), pH had a small rise, but the extent of pH of later solution was bigger. PMID:25078809

  10. Structural and tribological characterization of protective amorphous diamond-like carbon and amorphous CNx overcoats for next generation hard disks

    NASA Astrophysics Data System (ADS)

    Scharf, T. W.; Ott, R. D.; Yang, D.; Barnard, J. A.

    1999-03-01

    Further insight into processing-structure-property relationships have been carried out for existing and candidate carbon-based protective overcoats used in the magnetic recording industry. Specifically, 5 nm thick amorphous diamond-like carbon (a:C) and nitrogenated diamond-like carbon (a:CNx) overcoats were deposited by low deposition rate sputtering onto a thin film disk consisting of either CoCrPt/CrV/NiP/AlMg or CoCrPt/CrV/glass. The wear durability and frictional behavior of these hard disks were ascertained using a recently developed depth sensing reciprocating nanoscratch test. It was determined that the CN0.14/CoCrPt/CrV/glass disk exhibited the most wear resistance, least amount of plastic deformation, and lowest kinetic friction coefficient after the last wear event. Core level x-ray photoelectron spectroscopy (XPS) results of sputter cleaned overcoats indicated that nitrogen up to 14 at. % incorporated into the amorphous network resulted in these improvements near the overcoat/magnetic layer interface, since there was an increase in the number of N-sp3 C bonded sites in a predominantly N-sp2 C bonded matrix. However, nonsputter cleaned overcoats exhibited a more graphitic pyridine-like (nondoping configuration) structure near the surface as evidenced by the increase in C=N versus C-N bonds and the valence band XPS determined appearance of the 2p-π band near the Fermi level (EF). Therefore, XPS sputter cleaning revealed a gradient in the chemical nature of the overcoats through the thickness. In addition, micro-Raman spectroscopy established that a further increase of nitrogen (⩾18 at. %) weakened the overcoat structure due to the formation of terminated sites in the amorphous carbon network, since nitrogen failed to connect the sp2 domains within the network. This, in conjunction with an increase in the intensity of the 2p-π band from the valence band XPS spectra and the increase in the G-band position and ID/IG ratio from the Raman spectra

  11. Alginate hydrogel-mediated crystallization of calcium carbonate

    SciTech Connect

    Ma, Yufei; Feng, Qingling

    2011-05-15

    We documented a specific method for combining calcium ions and alginate molecules slowly and continuously in the mineralization system for the purpose of understanding the mediating function of alginate on the crystallization of calcium carbonate. The alginate was involved in the nucleation and the growth process of CaCO{sub 3}. The crystal size, morphology and roughness of crystal surface were significantly influenced by the type of the alginate, which could be accounted for by the length of the G blocks in alginate. A combination of Fourier transform infrared spectroscopy and thermogravimetric analysis showed that there were the chemical interactions between the alginate and the mineral phase. This strategic approach revealed the biologically controlled CaCO{sub 3} mineralization within calcium alginate hydrogels via the selective nucleation and the confined crystallization of CaCO{sub 3}. The results presented here could contribute to the understanding of the mineralization process in hydrogel systems. -- Graphical abstract: Schematic illustration of the growth of calcite aggregates with different morphologies obtained from (a) Low G alginate gels and (b) High G alginate gels. Display Omitted highlights: > We use a specific method for combining calcium ions and alginate molecules slowly and continuously in the mineralization system to understand the mediating function of alginate on the crystallization of CaCO{sub 3} crystals. > The crystal size, morphology and crystal surface roughness are influenced by the length of G blocks in alginate. There are chemical interactions between the alginate and the mineral phase. > We propose a potential mechanism of CaCO{sub 3} crystallization within High G and Low G calcium alginate hydrogel.

  12. Nacre-like calcium carbonate controlled by ionic liquid/graphene oxide composite template.

    PubMed

    Yao, Chengli; Xie, Anjian; Shen, Yuhua; Zhu, Jinmiao; Li, Hongying

    2015-06-01

    Nacre-like calcium carbonate nanostructures have been mediated by an ionic liquid (IL)-graphene oxide (GO) composite template. The resultant crystals were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, and X-ray powder diffractometry (XRD). The results showed that either 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF4) or graphene oxide can act as a soft template for calcium carbonate formation with unusual morphologies. Based on the time-dependent morphology changes of calcium carbonate particles, it is concluded that nacre-like calcium carbonate nanostructures can be formed gradually utilizing [BMIM]BF4/GO composite template. During the process of calcium carbonate formation, [BMIM]BF4 acted not only as solvents but also as morphology templates for the fabrication of calcium carbonate materials with nacre-like morphology. Based on the observations, the possible mechanisms were also discussed. PMID:25842135

  13. Transglutaminase-induced crosslinking of gelatin-calcium carbonate composite films.

    PubMed

    Wang, Yuemeng; Liu, Anjun; Ye, Ran; Wang, Wenhang; Li, Xin

    2015-01-01

    The effects of transglutaminase (TGase) on the rheological profiles and interactions of gelatin-calcium carbonate solutions were studied. In addition, mechanical properties, water vapour permeability and microstructures of gelatin-calcium carbonate films were also investigated and compared. Fluorescence data suggested that the interaction of TGase and gelation-calcium carbonate belonged to a static quenching mechanism, and merely one binding site between TGase and gelatin-calcium carbonate was identified. Moreover, differential scanning calorimetry (DSC), the mechanical properties and the water vapour permeability studies revealed that TGase favoured the strong intramolecular polymerisation of the peptides in gelatin. The microstructures of the surfaces and cross sections in gelatin-calcium carbonate films were shown by scanning electron microscope (SEM) micrographs. The results of the fourier transform infrared spectroscopy (FTIR) indicated that TGase caused conformational changes in the proteins films. Therefore, TGase successfully facilitated the formation of gelatin-calcium carbonate composite films. PMID:25053075

  14. Calcium carbonate nucleation driven by ion binding in a biomimetic matrix revealed by in situ electron microscopy

    NASA Astrophysics Data System (ADS)

    Smeets, Paul J. M.; Cho, Kang Rae; Kempen, Ralph G. E.; Sommerdijk, Nico A. J. M.; de Yoreo, James J.

    2015-04-01

    The characteristic shapes, structures and properties of biominerals arise from their interplay with a macromolecular matrix. The developing mineral interacts with acidic macromolecules, which are either dissolved in the crystallization medium or associated with insoluble matrix polymers, that affect growth habits and phase selection or completely inhibit precipitation in solution. Yet little is known about the role of matrix-immobilized acidic macromolecules in directing mineralization. Here, by using in situ liquid-phase electron microscopy to visualize the nucleation and growth of CaCO3 in a matrix of polystyrene sulphonate (PSS), we show that the binding of calcium ions to form Ca-PSS globules is a key step in the formation of metastable amorphous calcium carbonate (ACC), an important precursor phase in many biomineralization systems. Our findings demonstrate that ion binding can play a significant role in directing nucleation, independently of any control over the free-energy barrier to nucleation.

  15. Mechanochemical-hydrothermal synthesis of calcium phosphate powders with coupled magnesium and carbonate substitution

    NASA Astrophysics Data System (ADS)

    Suchanek, Wojciech L.; Byrappa, Kullaiah; Shuk, Pavel; Riman, Richard E.; Janas, Victor F.; TenHuisen, Kevor S.

    2004-03-01

    Magnesium- and carbonate-substituted calcium phosphate powders (Mg-, CO 3-CaP) with various crystallinity levels were prepared at room temperature via a heterogeneous reaction between MgCO 3/Ca(OH) 2 powders and an (NH 4) 2HPO 4 solution using the mechanochemical-hydrothermal route. X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis were performed. It was determined that the powders containing both Mg 2+ and CO 32- ions were incorporated uniformly into an amorphous calcium phosphate phase while in contrast, the as-prepared powder free of these dopants was crystalline phase-pure, stoichiometric hydroxyapatite. Dynamic light scattering revealed that the average particle size of the room temperature Mg-, CO 3-CaP powders was in the range of 482 nm-700 nm with a specific surface area between 53 and 91 m 2/g. Scanning electron microscopy confirmed that the Mg-, CO 3-CaP powders consisted of agglomerates of equiaxed, ≈20-35 nm crystals.

  16. Mapping amorphous calcium phosphate transformation into crystalline mineral from the cell to the bone in zebrafish fin rays.

    PubMed

    Mahamid, Julia; Aichmayer, Barbara; Shimoni, Eyal; Ziblat, Roy; Li, Chenghao; Siegel, Stefan; Paris, Oskar; Fratzl, Peter; Weiner, Steve; Addadi, Lia

    2010-04-01

    The continuously forming fin bony rays of zebrafish represent a simple bone model system in which mineralization is temporally and spatially resolved. The mineralized collagen fibrils of the fin bones are identical in structure to those found in all known bone materials. We study the continuous mineralization process within the tissue by using synchrotron microbeam x-ray diffraction and small-angle scattering, combined with cryo-scanning electron microscopy. The former provides information on the mineral phase and the mineral particles size and shape, whereas the latter allows high-resolution imaging of native hydrated tissues. The integration of the two techniques demonstrates that new mineral is delivered and deposited as packages of amorphous calcium phosphate nanospheres, which transform into platelets of crystalline apatite within the collagen matrix. PMID:20308589

  17. Structural and dynamical studies of acid-mediated conversion in amorphous-calcium-phosphate based dental composites

    SciTech Connect

    Zhang, Fan; Allen, Andrew J.; Levine, Lyle E.; Vaudin, Mark D.; Skrtic, Drago; Antonucci, Joseph M.; Hoffman, Kathleen M.; Giuseppetti, Anthony A.; Ilavsky, Jan

    2014-07-28

    Our objective was to investigate the complex structural and dynamical conversion process of the amorphous-calcium-phosphate (ACP)-to-apatite transition in ACP based dental composite materials. Composite disks were prepared using zirconia hybridized ACP fillers (0.4 mass fraction) and photo-activated Bis-GMA/TEGDMA resin (0.6 mass fraction). We performed an investigation of the solution-mediated ACP-to-apatite conversion mechanism in controlled acidic aqueous environment with in situ ultra-small angle X-ray scattering based coherent X-ray photon correlation spectroscopy and ex situ X-ray diffraction, as well as other complementary techniques. We established that the ACP-to-apatite conversion in ACP composites is a two-step process, owing to the sensitivity to local structural changes provided by coherent X-rays. Initially, ACP undergoes a local microstructural rearrangement without losing its amorphous character. We established the catalytic role of the acid and found the time scale of this rearrangement strongly depends on the pH of the solution, which agrees with previous findings about ACP without the polymer matrix being present. In the second step, ACP is converted to an apatitic form with the crystallinity of the formed crystallites being poor. Separately, we also confirmed that in the regular Zr-modified ACP the rate of ACP conversion to hydroxyapatite is slowed significantly compared to unmodified ACP, which is beneficial for targeted slow release of functional calcium and phosphate ions from dental composite materials. Significantly, for the first time, we were able to follow the complete solution-mediated transition process from ACP to apatite in this class of dental composites in a controlled aqueous environment. A two-step process, suggested previously, was conclusively identified.

  18. Structural and dynamical studies of acid-mediated conversion in amorphous-calcium-phosphate based dental composites

    DOE PAGESBeta

    Zhang, Fan; Allen, Andrew J.; Levine, Lyle E.; Vaudin, Mark D.; Skrtic, Drago; Antonucci, Joseph M.; Hoffman, Kathleen M.; Giuseppetti, Anthony A.; Ilavsky, Jan

    2014-07-28

    Our objective was to investigate the complex structural and dynamical conversion process of the amorphous-calcium-phosphate (ACP)-to-apatite transition in ACP based dental composite materials. Composite disks were prepared using zirconia hybridized ACP fillers (0.4 mass fraction) and photo-activated Bis-GMA/TEGDMA resin (0.6 mass fraction). We performed an investigation of the solution-mediated ACP-to-apatite conversion mechanism in controlled acidic aqueous environment with in situ ultra-small angle X-ray scattering based coherent X-ray photon correlation spectroscopy and ex situ X-ray diffraction, as well as other complementary techniques. We established that the ACP-to-apatite conversion in ACP composites is a two-step process, owing to the sensitivity to localmore » structural changes provided by coherent X-rays. Initially, ACP undergoes a local microstructural rearrangement without losing its amorphous character. We established the catalytic role of the acid and found the time scale of this rearrangement strongly depends on the pH of the solution, which agrees with previous findings about ACP without the polymer matrix being present. In the second step, ACP is converted to an apatitic form with the crystallinity of the formed crystallites being poor. Separately, we also confirmed that in the regular Zr-modified ACP the rate of ACP conversion to hydroxyapatite is slowed significantly compared to unmodified ACP, which is beneficial for targeted slow release of functional calcium and phosphate ions from dental composite materials. Significantly, for the first time, we were able to follow the complete solution-mediated transition process from ACP to apatite in this class of dental composites in a controlled aqueous environment. A two-step process, suggested previously, was conclusively identified.« less

  19. Structural and dynamical studies of acid-mediated conversion in amorphous-calcium-phosphate based dental composites

    PubMed Central

    Zhang, Fan; Allen, Andrew J.; Levine, Lyle E.; Vaudin, Mark D.; Skrtic, Drago; Antonucci, Joseph M.; Hoffman, Kathleen M.; Giuseppetti, Anthony A.; Ilavsky, Jan

    2014-01-01

    Objective To investigate the complex structural and dynamical conversion process of the amorphous-calcium-phosphate (ACP) -to-apatite transition in ACP based dental composite materials. Methods Composite disks were prepared using zirconia hybridized ACP fillers (0.4 mass fraction) and photo-activated Bis-GMA/TEGDMA resin (0.6 mass fraction). We performed an investigation of the solution-mediated ACP-to-apatite conversion mechanism in controlled acidic aqueous environment with in situ ultra-small angle X-ray scattering based coherent X-ray photon correlation spectroscopy and ex situ X-ray diffraction, as well as other complementary techniques. Results We established that the ACP-to-apatite conversion in ACP composites is a two-step process, owing to the sensitivity to local structural changes provided by coherent X-rays. Initially, ACP undergoes a local microstructural rearrangement without losing its amorphous character. We established the catalytic role of the acid and found the time scale of this rearrangement strongly depends on the pH of the solution, which agrees with previous findings about ACP without the polymer matrix being present. In the second step, ACP is converted to an apatitic form with the crystallinity of the formed crystallites being poor. Separately, we also confirmed that in the regular Zr-modified ACP the rate of ACP conversion to hydroxyapatite is slowed significantly compared to unmodified ACP, which is beneficial for targeted slow release of functional calcium and phosphate ions from dental composite materials. Significance For the first time, we were able to follow the complete solution-mediated transition process from ACP to apatite in this class of dental composites in a controlled aqueous environment. A two-step process, suggested previously, was conclusively identified. PMID:25082155

  20. Effects of temperature during the irradiation of calcium carbonate.

    PubMed

    Negrón-Mendoza, Alicia; Camargo-Raya, Claudia; Gómez-Vidales, Virginia; Uribe, Roberto M; Ramos-Bernal, Sergio

    2016-05-01

    Calcium carbonate received gamma irradiation at different doses (0-309kGy) and temperature regimes (77-298K) to study the effects of irradiation temperature. The changes were followed by EPR spectroscopy. We observed the formation of a composite EPR spectrum, even at low radiation doses and temperature. There was a strong effect on the evaluation of the radicals formed as a function of irradiation temperature, probably due to the diffusion in the frozen powder and the recombination of some radicals at room temperature. PMID:26901240

  1. The influence of xanthan on the crystallization of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Yang, Xiaodeng; Xu, Guiying

    2011-01-01

    Calcium carbonate (CaCO 3) was crystallized in xanthan (XC) aqueous solutions. The CaCO 3 particles were characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and thermogravimetry analysis (TGA) methods. The concentrations of XC, Ca 2+ and CO 32- ions and the ratios [Ca 2+]/[CO 32-] and [Mg 2+]/[Ca 2+] show evident influence on the aggregation and growth of CaCO 3 particles. The presence of Mg 2+ ions influences not only the morphology, but also the polymorph of CaCO 3.

  2. Calcium carbonate production, coral reef growth, and sea level change.

    PubMed

    Smith, S V; Kinsey, D W

    1976-11-26

    Shallow, seaward portions of modern coral reefs produce about 4 kilograms of calcium carbonate per square meter per year, and protected areas produce about 0.8 kilogram per square meter per year. The difference is probably largely a function of water motion. The more rapid rate, equivalent to a maximum vertical accretion of 3 to 5 millimeters per year, places an upper limit on the potential of modern coral reef communities to create a significant vertical structure on a rising sea. PMID:17748553

  3. Calcium isotope evidence for suppression of carbonate dissolution in carbonate-bearing organic-rich sediments

    NASA Astrophysics Data System (ADS)

    Turchyn, Alexandra V.; DePaolo, Donald J.

    2011-11-01

    Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ 44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ 44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ 44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ 44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these

  4. Electrochemical Tuning of Amorphous Carbon Amount and Surface Oxidation Degree of Graphitic Quantum Dots.

    PubMed

    Wang, Jun; Li, Yan; Zhang, Bo-Ping; Ma, Ning; Ge, Juan; Li, Ling; Li, Ting; Liu, Qian-Qian

    2016-04-01

    Graphitic quantum dots (GQDs) have attracted much interesting of researchers because of its amazing optical properties and its ability to be used for many applications. Now, there are various methods have been reported for preparation of GQDs. Among them electrochemical method is simple technology, while it can afford various conditions to realize controllable prepared of GQDs. In this study, we tuned the PH values of electrolyte to probe the relationship of electrolyte environment and GQDs' optical properties as well as to seek the effective controllable condition for GQDs' preparation. It is found that the density of oxygen-related functional groups and the amount of amorphous carbon of GQDs were related to the PH values of electrolyte. The amount of amorphous carbon decreased as the PH values increased in the region of 6.6 to 7.1. Although, the positions of photoluminescence (PL) peak almost no changed of GQDs with different density of oxygen-related functional groups, GQDs with the lowest amount of amorphous carbon achieved the maximum PL intensity. Therefore, controlling amorphous carbon's amount by electrochemical method may afford a new direction to improve the fluorescence (FL) emission of GQDs. PMID:27451661

  5. Interfacial electrical properties of ion-beam sputter deposited amorphous carbon on silicon

    NASA Technical Reports Server (NTRS)

    Khan, A. A.; Woollam, J. A.; Chung, Y.; Banks, B.

    1983-01-01

    Amorphous, 'diamond-like' carbon films have been deposited on Si substrates, using ion-beam sputtering. The interfacial properties are studied using capacitance and conductance measurements. Data are analyzed using existing theories for interfacial electrical properties. The density of electronic states at the interface, along with corresponding time constants are determined.

  6. Spectral features of biogenic calcium carbonates and implications for astrobiology

    NASA Astrophysics Data System (ADS)

    Berg, B. L.; Ronholm, J.; Applin, D. M.; Mann, P.; Izawa, M.; Cloutis, E. A.; Whyte, L. G.

    2014-09-01

    The ability to discriminate biogenic from abiogenic calcium carbonate (CaCO3) would be useful in the search for extant or extinct life, since CaCO3 can be produced by both biotic and abiotic processes on Earth. Bioprecipitated CaCO3 material was produced during the growth of heterotrophic microbial isolates on medium enriched with calcium acetate or calcium citrate. These biologically produced CaCO3, along with natural and synthetic non-biologically produced CaCO3 samples, were analysed by reflectance spectroscopy (0.35-2.5 μm), Raman spectroscopy (532 and 785 nm), and laser-induced fluorescence spectroscopy (365 and 405 nm excitation). Optimal instruments for the discrimination of biogenic from abiogenic CaCO3 were determined to be reflectance spectroscopy, and laser-induced fluorescence spectroscopy. Multiple absorption features in the visible light region occurred in reflectance spectra for most biogenic CaCO3 samples, which are likely due to organic pigments. Multiple fluorescence peaks occurred in emission spectra (405 nm excitation) of biogenic CaCO3 samples, which also are best attributed to the presence of organic compounds; however, further analyses must be performed in order to better determine the cause of these features to establish criteria for confirming the origin of a given CaCO3 sample. Raman spectroscopy was not useful for discrimination since any potential Raman peaks in spectra of biogenic carbonates collected by both the 532 and 785 nm lasers were overwhelmed by fluorescence. However, this also suggests that biogenic carbonates may be identified by the presence of this organic-associated fluorescence. No reliable spectroscopic differences in terms of parameters such as positions or widths of carbonate-associated absorption bands were found between the biogenic and abiogenic carbonate samples. These results indicate that the presence or absence of organic matter intimately associated with carbonate minerals is the only potentially useful

  7. Template confined synthesis of amorphous carbon nanotubes and its confocal Raman microscopy

    SciTech Connect

    Maity, Supratim; Roychowdhury, Tuhin; Chattopadhyay, Kalyan Kumar

    2014-04-24

    Amorphous carbon nanotubes (aCNTs) were synthesized by AAO (anodic aluminum oxide) template at a temperature 500 °C in nitrogen atmosphere using the citric acid as a carbon source without the help of any catalyst particles. Morphological analysis of the as prepared samples was carried out by field emission scanning electron microscopy (FESEM). Confocal Raman imaging has been studied and an attempt has been made to find out the graphitic (sp{sup 2}) and disordered phase of the CNTs.

  8. Electron beam-induced nanopatterning of multilayer graphene and amorphous carbon films with metal layers

    SciTech Connect

    Rodriguez-Manzo, Julio A.; Banhart, Florian

    2011-05-02

    Thin Co and Ni lamellae grow under electron irradiation of metal crystals supported on multilayer graphene or amorphous carbon films. The lateral growth of a lamella from a source crystal is achieved by directing an electron beam to the periphery of the metal crystal and moving the beam over the surrounding carbon. Patterns of linear, branched, or ringlike metal lamellae can be created. The patterning is carried out in situ in a transmission electron microscope, allowing simultaneous structuring and imaging. The process is driven by the metal-carbon interaction at a beam-activated carbon surface.

  9. Effects of Atomic-Scale Structure on the Fracture Properties of Amorphous Carbon - Carbon Nanotube Composites

    NASA Technical Reports Server (NTRS)

    Jensen, Benjamin D.; Wise, Kristopher E.; Odegard, Gregory M.

    2015-01-01

    The fracture of carbon materials is a complex process, the understanding of which is critical to the development of next generation high performance materials. While quantum mechanical (QM) calculations are the most accurate way to model fracture, the fracture behavior of many carbon-based composite engineering materials, such as carbon nanotube (CNT) composites, is a multi-scale process that occurs on time and length scales beyond the practical limitations of QM methods. The Reax Force Field (ReaxFF) is capable of predicting mechanical properties involving strong deformation, bond breaking and bond formation in the classical molecular dynamics framework. This has been achieved by adding to the potential energy function a bond-order term that varies continuously with distance. The use of an empirical bond order potential, such as ReaxFF, enables the simulation of failure in molecular systems that are several orders of magnitude larger than would be possible in QM techniques. In this work, the fracture behavior of an amorphous carbon (AC) matrix reinforced with CNTs was modeled using molecular dynamics with the ReaxFF reactive forcefield. Care was taken to select the appropriate simulation parameters, which can be different from those required when using traditional fixed-bond force fields. The effect of CNT arrangement was investigated with three systems: a single-wall nanotube (SWNT) array, a multi-wall nanotube (MWNT) array, and a SWNT bundle system. For each arrangement, covalent bonds are added between the CNTs and AC, with crosslink fractions ranging from 0-25% of the interfacial CNT atoms. The SWNT and MWNT array systems represent ideal cases with evenly spaced CNTs; the SWNT bundle system represents a more realistic case because, in practice, van der Waals interactions lead to the agglomeration of CNTs into bundles. The simulation results will serve as guidance in setting experimental processing conditions to optimize the mechanical properties of CNT

  10. Controlled superficial assembly of DNA-amorphous calcium phosphate nanocomposite spheres for surface-mediated gene delivery.

    PubMed

    Oyane, Ayako; Araki, Hiroko; Nakamura, Maki; Shimizu, Yoshiki; Shubhra, Quazi T H; Ito, Atsuo; Tsurushima, Hideo

    2016-05-01

    Surface-mediated gene delivery systems have many potential applications in tissue engineering. We recently fabricated an assembly consisting of DNA-amorphous calcium phosphate (DNA-ACP) nanocomposite spheres on a polymer substrate via coprecipitation in a labile supersaturated calcium phosphate (CaP) solution and demonstrated the assembly's high gene delivery efficacy. In this study, we conducted a detailed investigation of the coprecipitation process in solution and revealed that the negatively charged DNA molecules were immobilized in the ACP spheres during the initial stage of coprecipitation and functioned as both sphere-dispersing and size-regulating agents. As a result, the DNA-ACP nanocomposites grew into size-regulated submicrospheres in solution and assembled onto the substrate via gravity sedimentation. The assembled nanocomposite spheres were chemically anchored to the substrate surface through an intermediate layer of CaP-based nanoparticles that was formed heterogeneously at the substrate surface. The coprecipitation conditions, i.e., coprecipitation time and Ca and P concentrations in solution, greatly affected the state of assembly of the nanocomposite spheres, thereby influencing the gene expression level of the cells cultured on the substrate. Increasing the number density and decreasing the size of the nanocomposite spheres did not always increase the assembly's gene delivery efficacy (per surface area of the substrate) due to adverse effects on cellular viability. As demonstrated herein, controlling the coprecipitation conditions is important for designing a cell-stimulating and biocompatible scaffold surface consisting of an assembly of DNA-ACP nanocomposite spheres. PMID:26896659

  11. Analysis of barium hydroxide and calcium hydroxide slurry carbonation reactors

    SciTech Connect

    Patch, K.D.; Hart, R.P.; Schumacher, W.A.

    1980-05-01

    The removal of CO/sub 2/ from air was investigated by using a continuous-agitated-slurry carbonation reactor containing either barium hydroxide (Ba(OH)/sub 2/) or calcium hydroxide (Ca(OH)/sub 2/). Such a process would be applied to scrub /sup 14/CO/sub 2/ from stack gases at nuclear-fuel reprocessing plants. Decontamination factors were characterized for reactor conditions which could alter hydrodynamic behavior. An attempt was made to characterize reactor performance with models assuming both plug flow and various degrees of backmixing in the gas phase. The Ba(OH)/sub 2/ slurry enabled increased conversion, but apparently the process was controlled under some conditions by phenomena differing from those observed for carbonation by Ca(OH)/sub 2/. Overall reaction mechanisms are postulated.

  12. CALCIUM CARBONATE PRODUCTION BY COCCOLITHOPHORID ALGAE IN LONG TERM CARBON DIOXIDE SEQUESTRATION

    SciTech Connect

    V. J. Fabry

    2003-10-30

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids--single-celled, marine algae that are the major global producers of calcium carbonate--to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds or bioreactors to abate CO{sub 2} emissions from power plants.

  13. CALCIUM CARBONATE PRODUCTION BY COCCOLITHOPHORID ALGAE IN LONG TERM, CARBON DIOXIDE SEQUESTRATION

    SciTech Connect

    V.J. Fabry, Ph.D.

    2001-12-15

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids--single-celled, marine algae that are the major global producers of calcium carbonate--to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  14. CALCIUM CARBONATE PRODUCTION BY COCCOLITHOPHORID ALGAE IN LONG TERM, CARBON DIOXIDE SEQUESTRATION

    SciTech Connect

    V.J. Fabry

    2001-07-01

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids single-celled, marine algae that are the major global producers of calcium carbonate to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  15. CALCIUM CARBONATE PRODUCTION BY COCCOLITHOPHORID ALGAE IN LONG TERM, CARBON DIOXIDE SEQUESTRATION

    SciTech Connect

    V.J. Fabry, Ph.D.

    2002-12-15

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids--single-celled, marine algae that are the major global producers of calcium carbonate--to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  16. CALCIUM CARBONATE PRODUCTION BY COCCOLITHOPHORID ALGAE IN LONG TERM, CARBON DIOXIDE SEQUESTRATION

    SciTech Connect

    V.J. Fabry, Ph.D.

    2002-07-09

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids--single-celled, marine algae that are the major global producers of calcium carbonate--to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  17. CALCIUM CARBONATE PRODUCTION BY COCCOLITHAPHORID ALGAE IN LONG TERM, CARBON DIOXIDE SEQUESTRATION

    SciTech Connect

    V. J.Fabry

    2004-01-30

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids--single-celled, marine algae that are the major global producers of calcium carbonate--to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  18. CALCIUM CARBONATE PRODUCTION BY COCCOLITHOPHORID ALGAE IN LONG TERM, CARBON DIOXIDE SEQUESTRATION

    SciTech Connect

    V.J. Fabry, Ph.D.

    2001-09-10

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids--single-celled, marine algae that are the major global producers of calcium carbonate--to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  19. CALCIUM CARBONATE PRODUCTION BY COCCOLITHOPHORID ALGAE IN LONG TERM, CARBON DIOXIDE SEQUESTRATION

    SciTech Connect

    V.J. Fabry, Ph.D.

    2003-04-15

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids--single-celled, marine algae that are the major global producers of calcium carbonate--to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  20. CALCIUM CARBONATE PRODUCTION BY COCCOLITHOPHORID ALGAE IN LONG TERM, CARBON DIOXIDE SEQUESTRATION

    SciTech Connect

    V.J. Fabry, Ph.D.

    2003-07-15

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids--single-celled, marine algae that are the major global producers of calcium carbonate--to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  1. CALCIUM CARBONATE PRODUCTION BY COCCOLITHOPHORID ALGAE IN LONG TERM, CARBON DIOXIDE SEQUESTRATION

    SciTech Connect

    V.J. Fabry, Ph.D.

    2002-09-30

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids--single-celled, marine algae that are the major global producers of calcium carbonate--to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  2. Calcium Carbonate Produced by Coccolithophorid Algae in Long Term, Carbon Dioxide Sequestration

    SciTech Connect

    V.J. Fabry

    2007-06-30

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO2 through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids - single-celled, marine algae that are the major global producers of calcium carbonate - to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  3. CALCIUM CARBONATE PRODUCTION BY COCCOLITHOPHORID ALGAE IN LONG TERM, CARBON DIOXIDE SEQUESTRATION

    SciTech Connect

    V. J. Fabry

    2005-01-24

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids ? single-celled, marine algae that are the major global producers of calcium carbonate ? to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  4. Calcium Carbonate Production by Coccolithophorid Algae in Long Term, Carbon Dioxide Sequestration

    SciTech Connect

    V.J. Fabry

    2005-04-29

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids--single-celled, marine algae that are the major global producers of calcium carbonate--to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  5. CALCIUM CARBONATE PRODUCTION BY COCCOLITHOPHORID ALGAE IN LONG TERM, CARBON DIOXIDE SEQUESTRATION

    SciTech Connect

    V.J. Fabry

    2004-04-26

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids single-celled, marine algae that are the major global producers of calcium carbonate to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  6. CALCIUM CARBONATE PRODUCTION BY COCCOLITHOPHORID ALGAE IN LONG TERM, CARBON DIOXIDE SEQUESTRATION

    SciTech Connect

    V.J. Fabry

    2004-10-30

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids--single-celled, marine algae that are the major global producers of calcium carbonate--to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds or bioreactors to abate CO{sub 2} emissions from power plants.

  7. Calcium Carbonate Production by Coccolithophorid Alge in Long Term Carbon Dioxide Sequestration

    SciTech Connect

    V. J. Fabry

    2006-09-30

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids--single-celled, marine algae that are the major global producers of calcium carbonate--to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  8. Calcium Carbonate Production by Coccolithophorid Algae in Long Term, Carbon Dioxide Sequestration

    SciTech Connect

    V. J. Fabry

    2006-06-30

    Predictions of increasing levels of anthropogenic carbon dioxide (CO{sub 2}) and the specter of global warming have intensified research efforts to identify ways to sequester carbon. A number of novel avenues of research are being considered, including bioprocessing methods to promote and accelerate biosequestration of CO{sub 2} from the environment through the growth of organisms such as coccolithophorids, which are capable of sequestering CO{sub 2} relatively permanently. Calcium and magnesium carbonates are currently the only proven, long-term storage reservoirs for carbon. Whereas organic carbon is readily oxidized and releases CO{sub 2} through microbial decomposition on land and in the sea, carbonates can sequester carbon over geologic time scales. This proposal investigates the use of coccolithophorids--single-celled, marine algae that are the major global producers of calcium carbonate--to sequester CO{sub 2} emissions from power plants. Cultivation of coccolithophorids for calcium carbonate (CaCO{sub 3}) precipitation is environmentally benign and results in a stable product with potential commercial value. Because this method of carbon sequestration does not impact natural ecosystem dynamics, it avoids controversial issues of public acceptability and legality associated with other options such as direct injection of CO{sub 2} into the sea and ocean fertilization. Consequently, cultivation of coccolithophorids could be carried out immediately and the amount of carbon sequestered as CaCO{sub 3} could be readily quantified. The significant advantages of this approach warrant its serious investigation. The major goals of the proposed research are to identify the growth conditions that will result in the maximum amount of CO{sub 2} sequestration through coccolithophorid calcite production and to evaluate the costs/benefits of using coccolithophorid cultivation ponds to abate CO{sub 2} emissions from power plants.

  9. Uptake of chloride and carbonate ions by calcium monosulfoaluminate hydrate

    SciTech Connect

    Mesbah, Adel; Cau-dit-Coumes, Celine; Frizon, Fabien

    2012-08-15

    Decommissioning of old nuclear reactors may produce waste streams containing chlorides and carbonates, including radioactive {sup 36}Cl{sup -} and {sup 14}CO{sub 3}{sup 2-}. Their insolubilization by calcium monosulfoaluminate hydrate was investigated. Carbonates were readily depleted from the solution, giving at thermodynamic equilibrium monocarboaluminate, monocarboaluminate + calcite, or calcite only, depending on the initial ratio between the anion and calcium monosulfoaluminate hydrate. Chloride ions reacted more slowly and were precipitated as Kuzel's salt, Kuzel's and Friedel's salts, or Friedel's salt only. Rietveld refinement of X-Ray powder diffraction patterns was successfully used to quantify the phase distributions, which were compared to thermodynamic calculations. Moreover, analysing the lattice parameters of Kuzel's salt as a function of its chloride content showed the occurrence of a restricted solid solution towards the sulfate side with general formula 3CaO{center_dot}Al{sub 2}O{sub 3}{center_dot}xCaCl{sub 2}{center_dot}(1 - x)CaSO{sub 4}{center_dot}(12 - 2x){center_dot}H{sub 2}O (0.36 {<=} x {<=} 0.50).

  10. Constitutive modeling of calcium carbonate supersaturated seawater mixtures

    NASA Astrophysics Data System (ADS)

    Reis, Martina; Sousa, Maria De Fátima; Bertran, Celso; Bassi, Adalberto

    2014-11-01

    Calcium carbonate supersaturated seawater mixtures have attracted attention of many researchers since the deposition of CaCO3(s) from such solutions can lead to scaling problems in oil fields. However, despite their evident practical importance in petroleum engineering, the hydro and thermodynamic behaviors of these mixtures have not been well-understood yet. In this work, a constitutive model based on the foundations of the constitutive theory of continuum mechanics, and the Müller-Liu entropy principle is proposed. The calcium carbonate supersaturated seawater mixture is regarded as a reactive viscous fluid with heat and electrical conductions. The obtained results indicate that the thermodynamic behavior of CaCO3 supersaturated seawater mixtures is closely related to the individual dynamics of each constituent of the mixture, particularly to the linear momentum, and mass exchanges. Furthermore, the results show that, unlike classical continuum mixtures, the extra entropy flux is not null, and higher-order gradients of deformation contribute to the residual entropy production of the class of mixtures under study. The results of this work may be relevant for the prevention of the mineral scale formation in oil fields. The first author acknowledges the São Paulo Research Foundation (Grant 2013/ 20872-2) for its funding.

  11. Effect of calcium carbonate saturation of seawater on coral calcification

    USGS Publications Warehouse

    Gattuso, J.-P.; Frankignoulle, M.; Bourge, I.; Romaine, S.; Buddemeier, R.W.

    1998-01-01

    The carbonate chemistry of seawater is usually not considered to be an important factor influencing calcium-carbonate-precipitation by corals because surface seawater is supersaturated with respect to aragonite. Recent reports, however, suggest that it could play a major role in the evolution and biogeography of recent corals. We investigated the calcification rates of five colonies of the zooxanthellate coral Stylophora pistillata in synthetic seawater using the alkalinity anomaly technique. Changes in aragonite saturation from 98% to 585% were obtained by manipulating the calcium concentration. The results show a nonlinear increase in calcification rate as a function of aragonite saturation level. Calcification increases nearly 3-fold when aragonite saturation increases from 98% to 390%, i.e., close to the typical present saturation state of tropical seawater. There is no further increase of calcification at saturation values above this threshold. Preliminary data suggest that another coral species, Acropora sp., displays a similar behaviour. These experimental results suggest: (l) that the rate of calcification does not change significantly within the range of saturation levels corresponding to the last glacial-interglacial cycle, and (2) that it may decrease significantly in the future as a result of the decrease in the saturation level due to anthropogenic release of CO2 into the atmosphere. Experimental studies that control environmental conditions and seawater composition provide unique opportunities to unravel the response of corals to global environmental changes.

  12. TEM-simulation of amorphous carbon films: influence of supercell packaging.

    PubMed

    Schultrich, H; Schultrich, B

    2001-07-01

    Recent developments in thin film technology allow to prepare deliberately amorphous carbon films with structures widely varying between graphite-like (sp2) and diamond-like (sp3) atomic bonds. This leads to amorphous structures with correspondingly varying densities. By periodically changing deposition conditions, nanometer multilayers may be prepared consisting of carbon layers of different density. Simulation of the electron microscopic imaging allows to differentiate between such real structural details (on the nanometer scale) and artefacts induced by the imaging procedure. But it must be assured that the modeled structure reflects the real one with sufficient accuracy. Thorough comparison of different simulation strategies shows that for the adequate simulation of TEM imaging of amorphous materials, the thickness of the layer with independently distributed atoms has to exceed a certain limit. Then, the statistical scattering of the randomly distributed atoms will be averaged. Otherwise, if the model of the transmission electron microscopy sample is constructed as iteration of thin identical supercells, the superposition of scattering waves with constant phase differences results in enhanced local fluctuations burying the multilayer structure. For thicker packages of supercells with independent random distributions, the effect of statistical atomic arrangements is more and more leveled off. Hence, nanometer structures based on regions with different density will be visible more distinctively in the random background. For carbon, this critical thickness amounts to about 4 nm. This is of special importance for the visualization of nanoscaled heterogeneities like multilayers or nanotube-like inclusions in amorphous matrices. PMID:11419873

  13. Fabrication of PbS nanoparticle coated amorphous carbon nanotubes: Structural, thermal and field emission properties

    SciTech Connect

    Jana, S.; Banerjee, D.; Jha, A.; Chattopadhyay, K.K.

    2011-10-15

    Graphical abstract: Simple chemical synthesis of PbS nanoparticle coated amorphous carbon nanotubes have shown better thermal stability and enhanced electron field emission properties. Highlights: {yields} PbS nanocrystals coated amorphous carbon nanotubes have been synthesized through a simple chemical route at low temperature. {yields} The composite is thermally more stable than amorphous CNTs. {yields} Composite have shown excellent cold cathode field emission property. -- Abstract: A simple chemical route for the synthesis of PbS nanoparticle coated amorphous carbon nanotubes (aCNTs) was described. The nanocomposite was prepared from an aqueous suspension of acid functionalized aCNTs, lead acetate (PbAc), and thiourea (TU) at room temperature. The phase formation and composition of the samples were characterized by X-ray diffraction and energy dispersive analysis of X-ray studies. The Fourier transformed infrared spectra analysis revealed the attachment of PbS nanoparticles on the acid functionalized aCNT surfaces. Morphology of the samples was analyzed with a field emission scanning electron microscope. UV-Vis study also confirmed the attachment of PbS nanoparticles on the walls of aCNTs. Thermal gravimetric analysis showed that the PbS coated aCNTs are more thermally stable than functionalized aCNTs. The PbS coated aCNTs showed enhanced field emission properties with a turn-on field 3.34 V {mu}m{sup -1} and the result is comparable to that of pure crystalline CNTs.

  14. The role of amorphous precursors in the crystallization of La and Nd carbonates

    NASA Astrophysics Data System (ADS)

    Vallina, Beatriz; Rodriguez-Blanco, Juan Diego; Brown, Andrew P.; Blanco, Jesus A.; Benning, Liane G.

    2015-07-01

    Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have characterized these precursors and the crystallization pathways and products with solid-state, spectroscopic and microscopic techniques to explain the differences in crystallization mechanisms between the La and Nd systems. ALC and ANC consist of highly hydrated, 10-20 nm spherical nanoparticles with a general formula of REE2(CO3)3.5H2O (REE = La, Nd). The stabilities differ by ~2 orders of magnitude, with ANC being far more stable than ALC. This difference is due to the Nd3+ ion having a far higher hydration energy compared to the La3+ ion. This, together with temperature and reaction times, leads to clear differences not only in the kinetics and mechanisms of crystallization of the amorphous precursor La- and Nd-carbonate phases but also in the resulting crystallite sizes and morphologies of the end products. All crystalline La and Nd carbonates developed spherulitic morphologies when crystallization occurred from hydrous phases in solution at temperatures above 60 °C (La system) and 95 °C (Nd system). We suggest that spherulitic growth occurs due to a rapid breakdown of the amorphous precursors and a concurrent rapid increase in supersaturation levels in the aqueous solution. The kinetic data show that the crystallization pathway for both La and Nd carbonate systems is dependent on the reaction temperature and the ionic potential of the REE3+ ion.Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have

  15. The IR emission features - Emission from PAH molecules and amorphous carbon particles

    NASA Technical Reports Server (NTRS)

    Allamandola, L. J.; Tielens, A. G. G. M.; Barker, J. R.

    1987-01-01

    Given the current understanding of polycyclic aromatic hydrocarbons (PAHs), the spectroscopic data suggest that are at least two components which contribute to the interstellar emission spectrum: (1) free molecule-sized PAHs producing the narrow features and (2) amorphous carbon particles (which are primarily composed of an irregular 'lattice' of PAHs) contributing to the broad underlying components. An exact treatment of the IR fluorescence from highly vibrationally excited large molecules demonstrates that species containing between 20 and 30 carbon atoms are responsible for the narrow features, although the spectra match more closely with the spectra of amorphous carbon particles. It is concluded that, since little is known about the spectroscopic properties of free PAHs and PAH clusters, much laboratory work is required along with an observational program focusing on the spatial characteristics of the spectra.

  16. The IR emission features - Emission from PAH molecules and amorphous carbon particles

    NASA Technical Reports Server (NTRS)

    Allamandola, L. J.; Tielens, A. G. G. M.; Barker, J. R.

    1987-01-01

    Techniques for the assessment of the importance of the various forms of PAHs, and recent infrared observations concerning the PAH problem, are considered. Spectroscopic data suggest that the observed interstellar spectrum is due to both free molecule-sized PAHs producing the narrow features, and amorphous carbon particles contributing to the broad underlying components. Explanations for the multicomponent emission spectrum are discussed. A model of the emission mechanism for the example of chrysene is presented, and an exact treatment of the IR fluorescence from highly vibrationally excited large molecules shows that species containing 20-30 carbon atoms are responsible for the narrow features, although the spectra more closely resemble those of amorphous carbon particles. It is suggested that future emphasis should be placed on the spatial characteristics of the component spectra.

  17. Enamel-like apatite crown covering amorphous mineral in a crayfish mandible.

    PubMed

    Bentov, Shmuel; Zaslansky, Paul; Al-Sawalmih, Ali; Masic, Admir; Fratzl, Peter; Sagi, Amir; Berman, Amir; Aichmayer, Barbara

    2012-01-01

    Carbonated hydroxyapatite is the mineral found in vertebrate bones and teeth, whereas invertebrates utilize calcium carbonate in their mineralized organs. In particular, stable amorphous calcium carbonate is found in many crustaceans. Here we report on an unusual, crystalline enamel-like apatite layer found in the mandibles of the arthropod Cherax quadricarinatus (freshwater crayfish). Despite their very different thermodynamic stabilities, amorphous calcium carbonate, amorphous calcium phosphate, calcite and fluorapatite coexist in well-defined functional layers in close proximity within the mandible. The softer amorphous minerals are found primarily in the bulk of the mandible whereas apatite, the harder and less soluble mineral, forms a wear-resistant, enamel-like coating of the molar tooth. Our findings suggest a unique case of convergent evolution, where similar functional challenges of mastication led to independent developments of structurally and mechanically similar, apatite-based layers in the teeth of genetically remote phyla: vertebrates and crustaceans. PMID:22588301

  18. Enamel-like apatite crown covering amorphous mineral in a crayfish mandible

    PubMed Central

    Bentov, Shmuel; Zaslansky, Paul; Al-Sawalmih, Ali; Masic, Admir; Fratzl, Peter; Sagi, Amir; Berman, Amir; Aichmayer, Barbara

    2012-01-01

    Carbonated hydroxyapatite is the mineral found in vertebrate bones and teeth, whereas invertebrates utilize calcium carbonate in their mineralized organs. In particular, stable amorphous calcium carbonate is found in many crustaceans. Here we report on an unusual, crystalline enamel-like apatite layer found in the mandibles of the arthropod Cherax quadricarinatus (freshwater crayfish). Despite their very different thermodynamic stabilities, amorphous calcium carbonate, amorphous calcium phosphate, calcite and fluorapatite coexist in well-defined functional layers in close proximity within the mandible. The softer amorphous minerals are found primarily in the bulk of the mandible whereas apatite, the harder and less soluble mineral, forms a wear-resistant, enamel-like coating of the molar tooth. Our findings suggest a unique case of convergent evolution, where similar functional challenges of mastication led to independent developments of structurally and mechanically similar, apatite-based layers in the teeth of genetically remote phyla: vertebrates and crustaceans. PMID:22588301

  19. In situ calcium carbonate dissolution in the Pacific Ocean

    SciTech Connect

    Feely, R. A.; Sabine, Chris; Lee, K.; Millero, F. J.; Lamb, M. F.; Greeley, D.; Bullister, J.L.; Key, Robert; Peng, T.-H.; Kozyr, Alexander; Ono, Tsueno

    2002-01-01

    Over the past several years researchers have been working to synthesize the WOCE/ JGOFS global CO2 survey data to better understand carbon cycling processes in the oceans. The Pacific Ocean data set has over 35,000 sample locations with at least two carbon parameters, oxygen, nutrients, CFC tracers, and hydrographic parameters. In this paper we estimate the in situ CaCO3 dissolution rates in the Pacific Ocean water column. Calcium carbonate dissolution rates ranging from 0.01 1.1 mmol kg1 yr1 are observed in intermediate and deepwater beginning near the aragonite saturation horizon. In the North Pacific Intermediate Water between 400 and 800 m, CaCO3 dissolution rates are more than 7 times faster than observed in middle and deep water depths (average = 0.051 mmol kg1 yr1). The total amount of CaCO3 that is dissolved within the Pacific is determined by integrating excess alkalinity throughout the water column. The total inventory of CaCO3 added by particle dissolution in the Pacific Ocean, north of 40S, is 157 Pg C. This amounts to an average dissolution rate of approximately 0.31 Pg C yr1. This estimate is approximately 74% of the export production of CaCO3 estimated for the Pacific Ocean. These estimates should be considered to be upper limits for in situ carbonate dissolution in the Pacific Ocean, since a portion of the alkalinity increase results from inputs from sediments.

  20. Calcium carbonate nucleation in an alkaline lake surface water, Pyramid Lake, Nevada, USA

    USGS Publications Warehouse

    Reddy, Michael M.; Hoch, Anthony

    2012-01-01

    Calcium concentration and calcite supersaturation (Ω) needed for calcium carbonate nucleation and crystal growth in Pyramid Lake (PL) surface water were determined during August of 1997, 2000, and 2001. PL surface water has Ω values of 10-16. Notwithstanding high Ω, calcium carbonate growth did not occur on aragonite single crystals suspended PL surface water for several months. However, calcium solution addition to PL surface-water samples caused reproducible calcium carbonate mineral nucleation and crystal growth. Mean PL surface-water calcium concentration at nucleation was 2.33 mM (n = 10), a value about nine times higher than the ambient PL surface-water calcium concentration (0.26 mM); mean Ω at nucleation (109 with a standard deviation of 8) is about eight times the PL surface-water Ω. Calcium concentration and Ω regulated the calcium carbonate formation in PL nucleation experiments and surface water. Unfiltered samples nucleated at lower Ω than filtered samples. Calcium concentration and Ω at nucleation for experiments in the presence of added particles were within one standard deviation of the mean for all samples. Calcium carbonate formation rates followed a simple rate expression of the form, rate (mM/min) = A (Ω) + B. The best fit rate equation "Rate (Δ mM/Δ min) = -0.0026 Ω + 0.0175 (r = 0.904, n = 10)" was statistically significant at greater than the 0.01 confidence level and gives, after rearrangement, Ω at zero rate of 6.7. Nucleation in PL surface water and morphology of calcium carbonate particles formed in PL nucleation experiments and in PL surface-water samples suggest crystal growth inhibition by multiple substances present in PL surface water mediates PL calcium carbonate formation, but there is insufficient information to determine the chemical nature of all inhibitors.

  1. Calcium Carbonate Nucleation in an Alkaline Lake Surface Water, Pyramid Lake, Nevada, USA

    USGS Publications Warehouse

    Reddy, M.M.; Hoch, A.

    2012-01-01

    Calcium concentration and calcite supersaturation (??) needed for calcium carbonate nucleation and crystal growth in Pyramid Lake (PL) surface water were determined during August of 1997, 2000, and 2001. PL surface water has ?? values of 10-16. Notwithstanding high ??, calcium carbonate growth did not occur on aragonite single crystals suspended PL surface water for several months. However, calcium solution addition to PL surface-water samples caused reproducible calcium carbonate mineral nucleation and crystal growth. Mean PL surface-water calcium concentration at nucleation was 2.33 mM (n = 10), a value about nine times higher than the ambient PL surface-water calcium concentration (0.26 mM); mean ?? at nucleation (109 with a standard deviation of 8) is about eight times the PL surface-water ??. Calcium concentration and ?? regulated the calcium carbonate formation in PL nucleation experiments and surface water. Unfiltered samples nucleated at lower ?? than filtered samples. Calcium concentration and ?? at nucleation for experiments in the presence of added particles were within one standard deviation of the mean for all samples. Calcium carbonate formation rates followed a simple rate expression of the form, rate (mM/min) = A (??) + B. The best fit rate equation "Rate (?? mM/?? min) = -0.0026 ?? + 0.0175 (r = 0.904, n = 10)" was statistically significant at greater than the 0.01 confidence level and gives, after rearrangement, ?? at zero rate of 6.7. Nucleation in PL surface water and morphology of calcium carbonate particles formed in PL nucleation experiments and in PL surface-water samples suggest crystal growth inhibition by multiple substances present in PL surface water mediates PL calcium carbonate formation, but there is insufficient information to determine the chemical nature of all inhibitors. ?? 2011 U.S. Government.

  2. Reactive Infiltration of Silicon Melt Through Microporous Amorphous Carbon Preforms

    NASA Technical Reports Server (NTRS)

    Sangsuwan, P.; Tewari, S. N.; Gatica, J. E.; Singh, M.; Dickerson, R.

    1999-01-01

    The kinetics of unidirectional capillary infiltration of silicon melt into microporous carbon preforms have been investigated as a function of the pore morphology and melt temperature. The infiltrated specimens showed alternating bands of dark and bright regions, which corresponded to the unreacted free carbon and free silicon regions, respectively. The decrease in the infiltration front velocity for increasing infiltration distances, is in qualitative agreement with the closed-form solution of capillarity driven fluid flow through constant cross section cylindrical pores. However, drastic changes in the thermal response and infiltration front morphologies were observed for minute differences in the preforms microstructure. This suggests the need for a dynamic percolation model that would account for the exothermic nature of the silicon-carbon chemical reaction and the associated pore closing phenomenon.

  3. Plasma deposition of amorphous hydrogenated carbon films on III-V semiconductors

    NASA Technical Reports Server (NTRS)

    Pouch, John J.; Warner, Joseph D.; Liu, David C.; Alterovitz, Samuel A.

    1988-01-01

    Amorphous hydrogenated carbon films were grown on GaAs, InP and fused silica substrates using plasmas generated from hydrocarbon gases. Methane and n-butane sources were utilized. The effects of flow rate and power density on film growth were investigated. Carbon was the major constituent in the films. The degree of asymmetry at the carbon-semiconductor interface was approximately independent of the power density. Different H-C bonding configurations were detected by the technique of secondary-ion mass spectrometry. Band gaps up to 3 eV were obtained from optical absorption studies. Breakdown strengths as high as 600 MV/m were measured.

  4. 40 CFR 415.300 - Applicability; description of the calcium carbonate production subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 30 2012-07-01 2012-07-01 false Applicability; description of the calcium carbonate production subcategory. 415.300 Section 415.300 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS INORGANIC CHEMICALS MANUFACTURING POINT SOURCE CATEGORY Calcium Carbonate...

  5. THE INFLUENCE OF CALCIUM CARBONATE GRAIN COATINGS ON CONTAMINANT REACTIVITY IN VADOSE ZONE SEDIMENTS

    EPA Science Inventory

    Fundamental research is proposed to investigate the role of calcium carbonate grain coatings on the vadose zone chemical reactivity of key Hanford contaminants (i.e., 60Co2+, 90Sr2+, CrO42-, and 99TcO4-). Calcium carbonate is widely distributed through the Hanford vadose zone as...

  6. Calcium absorbability from milk products, an imitation milk, and calcium carbonate

    SciTech Connect

    Recker, R.R.; Bammi, A.; Barger-Lux, M.J.; Heaney, R.P.

    1988-01-01

    Whole milk, chocolate milk, yogurt, imitation milk (prepared from dairy and nondairy products), cheese, and calcium carbonate were labeled with /sup 45/Ca and administered as a series of test meals to 10 healthy postmenopausal women. Carrier Ca content of the test meals was held constant at 250 mg and subjects fasted before each meal. The absorbability of Ca from the six sources was compared by measuring fractional absorption by the double isotope method. The mean absorption values for all six sources were tightly clustered between 21 and 26% and none was significantly different from the others using one-way analysis of variance. We conclude that none of the sources was significantly superior or inferior to the others.

  7. Effect of temperature on the reaction pathway of calcium carbonate formation via precursor phases

    NASA Astrophysics Data System (ADS)

    Purgstaller, Bettina; Mavromatis, Vasileios; Konrad, Florian; Dietzel, Martin

    2016-04-01

    It has been earlier postulated that some biogenic and sedimentary calcium carbonate (CaCO3) minerals (e.g. calcite and aragonite) are secondary in origin and have originally formed via a metastable calcium carbonate precursor phase (e.g. amorphous CaCO3, [1-2]). Such formation pathways are likely affected by various physicochemical parameters including aqueous Mg and temperature. In an effort to improve our understanding on the formation mechanism of CaCO3 minerals, precipitation experiments were carried out by the addition of a 0.6 M (Ca,Mg)Cl2 solution at distinct Mg/Ca ratios (1/4 and 1/8) into a 1 M NaHCO3 solution under constant pH conditions(8.3 ±0.1). The formation of CaCO3 was systematically examined as a function of temperature (6, 12, 18 and 25 ±0.3° C). During the experimental runs mineral precipitation was monitored by in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. The results revealed two pathways of CaCO3 formation depending on the initial Mg/Ca ratio and temperature: (i) In experiments with a Mg/Ca ratio of 1/4 at ≤ 12° C as well as in experiments with a Mg/Ca ratio of 1/8 at ≤ 18° C, ikaite (CaCO3 6H2O) acts as a precursor phase for aragonite formation. (ii) In contrast higher temperatures induced the formation of Mg-rich amorphous CaCO3 (Mg-ACC) which was subsequently transformed to Mg-rich calcite. In situ Raman spectra showed that the transformation of Mg-ACC to Mg-calcite occurs at a higher rate (˜ 8 min) compared to that of ikaite to aragonite (> 2 h). Thus, the formation of aragonite rather than of Mg-calcite occurs due to the slower release of Ca2+and CO32‑ ions into the Mg-rich reactive solution during retarded ikaite dissolution. This behavior is generally consistent with the observation that calcite precipitation is inhibited at elevated aqueous Mg/Ca ratios. [1] Addadi L., Raz S. and Weiner S. (2003) Advanced Materials 15, 959-970. [2] Rodriguez-Blanco J. D

  8. Shape control of nickel nanostructures incorporated in amorphous carbon films: From globular nanoparticles toward aligned nanowires

    NASA Astrophysics Data System (ADS)

    El Mel, A. A.; Bouts, N.; Grigore, E.; Gautron, E.; Granier, A.; Angleraud, B.; Tessier, P. Y.

    2012-06-01

    The growth of nickel/carbon nanocomposite thin films by a hybrid plasma process, which combines magnetron sputtering and plasma enhanced chemical vapor deposition, has been investigated. This study has shown that the films consist of nickel-rich nanostructures embedded in an amorphous carbon matrix. The size, the distribution, the density, and the shape of these nanostructures are directly dependent to the total carbon content within the films. At low carbon content (˜28 at. %), dense nanowire array perpendicularly oriented to the surface of the substrate can be fabricated. For an intermediate carbon concentration (˜35 at. %), the nickel phase was organized into elongated nanoparticles. These nanoparticles became spherical when reaching a higher carbon content (˜54 at. %). The extensive structural study allowed the representation of a structure zone diagram, as well as, the development of a scenario describing the growth mechanisms that take place during the deposition of such nanocomposite material.

  9. Synthesis and Characterization of Single-Wall Carbon Nanotube-Amorphous Diamond Thin-Film Composites

    SciTech Connect

    Schittenhelm, Henrik; Geohegan, David B; Jellison Jr, Gerald Earle; Puretzky, Alexander A; Lance, Michael J; Britt, Phillip F

    2002-01-01

    Thin-film single-wall carbon nanotube (SWNT) composites synthesized by pulsed laser deposition (PLD) are reported. Ultrahard, transparent, pure-carbon, electrically insulating, amorphous diamond thin films were deposited by PLD as scratch-resistant, encapsulating matrices for disperse, electrically conductive mats of SWNT bundles. In situ resistance measurements of the mats during PLD, as well as ex situ Raman spectroscopy, current-voltage measurements, spectroscopic ellipsometry, and field-emission scanning electron microscopy, are used to understand the interaction between the SWNT and the highly energetic ({approx}100 eV) carbon species responsible for the formation of the amorphous diamond thin film. The results indicate that a large fraction of SWNT within the bundles survive the energetic bombardment from the PLD plume, preserving the metallic behavior of the interconnected nanotube mat, although with higher resistance. Amorphous diamond film thicknesses of only 50 nm protect the SWNT against wear, providing scratch hardness up to 25 GPa in an optically transmissive, all-carbon thin-film composite.

  10. Rheological properties of polyolefin composites highly filled with calcium carbonate

    NASA Astrophysics Data System (ADS)

    Nobile, Maria Rossella; Fierro, Annalisa; Jakubowska, Paulina; Sterzynski, Tomasz

    2016-05-01

    In this paper the rheological properties of highly filled polyolefin composites (HFPCs) have been investigated. Calcium carbonate (CaCO3), with stearic acid modified surface, was used as filler. Ternary compounds have been obtained by the inclusion of a CaCO3/polypropylene master batch into the high density polyethylene matrix. The highly filled polyolefin composites with CaCO3 content in the range between 40 and 64 wt% have been prepared in the molten state using a single-screw extruder, the temperature of the extrusion die was set at 230°C. The melt rheological properties of the HFPCs have been extensively investigated both in oscillatory and steady shear flow.

  11. Artificial dental root made of natural calcium carbonate (Bioracine).

    PubMed

    Camprasse, S; Camprasse, G; Pouzol, M; Lopez, E

    1990-01-01

    'Bioracine' is an artificial dental root made of natural calcium carbonate (Pinctade maxima mother of pearl). This non-biodegradable material is very close to bone tissue in its physicochemical composition and presents remarkable hardness, resistance and elasticity. Bioracine is a buried dental implant with a special screw thread, presenting a large surface which shows pores of 2-3 mum. A histological study of the interface between the implant and human maxillary bone demonstrated an extraordinary cellular union between these two tissues. Furthermore, bioracine presents two new technical innovations: a periprosthetic epithelial attachment of connective tissue with an active shock absorbing system. Bioracine is an exceptional dental root substitute that matches the biological properties of natural bone. PMID:10147506

  12. Calcium carbonate obstructive urolithiasis in a red kangaroo (Macropus rufus).

    PubMed

    Lindemann, Dana M; Gamble, Kathryn C; Corner, Sarah

    2013-03-01

    A 6-yr-old male red kangaroo (Macropus rufus) presented for a history of inappetance, abnormal behavior, and unconfirmed elimination for 6 hr prior to presentation. Based on abdominal ultrasound, abdominocentesis, and cystocentesis, a presumptive diagnosis of urinary tract obstruction with uroabdomen and hydronephrosis was reached. Abdominal radiographs did not assist in reaching an antemortem diagnosis. Postmortem examination confirmed a urinary bladder rupture secondary to urethral obstruction by a single urethrolith. Bilateral hydronephrosis and hydroureter were identified and determined to be a result of bilateral ureteroliths. Urolith analysis revealed a composition of 100% calcium carbonate. A dietary analysis was performed, implicating an increased Ca:P ratio from a food preparation miscommunication as a contributing factor. Appropriate husbandry changes were made, and mob surveillance procedures were performed, which resolved the urolithiasis risk for the remaining five animals. PMID:23505728

  13. Magnesium substitution in the structure of orthopedic nanoparticles: A comparison between amorphous magnesium phosphates, calcium magnesium phosphates, and hydroxyapatites.

    PubMed

    Nabiyouni, Maryam; Ren, Yufu; Bhaduri, Sarit B

    2015-01-01

    As biocompatible materials, magnesium phosphates have received a lot of attention for orthopedic applications. During the last decade multiple studies have shown advantages for magnesium phosphate such as lack of cytotoxicity, biocompatibility, strong mechanical properties, and high biodegradability. The present study investigates the role of Mg(+2) and Ca(+2) ions in the structure of magnesium phosphate and calcium phosphate nanoparticles. To directly compare the effect of Mg(+2) and Ca(+2) ions on structure of nanoparticles and their biological behavior, three groups of nanoparticles including amorphous magnesium phosphates (AMPs) which release Mg(+2), calcium magnesium phosphates (CMPs) which release Mg(+2) and Ca(+2), and hydroxyapatites (HAs) which release Ca(+2) were studied. SEM, TEM, XRD, and FTIR were used to evaluate the morphology, crystallinity, and chemical properties of the particles. AMP particles were homogeneous nanospheres, whereas CMPs were combinations of heterogeneous nanorods and nanospheres, and HAs which contained heterogeneous nanosphere particles. Cell compatibility was monitored in all groups to determine the cytotoxicity effect of particles on studied MC3T3-E1 preosteoblasts. AMPs showed significantly higher attachment rate than the HAs after 1 day and both AMPs and CMPs showed significantly higher proliferation rate when compared to HAs after 7days. Gene expression level of osteoblastic markers ALP, COL I, OCN, OPN, RUNX2 were monitored and they were normalized to GAPDH housekeeping gene. Beta actin expression level was monitored as the second housekeeping gene to confirm the accuracy of results. In general, AMPs and CMPs showed higher expression level of osteoblastic genes after 7 days which can further confirm the stimulating role of Mg(+2) and Ca(+2) ions in increasing the proliferation rate, differentiation, and mineralization of MC3T3-E1 preosteoblasts. PMID:25953534

  14. Formate oxidation-driven calcium carbonate precipitation by Methylocystis parvus OBBP.

    PubMed

    Ganendra, Giovanni; De Muynck, Willem; Ho, Adrian; Arvaniti, Eleni Charalampous; Hosseinkhani, Baharak; Ramos, Jose Angel; Rahier, Hubert; Boon, Nico

    2014-08-01

    Microbially induced carbonate precipitation (MICP) applied in the construction industry poses several disadvantages such asammonia release to the air and nitric acid production. An alternative MICP from calcium formate by Methylocystis parvus OBBP is presented here to overcome these disadvantages. To induce calcium carbonate precipitation, M. parvus was incubated at different calcium formate concentrations and starting culture densities. Up to 91.4% ± 1.6% of the initial calcium was precipitated in the methane-amended cultures compared to 35.1% ± 11.9% when methane was not added. Because the bacteria could only utilize methane for growth, higher culture densities and subsequently calcium removals were exhibited in the cultures when methane was added. A higher calcium carbonate precipitate yield was obtained when higher culture densities were used but not necessarily when more calcium formate was added. This was mainly due to salt inhibition of the bacterial activity at a high calcium formate concentration. A maximum 0.67 ± 0.03 g of CaCO3 g of Ca(CHOOH)2(-1) calcium carbonate precipitate yield was obtained when a culture of 10(9) cells ml(-1) and 5 g of calcium formate liter(-)1 were used. Compared to the current strategy employing biogenic urea degradation as the basis for MICP, our approach presents significant improvements in the environmental sustainability of the application in the construction industry. PMID:24837386

  15. Effects of DPPC/Cholesterol liposomes on the properties of freshly precipitated calcium carbonate.

    PubMed

    Szcześ, A

    2013-01-01

    DPPC/Cholesterol liposomes of average diameter below 100nm were used as a matrix for calcium carbonate precipitation. Adsorption of calcium ions on the vesicles was determined via zeta potential measurement. It was found that with increasing calcium ions concentration the electrokinetic potential of the vesicles varied toward more positive values. The changes became smaller with the cholesterol content increase. Accumulation of calcium ions close to the vesicles membranes lead to attraction of CO(3)(2-) ions and enhances nucleation and growth of small calcium carbonate crystals that aggregates within lipid vesicles forming porous balls aggregates. However, dipalmitoylphosphatidylcholine (DPPC) does not change the CaCO(3) crystal forms and calcite is the only form obtained during precipitation. Moreover, the influence of the phospholipid on the calcium carbonate precipitation is enhanced by the induction of cholesterol to the lipid membranes. PMID:22796770

  16. Carbon nanotube-amorphous silicon hybrid solar cell with improved conversion efficiency.

    PubMed

    Funde, Adinath M; Nasibulin, Albert G; Syed, Hashmi Gufran; Anisimov, Anton S; Tsapenko, Alexey; Lund, Peter; Santos, J D; Torres, I; Gandía, J J; Cárabe, J; Rozenberg, A D; Levitsky, Igor A

    2016-05-01

    We report a hybrid solar cell based on single walled carbon nanotubes (SWNTs) interfaced with amorphous silicon (a-Si). The high quality carbon nanotube network was dry transferred onto intrinsic a-Si forming Schottky junction for metallic SWNT bundles and heterojunctions for semiconducting SWNT bundles. The nanotube chemical doping and a-Si surface treatment minimized the hysteresis effect in current-voltage characteristics allowing an increase in the conversion efficiency to 1.5% under an air mass 1.5 solar spectrum simulator. We demonstrated that the thin SWNT film is able to replace a simultaneously p-doped a-Si layer and transparent conductive electrode in conventional amorphous silicon thin film photovoltaics. PMID:27005494

  17. Carbon nanotube-amorphous silicon hybrid solar cell with improved conversion efficiency

    NASA Astrophysics Data System (ADS)

    Funde, Adinath M.; Nasibulin, Albert G.; Gufran Syed, Hashmi; Anisimov, Anton S.; Tsapenko, Alexey; Lund, Peter; Santos, J. D.; Torres, I.; Gandía, J. J.; Cárabe, J.; Rozenberg, A. D.; Levitsky, Igor A.

    2016-05-01

    We report a hybrid solar cell based on single walled carbon nanotubes (SWNTs) interfaced with amorphous silicon (a-Si). The high quality carbon nanotube network was dry transferred onto intrinsic a-Si forming Schottky junction for metallic SWNT bundles and heterojunctions for semiconducting SWNT bundles. The nanotube chemical doping and a-Si surface treatment minimized the hysteresis effect in current-voltage characteristics allowing an increase in the conversion efficiency to 1.5% under an air mass 1.5 solar spectrum simulator. We demonstrated that the thin SWNT film is able to replace a simultaneously p-doped a-Si layer and transparent conductive electrode in conventional amorphous silicon thin film photovoltaics.

  18. A near-wearless and extremely long lifetime amorphous carbon film under high vacuum

    PubMed Central

    Wang, Liping; Zhang, Renhui; Jansson, Ulf; Nedfors, Nils

    2015-01-01

    Prolonging wear life of amorphous carbon films under vacuum was an enormous challenge. In this work, we firstly reported that amorphous carbon film as a lubricant layer containing hydrogen, oxygen, fluorine and silicon (a-C:H:O:F:Si) exhibited low friction (~0.1), ultra-low wear rate (9.0 × 10–13 mm3 N–1 mm–1) and ultra-long wear life (>2 × 106 cycles) under high vacuum. We systematically examined microstructure and composition of transfer film for understanding of the underlying frictional mechanism, which suggested that the extraordinarily excellent tribological properties were attributed to the thermodynamically and structurally stable FeF2 nanocrystallites corroborated using first-principles calculations, which were induced by the tribochemical reaction. PMID:26059254

  19. In Situ Mechanical Property Measurements of Amorphous Carbon-Boron Nitride Nanotube Nanostructures

    NASA Technical Reports Server (NTRS)

    Kim, Jae-Woo; Lin, Yi; Nunez, Jennifer Carpena; Siochi, Emilie J.; Wise, Kristopher E.; Connell, John W.; Smith, Michael W.

    2011-01-01

    To understand the mechanical properties of amorphous carbon (a-C)/boron nitride nanotube (BNNT) nanostructures, in situ mechanical tests are conducted inside a transmission electron microscope equipped with an integrated atomic force microscope system. The nanotube structure is modified with amorphous carbon deposited by controlled electron beam irradiation. We demonstrate multiple in situ tensile, compressive, and lap shear tests with a-C/BNNT hybrid nanostructures. The tensile strength of the a-C/BNNT hybrid nanostructure is 5.29 GPa with about 90 vol% of a-C. The tensile strength and strain of the end-to-end joint structure with a-C welding is 0.8 GPa and 5.2% whereas the lap shear strength of the side-by-side joint structure with a-C is 0.25 GPa.

  20. In situ mechanical property measurements of amorphous carbon-boron nitride nanotube nanostructures

    NASA Astrophysics Data System (ADS)

    Kim, Jae-Woo; Carpena Núñez, Jennifer; Siochi, Emilie J.; Wise, Kristopher E.; Lin, Yi; Connell, John W.; Smith, Michael W.

    2012-01-01

    To understand the mechanical properties of amorphous carbon (a-C)/boron nitride nanotube (BNNT) nanostructures, in situ mechanical tests are conducted inside a transmission electron microscope equipped with an integrated atomic force microscope system. The nanotube structure is modified with amorphous carbon deposited by controlled electron beam irradiation. We demonstrate multiple in situ tensile, compressive, and lap shear tests with a-C/BNNT hybrid nanostructures. The tensile strength of the a-C/BNNT hybrid nanostructure is 5.29 GPa with about 90 vol% of a-C. The tensile strength and strain of the end-to-end joint structure with a-C welding is 0.8 GPa and 5.2% whereas the lap shear strength of the side-by-side joint structure with a-C is 0.25 GPa.

  1. Photo-oxidation of polymer-like amorphous hydrogenated carbon under visible light illumination

    SciTech Connect

    Baxamusa, Salmaan; Laurence, Ted; Worthington, Matthew; Ehrmann, Paul

    2015-11-10

    Amorphous hydrogenated carbon (a-C:H), a polymer-like network typically synthesized by plasma chemical vapor deposition, has long been understood to exhibit optical absorption of visible light (λ > 400 nm). In this report we explain that this absorption is accompanied by rapid photo-oxidation (within minutes) that behaves in most respects like classic polymer photo-oxidation with the exception that it occurs under visible light illumination rather than ultraviolet illumination.

  2. Vacuum ultraviolet photolysis of hydrogenated amorphous carbons . I. Interstellar H2 and CH4 formation rates

    NASA Astrophysics Data System (ADS)

    Alata, I.; Cruz-Diaz, G. A.; Muñoz Caro, G. M.; Dartois, E.

    2014-09-01

    Context. The interstellar hydrogenated amorphous carbons (HAC or a-C:H) observed in the diffuse medium are expected to disappear in a few million years, according to the destruction time scale from laboratory measurements. The existence of a-C:H results from the equilibrium between photodesorption, radiolysis, hydrogenation and resilience of the carbonaceous network. During this processing, many species are therefore injected into the gas phase, in particular H2, but also small organic molecules, radicals or fragments. Aims: We perform experiments on interstellar a-C:H analogs to quantify the release of these species in the interstellar medium. Methods: The vacuum ultraviolet (VUV) photolysis of interstellar hydrogenated amorphous carbon analogs was performed at low (10 K) to ambient temperature, coupled to mass-spectrometry detection and temperature-programed desorption. Using deuterium isotopic substitution, the species produced were unambiguously separated from background contributions. Results: The VUV photolysis of hydrogenated amorphous carbons leads to the efficient production of H2 molecules, but also to small hydrocarbons. Conclusions: These species are formed predominantly in the bulk of the a-C:H analog carbonaceous network, in addition to the surface formation. Compared with species made by the recombination of H atoms and physisorbed on surfaces, they diffuse out at higher temperatures. In addition to the efficient production rate, it provides a significant formation route in environments where the short residence time scale for H atoms inhibits H2 formation on the surface, such as PDRs. The photolytic bulk production of H2 with carbonaceous hydrogenated amorphous carbon dust grains can provide a very large portion of the contribution to the H2 molecule formation. These dust grains also release small hydrocarbons (such as CH4) into the diffuse interstellar medium, which contribute to the formation of small carbonaceous radicals after being dissociated

  3. Vacuum ultraviolet of hydrogenated amorphous carbons. II. Small hydrocarbons production in Photon Dominated Regions

    NASA Astrophysics Data System (ADS)

    Alata, I.; Jallat, A.; Gavilan, L.; Chabot, M.; Cruz-Diaz, G. A.; Munoz Caro, G. M.; Béroff, K.; Dartois, E.

    2015-12-01

    Context. Hydrogenated amorphous carbons (a-C:H) are a major component of the carbonaceous solids present in the interstellar medium. The production and existence of these grains is connected in particular with the balance between their photolysis, radiolysis, and hydrogenation. During grain processing, H2 and other small organic molecules, radicals, and fragments are released into the gas phase. Aims: We perform photolytic experiments on laboratory produced interstellar a-C:H analogues to monitor and quantify the release of species and compare to relevant observations in the interstellar medium. Methods: Hydrogenated amorphous carbon analogues at low temperature are exposed to ultraviolet (UV) photons, under ultra-high vacuum conditions. The species produced are monitored using mass spectrometry and post irradiation temperature-programmed desorption. Additional experiments are performed using deuterated analogues and the species produced are unambiguously separated from background contributions. We implement the laboratory measured yields for the released species in a time dependent model to investigate the effect of the UV photon irradiation of hydrogenated amorphous carbons in a photon dominated region, and estimate the associated time scale. Results: The UV photolysis of hydrogenated amorphous carbons leads to the production of H2 molecules and small hydrocarbons. The model shows that the photolytic evolution of a-C:Hs in photon dominated regions, such as the Horsehead Nebula, can raise the abundance of carbonaceous molecules by several orders of magnitude at intermediate visual extinctions, i.e., after the C+ maximum and before the dense cloud conditions prevail where models generally show a minimum abundance for such carbonaceous species. The injection time peak ranges from a thousand to ten thousand years in the models, considering only the destruction of such grains and no re-hydrogenation. This time scale is consistent with the estimated advection front of

  4. Co-precipitation of dissolved organic matter by calcium carbonate in Pyramid Lake, Nevada

    USGS Publications Warehouse

    Leenheer, Jerry A.; Reddy, Michael M.

    2008-01-01

    Our previous research has demonstrated that dissolved organic matter (DOM) influences calcium carbonate mineral formation in surface and ground water. To better understand DOM mediation of carbonate precipitation and DOM co-precipitation and/or incorporation with carbonate minerals, we characterized the content and speciation of DOM in carbonate minerals and in the lake water of Pyramid Lake, Nevada, USA. A 400-gram block of precipitated calcium carbonate from the Pyramid Lake shore was dissolved in 8 liters of 10% acetic acid. Particulate matter not dissolved by acetic acid was removed by centrifugation. DOM from the carbonate rock was fractionated into nine portions using evaporation, dialysis, resin adsorption, and selective precipitations to remove acetic acid and inorganic constituents. The calcium carbonate rock contained 0.23% DOM by weight. This DOM was enriched in polycarboxylic proteinaceous acids and hydroxy-acids in comparison with the present lake water. DOM in lake water was composed of aliphatic, alicyclic polycarboxylic acids. These compound classes were found in previous studies to inhibit calcium carbonate precipitation. DOM fractions from the carbonate rock were 14C-age dated at about 3,100 to 3,500 years before present. The mechanism of DOM co-precipitation and/or physical incorporation in the calcium carbonate is believed to be due to formation of insoluble calcium complexes with polycarboxylic proteinaceous acids and hydroxy-acids that have moderately large stability constants at the alkaline pH of the lake. DOM co-precipitation with calcium carbonate and incorporation in precipitated carbonate minerals removes proteinaceous DOM, but nearly equivalent concentrations of neutral and acidic forms of organic nitrogen in DOM remain in solution. Calcium carbonate precipitation during lime softening pretreatment of drinking water may have practical applications for removal of proteinaceous disinfection by-product precursors.

  5. Self-assembly of sp2 -bonded carbon nanostructures from amorphous precursors

    NASA Astrophysics Data System (ADS)

    Powles, R. C.; Marks, N. A.; Lau, D. W. M.

    2009-02-01

    Pure carbon phases such as fullerenes, nanotubes, and graphite are archetypal examples of the self-organizing capability of sp2 -bonded carbon. Naturally occurring phenomena and a wide variety of experimental apparatus are known to produce highly ordered sp2 -bonded carbons if the temperature or energy of the process is sufficiently high. Here we present molecular-dynamics simulations of sp2 ordering using highly disordered amorphous carbon precursors. Using the environment-dependent interaction potential to describe the interatomic forces, we show that ordered sp2 phases spontaneously arise upon heating at elevated temperatures. We identify two principal factors which control the collective organization: (i) the geometry of the system, in which clusters lead to onions, rods lead to nanotubes, and so on, and (ii) the effect of density, through which voids and internal surfaces control both local and long-range temporal evolutions. The simulations also shed light on the thermal stability of tetrahedral amorphous carbon and a fullerene-based structural model for glassy carbon.

  6. The effect of Argon ion irradiation on the thickness and structure of ultrathin amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Xie, J.; Komvopoulos, K.

    2016-03-01

    Carbon films synthesized by plasma-enhanced chemical vapor deposition (PECVD) and filtered cathodic vacuum arc (FCVA) exhibit a layered structure consisting of a bottom (interface) and a top (surface) layer rich in sp2 atomic carbon bonding and a middle (bulk) layer of much higher sp3 content. Because of significant differences in the composition, structure, and thickness of these layers, decreasing the film thickness may negatively affect its properties. In this study, transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) were used to examine the effect of Ar+ ion irradiation on the structure and thickness of ultrathin films of hydrogenated amorphous carbon (a-C:H) and hydrogen-free amorphous carbon (a-C) deposited by PECVD and FCVA, respectively. The TEM and EELS results show that 2-min ion irradiation decreases the film thickness without markedly changing the film structure and composition, whereas 4-min ion irradiation results in significant film thinning and a moderate decrease of the sp3 content of the bulk layer. This study demonstrates that Ar+ ion irradiation is an effective post-deposition process for reducing the thickness and tuning the structure of ultrathin carbon films. This capability has direct implications in the synthesis of ultrathin protective carbon overcoats for extremely high-density magnetic recording applications.

  7. Understanding the interaction of amorphous calcium polyphosphate with aqueous environments to optimize its use as a localized drug delivery matrix

    NASA Astrophysics Data System (ADS)

    Djogbenou, Nancy

    Amorphous calcium polyphosphate (CPP) shows potential as an implantable drug delivery matrix through a simple gelling protocol that has been shown to eliminate burst release and extend drug release time from the matrix. The nature of the interaction of CPP with aqueous environments and different drugs is not yet well understood. For this reason, CPP samples were manufactured using two different methods: the established gelation protocol, with and without drug, and mixing CPP with different volumes of aqueous solutions to better understand the effect of water exposure on the structural and drug release properties of CPP. Exposure to aqueous systems caused a reduction in the chain length of CPP that was dependant on gel time and mode of exposure. Longer gel times or increased volume of water used during exposure also caused the formation of crystalline material upon drying. In general, drug release was a function of aqueous exposure and the therapeutic agent used. Drug elution studies showed an increase in the burst release of vancomycin (VCM) from CPP gelled for extended periods. When total gel time was 10 hours or below samples that were gelled for only a short time during drug loading performed best. CPP loaded with BSA had a much slower release rate than VCM and appeared to release BSA by a different mechanism. Overall, this thesis shows that CCP drug delivery matrices can be produced with tailored properties simply by controlling processing conditions.

  8. A comparative evaluation of remineralizing ability of bioactive glass and amorphous calcium phosphate casein phosphopeptide on early enamel lesion

    PubMed Central

    Palaniswamy, Udaya Kumar; Prashar, Neha; Kaushik, Mamta; Lakkam, Surender Ram; Arya, Shikha; Pebbeti, Swetha

    2016-01-01

    Background: This study was done to evaluate remineralizing potential of bioactive glasses (BAGs) and amorphous calcium phosphate-casein phosphopeptide (ACP-CPP) on early enamel lesion. Materials and Methods: Twenty freshly extracted mandibular premolars were sectioned sagittally. The buccal half was impregnated in acrylic resin blocks and treated with 37% phosphoric acid in liquid form, to demineralize enamel surface to simulate early enamel lesion. The samples were divided into two groups. The samples in Group I were treated with ACP-CPP (GC Tooth Mousse) and in Group II with BAG (Sensodyne Repair and Protect) and stored in saliva to prevent dehydration. The samples were tested for microhardness. The data obtained was analyzed using ANOVA post hoc multiple comparison and independent sample t- test and presented as a mean and standard deviation. Results: All the samples showed a decrease in the microhardness after demineralization. After application of remineralizing agents, Group II showed a highly significant increase in the microhardness (P < 0.05) after 10 days, while Group I showed a significant increase in microhardness after 15 days (P < 0.05). Conclusion: Both the remineralizing agents tested in this study can be considered effective in repair and prevention of demineralization. BAG showed better results initially, but eventually both have similar remineralizing potential. PMID:27605985

  9. Combining casein phosphopeptide-amorphous calcium phosphate with fluoride: synergistic remineralization potential of artificially demineralized enamel or not?

    NASA Astrophysics Data System (ADS)

    Elsayad, Iman; Sakr, Amal; Badr, Yahia

    2009-07-01

    Recaldent is a product of casein phosphopeptide-amorphous calcium phosphate (CPP-ACP). The remineralizing potential of CPP-ACP per se, or when combined with 0.22% Fl gel on artificially demineralized enamel using laser florescence, is investigated. Mesial surfaces of 15 sound human molars are tested using a He-Cd laser beam at 441.5 nm with 18-mW power as an excitation source on a suitable setup based on a Spex 750-M monochromator provided with a photomultiplier tube (PMT) for detection of collected autofluorescence from sound enamel. Mesial surfaces are subjected to demineralization for ten days. The spectra from demineralized enamel are measured. Teeth are divided into three groups according to the remineralizing regimen: group 1 Recaldent per se, group 2 Recaldent combined with fluoride gel and ACP, and group 3 artificial saliva as a positive control. After following these protocols for three weeks, the spectra from the remineralized enamel are measured. The spectra of enamel autofluorescence are recorded and normalized to peak intensity at about 540 nm to compare spectra from sound, demineralized, and remineralized enamel surfaces. A slight red shift occurred in spectra from demineralized enamel, while a blue shift may occur in remineralized enamel. Group 2 shows the highest remineralizing potential. Combining fluoride and ACP with CPP-ACP can give a synergistic effect on enamel remineralization.

  10. Role of casein phosphopeptide amorphous calcium phosphate in remineralization of white spot lesions and inhibition of Streptococcus mutans?

    PubMed Central

    Vashisht, Ruchi; Indira, Rajamani; Ramachandran, S; Kumar, Anil; Srinivasan, Manali Ramakrishnan

    2013-01-01

    Introduction: To promote the remineralization by ionic exchange mechanism instead of invasive techniques many remineralizing agents can be used. Objective: To evaluate the remineralization effects of casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) on white spot lesions (WSLs) and its inhibitory effect on Streptococcus mutans colonization. Materials and Methods: The study group consisted of 60 subjects exhibiting at least 1-WSL. Subjects were randomly divided into 2 groups: A test group using CPP-ACP cream (GC-Tooth Mousse, Leuven, Belgium) and a control group using only fluoride containing toothpaste for a period of 3-month. Baseline WSLs were scored using DIAGNOdent device (KaVo Germany) and the saliva samples were collected to measure S. mutans counts. After the 3-month period the WSLs were again recorded and the saliva collection was repeated. Result: DIAGNOdent measurements were increased by time (P = 0.002) in the control group and no statistically significant difference (P = 0.217) was found in the test group by the 3-month period. In both groups, the mutans counts were decreased in the 3-month experimental period. Conclusion: These clinical and laboratory results suggested that CPP-ACP containing cream had a slight remineralization effect on the WSL in the 3-month evaluation period however, longer observation is recommended to confirm whether the greater change in WSLs is maintained. PMID:23956538

  11. Contact nanofatigue shows crack growth in amorphous calcium phosphate on Ti, Co-Cr and Stainless steel.

    PubMed

    Saber-Samandari, Saeed; Gross, Karlis A

    2013-03-01

    Fatigue testing of load-bearing coated implants is usually very time-consuming and so a new contact nanofatigue test using a nanoindenter has been evaluated. A cube corner indenter provided the fastest indication of failure, through crack formation, compared to a spherical indenter. Contact nanofatigue was performed on a sintered hydroxyapatite and then on amorphous calcium phosphate splats produced on titanium, stainless steel and Co-Cr surfaces, made either at room temperature or on 250°C preheated surfaces. Sintered hydroxyapatite showed continual plastic deformation, but this is not that apparent for splats on metal surfaces. Substrate preheating was found to induce cracking in splats, explained by greater thermal residual stresses. Endurance during contact nanofatigue, measured as time to crack formation, was the lowest for splats on titanium followed by Co-Cr and stainless steel. The splat on titanium showed both cracking and plastic deformation during testing. Good agreement has been reached with previous studies with cracking directed to the substrate without splat delamination. Contact nanofatigue with the nanoindenter easily and quickly identifies cracking events that previously required detection with acoustic emission, and shows good feasibility for mechanical testing of discs and splats produced by thermal spraying, spray forming, laser-ablation, aerosol jet and ink jet printing. PMID:23164945

  12. The effect of two types chewing gum containing casein phosphopeptide-amorphous calcium phosphate and xylitol on salivary Streptococcus mutans

    PubMed Central

    Emamieh, Shila; Khaterizadeh, Yosra; Goudarzi, Hossein; Ghasemi, Amir; Baghban, Alireza Akbarzadeh; Torabzadeh, Hasan

    2015-01-01

    Aim: The aim was to evaluate the effect of sugar-free chewing gum containing casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) and xylitol on salivary Streptococcus mutans. Materials and Methods: A total of 60 dental students of 20-25 years old, who volunteered after checking their health condition and signing an informed consent, were randomly allocated to receive one of the following interventions: (A) Chewing gum containing CPP-ACP; (B) containing xylitol. Subjects within the experimental groups were taken the gums 3 times daily, after each meal for a period of 3 weeks. Pre- and post-intervention unstimulated saliva samples were quantified for S. mutans counts. Results: A statistically significant reduction of salivary S. mutans was displayed in both groups A and B after the intervention when compared with baseline (P < 0.001), and group A shows more statistically significant reduction of salivary S. mutans than group B (P = 0.011). Conclusion: Daily consumption of chewing gum containing CPP-ACP and xylitol significantly reduces the level of salivary S. mutans, but chewing gum containing CPP-ACP can reduce the level of salivary S. mutans in more than xylitol chewing gum. PMID:26069402

  13. Symposium Report. Battery materials : amorphous carbons and polymer electrolytes.

    SciTech Connect

    Gerald, R. E., II; Chemical Engineering

    2000-01-01

    results of a solid electrolyte system composed of LiI dissolved in PEO. Work on oriented polymer electrolyte samples is ongoing. Yuri Andreev (U. of St. Andrews) gave a historical overview of a number of crystal structures of polymer electrolytes solved using XRD in the group of Peter Bruce. The last speaker of the symposium was Peter Papanek (U. of Pennsylvania). He spoke about various disordered carbon materials used as anodes in Li-ion batteries. He also described his inelastic neutron scattering studies of carbon materials derived from pyrolyzed epoxy novolak resins. His data supports the graphene sheet model and is also consistent with calculations of interior and edge carbon atoms in pyrene that chemically reacted with lithium.

  14. Disorder and density of defects in hydrogenated amorphous silicon-carbon

    NASA Astrophysics Data System (ADS)

    Boulitrop, F.; Bullot, J.; Gauthier, M.; Schmidt, M. P.; Catherine, Y.

    1985-04-01

    We report subgap absorption measurements by photothermal deflection spectroscopy in a-Si 1- xC x: H alloys in the whole range of composition. We observe that incorporation of carbon in the silicon matrix increases both the inverse of the slope of the exponential absorption tail (which is due to the valence band tail) and the subgap absorption around 1.3 eV (due to defects). This result is correlated with former results on the broadening of the conduction band tail deduced from transport measurements in these alloys. It is concluded that carbon incorporation induces disorder and defect creation in the amorphous silicon matrix.

  15. Plasma-deposited amorphous hydrogenated carbon films and their tribological properties

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Pouch, J. J.; Alterovitz, S. A.

    1989-01-01

    Recent work on the properties of diamondlike carbon films and their dependence on preparation conditions are reviewed. The results of the study indicate that plasma deposition enables one to deposit a variety of amorphous hydrogenated carbon (a-C:H) films exhibiting more diamondlike behavior to more graphitic behavior. The plasma-deposited a-C:H can be effectively used as hard, wear-resistant, and protective lubricating films on ceramic materials such as Si(sub 3)N(sub 4) under a variety of environmental conditions such as moist air, dry nitrogen, and vacuum.

  16. Plasma-deposited amorphous hydrogenated carbon films and their tribological properties

    NASA Technical Reports Server (NTRS)

    Miyoshi, Kazuhisa; Pouch, John J.; Alterovitz, Samuel A.

    1989-01-01

    Recent work on the properties of diamondlike carbon films and their dependence on preparation conditions are reviewed. The results of the study indicate that plasma deposition enables one to deposit a variety of amorphous hydrogenated carbon (a-C:H ) films exhibiting more diamondlike behavior to more graphitic behavior. The plasma-deposited a-C:H can be effectively used as hard, wear-resistant, and protective lubricating films on ceramic materials such as Si(sub 3)N(sub 4) under a variety of environmental conditions such as moist air, dry nitrogrn, and vacuum.

  17. Extraction of radiostrontium coprecipitated with calcium carbonate in soil

    SciTech Connect

    Spalding, B.P.

    1985-01-01

    The fraction of soil ZSr coprecipitated with calcium carbonate (CaCO3) was determined by extraction into 0.1M hydrochloric acid (HCl)-0.5M potassium chloride (KCl) after an initial extraction with either 1M ammonium acetate (NH4OAc) or 1M KCl to remove soluble salts and exchangeable cations. This procedure was tested on soil samples supplemented with 85 g CaCO3/kg containing coprecipitated YVSr. A significant amount of both YVSr and Ca remained undissolved in this extractant but were subsequently removed by extraction with 8M HNO3. The extraction procedure was also applied to a group of 16 ZSr-contaminated soil and stream bed sediment samples. The amount of Cs + Mg extracted by 0.1M HCl-0.5M KCl, following KCl extraction, was well correlated with but slightly lower than the amounts expected for a complete dissolution of the CaCO3. Pre-extraction with NH4OAc, rather than KCl, dissolved significantly more CaCO3, resulting in a lower estimate of the soil CaCO3. Several soil samples, taken from a radioactive waste burial trench that had received sodium carbonate (Na2CO3) treatment injections, revealed that up to 98% of the total ZSr was observed in a CaCO3 phase. Untreated soils typically exhibited 80 to 95% of their ZSr in a cation exchangeable form, i.e., extractable by either NH4OAc or KCl.

  18. Synthesis and Optical Enhancement of Amorphous Carbon Nanotubes/Silver Nanohybrids via Chemical Route at Low Temperature

    PubMed Central

    Han, Tan Kim; Fen, Leo Bey; Nee, Ng Meng; Johan, Mohd Rafie

    2014-01-01

    We report the synthesis of amorphous carbon nanotubes/silver (αCNTs/Ag) nanohybrids via simple chemical route without additional reactant and surfactant at low temperature. Field emission scanning microscope (FESEM) and transmission electron microscope (TEM) confirmed formation of CNTs. X-ray diffraction (XRD) pattern confirmed the amorphous phase of carbon and the formation of Ag nanoparticles crystalline phase. Raman spectra revealed the amorphous nature of αCNTs. UV-visible spectroscopy showed enhancement of optical properties of αCNTs/Ag nanohybrids. PMID:24995365

  19. Importance of unburned coal carbon, black carbon, and amorphous organic carbon to phenanthrene sorption in sediments.

    PubMed

    Cornelissen, Gerard; Gustafsson, Orjan

    2005-02-01

    The aim of this paper was to estimate the contribution to total phenanthrene sorption from unburned coal and black carbon (BC; soot and charcoal) in sediment. We determined sorption isotherms for five Argonne Premium Coal standards over a wide concentration interval (0.01-10 000 ng/L). The coals showed strong and nonlinear sorption (carbon-normalized K(F) = 5.41-5.96; nF = 0.68-0.82). Coal sorption appeared to become more nonlinear with increasing coal maturity. The coal's specific surface area appeared to influence K(F). On the basis of the current coal sorption observations combined with earlier petrographic analyses and BC sorption experiments, we calculated for one particular sediment that coal, BC, and "other" OC were all important to PHE sorption in the environmentally relevant nanogram per liter range. This indicates that it is important to consider strong sorption to coal in the risk assessment of coal-impacted geosorbents (e.g., river beds) where coal is mined/shipped and manufactured gas plant sites. PMID:15757337

  20. Calcium in diet

    MedlinePlus

    ... of calcium dietary supplements include calcium citrate and calcium carbonate. Calcium citrate is the more expensive form of ... the body on a full or empty stomach. Calcium carbonate is less expensive. It is absorbed better by ...

  1. Hard and elastic amorphous carbon nitride thin films studied by 13C nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Gammon, W. J.; Malyarenko, D. I.; Kraft, O.; Hoatson, G. L.; Reilly, A. C.; Holloway, B. C.

    2002-10-01

    The chemical bonding of hard and elastic amorphous carbon nitride (a-CNx) thin films was examined using solid-state 13C NMR spectroscopy. The films were deposited by DC magnetron sputtering in a pure nitrogen discharge on Si(001) substrates at 300 °C. Nanoindentation tests reveal a recovery of 80%, a hardness of 5 GPa, and an elastic modulus of 47 GPa. This combination of low modulus and high strength means the material can be regarded as hard and elastic; the material gives when pressed on and recovers its shape when the load is released. The 13C NMR results conclusively demonstrate that hard and elastic a-CNx has an sp2 carbon bonded structure and that sp3 hybridized carbons are absent. Our results stand in contrast with earlier work that proposed that the interesting mechanical properties of hard and elastic a-CNx were due, in part, to sp3 bonded carbon.

  2. Calcium Carbonate Formation by Genetically Engineered Inorganic Binding Peptides

    NASA Astrophysics Data System (ADS)

    Gresswell, Carolyn Gayle

    Understanding how organisms are capable of forming (synthesize, crystallize, and organize) solid minerals into complex architectures has been a fundamental question of biomimetic materials chemistry and biomineralization for decades. This study utilizes short peptides selected using a cell surface display library for the specific polymorphs of calcium carbonate, i.e., aragonite and calcite, to identify two sets of sequences which can then be used to examine their effects in the formation, crystal structure, morphology of the CaCO3 minerals. A procedure of counter selection, along with fluorescence microscopy (FM) characterization, was adapted to insure that the sequences on the cells were specific to their respective substrate, i.e., aragonite or calcite. From the resulting two sets of sequences selected, five distinct strong binders were identified with a variety of biochemical characteristics and synthesized for further study. Protein derived peptides, using the known sequences of the proteins that are associated with calcite or aragonite, were also designed using a bioinformatics-based similarity analysis of the two sets of binders. In particular, an aragonite binding protein segment, AP7, a protein found in nacre, was chosen for this design and the resulting effects of the designed peptides and the AP7 were examined. Specifically, the binding affinities of the selected and the protein derived peptides off the cells were then tested using FM; these studies resulted in different binding characteristics of the synthesized and cellular bound peptides. Two of the peptides that displayed strong binding on the cells bound to neither of the CaCO 3 substrates and both the high and low similarity protein-derived peptides bound to both polymorphs. However, two of the peptides were found to only bind to their respective polymorph showing; these results are significant in that with this study it is demonstrated that the designed peptides based on experimental library

  3. Calcium carbonate corrosivity in an Alaskan inland sea

    NASA Astrophysics Data System (ADS)

    Evans, W.; Mathis, J. T.; Cross, J. N.

    2013-12-01

    Ocean acidification is the hydrogen ion increase caused by the oceanic uptake of anthropogenic CO2, and is a focal point in marine biogeochemistry, in part, because this chemical reaction reduces calcium carbonate (CaCO3) saturation states (Ω) to levels that are corrosive (i.e. Ω ≤ 1) to shell-forming marine organisms. However, other processes can drive CaCO3 corrosivity; specifically, the addition of tidewater glacier melt. To highlight this process, we present carbonate system data collected in May (spring) and September (autumn) starting 2009 through 2012 from Prince William Sound (PWS), a semi-enclosed inland sea located on the south-central coast of Alaska that is ringed with fjords containing tidewater glaciers. Initial sampling in PWS covered limited stations in the western sound, and Ω levels corrosive to aragonite, a form of CaCO3, were observed in association with glacial melt during autumn. Beginning in September 2011, expanded sampling spanned the western and central sound, and included two fjords proximal to tidewater glaciers: Icy Bay and Columbia Bay. The observed conditions in these fjords affected CaCO3 corrosivity in the upper water column (< 50 m) in PWS in two ways: (1) as spring-time formation sites of mode water with near-corrosive Ω levels seen below the mixed layer depth across the sound, and (2) as point sources for surface plumes of glacial melt with corrosive Ω levels (Ω for aragonite and calcite down to 0.60 and 1.02, respectively) and carbon dioxide partial pressures (pCO2) well below atmospheric levels. The cumulative effect of glacial melt is likely responsible for the seasonal widespread reduction of Ω in PWS; however, glacial melt-driven CaCO3 corrosivity is poorly reflected by pCO2 or pHT, indicating that any one of those carbonate parameters alone would inadequately track corrosive conditions in PWS. The unique conditions of the carbonate system in the surface glacial melt plumes enhances atmospheric CO2 uptake, which, if

  4. Enthalpy of formation of carbon-rich polymer-derived amorphous SiCN ceramics.

    SciTech Connect

    Morcos, R. M.; Mera, G.; Navrotsky, A.; Varga, T.; Riedel, R.; Poli, F.; Muller, K.; Materials Science Division; Univ. of California at Davis; Technische Univ. Darmstadt; Univ. of Stuttgart

    2008-10-01

    Carbon-rich silicon carbonitride (SiCN) ceramics derived from polysilylcarbodiimides represent a novel class of materials where the incorporation of a high amount of carbon was demonstrated to be beneficial for ultrahigh-temperature resistance against crystallization. Calorimetric measurements of heat of oxidative dissolution in a molten oxide solvent show that these amorphous SiCN ceramics produced at 1000 or 1100 C possess a small positive or near zero enthalpy of formation relative to their crystalline constituents, namely silicon nitride, silicon carbide, and graphite. The enthalpy of formation does not change strongly with increasing SiC mole fraction. Because the enthalpies of formation from crystalline constituents are at most slightly positive, and the entropies of formation are expected to be significantly positive because of disorder in the amorphous phase, it is likely that the free energies of formation from silicon carbide, silicon nitride, and graphite are negative and the high-temperature persistence of amorphous SiCN ceramics may originate from thermodynamic stabilization. However, this stabilization is less pronounced than that for SiCO polymer-derived ceramics studied earlier.

  5. Anomalous sound propagation and slow kinetics in dynamically compressed amorphous carbon

    NASA Astrophysics Data System (ADS)

    Reed, Evan J.; Maiti, Amitesh; Fried, Laurence E.

    2010-01-01

    We have performed molecular-dynamics simulations of dynamic compression waves propagating through amorphous carbon using the Tersoff potential and find that a variety of dynamic compression features appear for two different initial densities. These features include steady elastic shocks, steady chemically reactive shocks, unsteady elastic waves, and unsteady chemically reactive waves. We show how these features can be distinguished by analyzing time-dependent propagation speeds, time-dependent sound speeds, and comparison to multiscale shock technique (MSST) simulations. Understanding such features is a key challenge in quasi-isentropic experiments involving phase transformations. In addition to direct simulations of dynamic compression, we employ the MSST and find agreement with the direct method for this system for the shocks observed. We show how the MSST can be extended to include explicit material viscosity and demonstrate on an amorphous Lennard-Jones system.

  6. Silicon and aluminum doping effects on the microstructure and properties of polymeric amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoqiang; Hao, Junying; Xie, Yuntao

    2016-08-01

    Polymeric amorphous carbon films were prepared by radio frequency (R.F. 13.56 MHz) magnetron sputtering deposition. The microstructure evolution of the deposited polymeric films induced by silicon (Si) and aluminum(Al) doping were scrutinized through infrared spectroscopy, multi-wavelength Raman spectroscopy, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). The comparative results show that Si doping can enhance polymerization and Al doping results in an increase in the ordered carbon clusters. Si and Al co-doping into polymeric films leads to the formation of an unusual dual nanostructure consisting of cross-linked polymer-like hydrocarbon chains and fullerene-like carbon clusters. The super-high elasticity and super-low friction coefficients (<0.002) under a high vacuum were obtained through Si and Al co-doping into the films. Unconventionally, the co-doped polymeric films exhibited a superior wear resistance even though they were very soft. The relationship between the microstructure and properties of the polymeric amorphous carbon films with different elements doping are also discussed in detail.

  7. Vertical electric field stimulation of neural cells on porous amorphous carbon electrodes

    NASA Astrophysics Data System (ADS)

    Jain, Shilpee; Sharma, Ashutosh; Basu, Bikramjit

    2014-03-01

    We demonstrate the efficacy of amorphous macroporous carbon substrates as electrodes to stimulate neuronal cell proliferation in presence of external electric field. The electric field was applied perpendicular to carbon electrode, while growing mouse neuroblastoma (N2a) cells in vitro. The placement of the second electrode outside of the cell culture medium allows the investigation of cell response to electric field without the concurrent complexities of submerged electrodes such as potentially toxic electrode reactions, electro-kinetic flows and charge transfer (electrical current) in the cell medium. The macroporous carbon electrodes are uniquely characterized by a higher specific charge storage capacity (0.2 mC/cm2) and low impedance (3.3 k Ω at 1 kHz). When a uniform or a gradient electric field was applied perpendicular to the amorphous carbon substrate, it was found that the N2a cell viability and neurite length were higher at low electric field strengths (<= 2.5 V/cm) compared to that measured without an applied field (0 V/cm). Overall, the results of the present study unambiguously establish the uniform/gradient vertical electric field based culture protocol to stimulate neurite outgrowth and viability of nerve cells.

  8. Thermally induced transformations of amorphous carbon nanostructures fabricated by electron beam induced deposition.

    PubMed

    Kulkarni, Dhaval D; Rykaczewski, Konrad; Singamaneni, Srikanth; Kim, Songkil; Fedorov, Andrei G; Tsukruk, Vladimir V

    2011-03-01

    We studied the thermally induced phase transformations of electron-beam-induced deposited (EBID) amorphous carbon nanostructures by correlating the changes in its morphology with internal microstructure by using combined atomic force microscopy (AFM) and high resolution confocal Raman microscopy. These carbon deposits can be used to create heterogeneous junctions in electronic devices commonly known as carbon-metal interconnects. We compared two basic shapes of EBID deposits: dots/pillars with widths from 50 to 600 nm and heights from 50 to 500 nm and lines with variable heights from 10 to 150 nm but having a constant length of 6 μm. We observed that during thermal annealing, the nanoscale amorphous deposits go through multistage transformation including dehydration and stress-relaxation around 150 °C, dehydrogenation within 150-300 °C, followed by graphitization (>350 °C) and formation of nanocrystalline, highly densified graphitic deposits around 450 °C. The later stage of transformation occurs well below commonly observed graphitization for bulk carbon (600-800 °C). It was observed that the shape of the deposits contribute significantly to the phase transformations. We suggested that this difference is controlled by different contributions from interfacial footprints area. Moreover, the rate of graphitization was different for deposits of different shapes with the lines showing a much stronger dependence of its structure on the density than the dots. PMID:21319745

  9. The flame photometric determination of calcium in phosphate, carbonate, and silicate rocks

    USGS Publications Warehouse

    Kramer, H.

    1957-01-01

    A flame photometric method of determining calcium in phosphate, carbonate, and silicate locks has been developed Aluminum and phosphate interference was overcome by the addition of a large excess of magnesium. The method is rapid and suitable for routine analysis Results obtained are within ?? 2% of the calcium oxide content. ?? 1957.

  10. On diamond, graphitic and amorphous carbons in primitive extraterrestrial solar system materials

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Frans J. M.

    1990-01-01

    Carbon is among the most abundant elements in the universe and carbon chemistry in meteorites and comets is an important key to understanding many Solar System and interstellar processes. Yet, the mineralogical properties and interrelations between various structural forms of elemental carbon remain ambiguous. Crystalline elemental carbons include rhombohedral graphite, hexagonal graphite, cubic diamond, hexagonal diamond (i.e., lonsdaleite or carbon-2H) and chaoite. Elemental carbon also occurs as amorphous carbon and poorly graphitized (or turbostratic) carbon but of all the forms of elemental carbon only graphite is stable under physical conditions that prevail in small Solar System bodies and in the interstellar medium. The recent discovery of cubic diamond in carbonaceous chondrites and hexagonal diamond in chondritic interplanetary dust particles (IDPs) have created a renewed interest in the crystalline elemental carbons that were not formed by shock processes on a parent body. Another technique, Raman spectroscopy, confirms a widespread occurrence of disordered graphite in the Allende carbonaceous chondrite and in chondritic IDPs. Elemental carbons have also been identified by their characteristic K-edge features in electron energy loss spectra (EELS). However, the spectroscopic data do not necessarily coincide with those obtained by selected area electron diffraction (SAED). In order to interpret these data in terms of rational crystalline structures, it may be useful to consider the principles underlying electron diffraction and spectroscopic analyses. Electron diffraction depends on electron scattering, on the type of atom and the distance between atoms in a crystal lattice. Spectroscopic data are a function of the type of atom and the energy of bonds between atoms. Also, SAED is a bulk sampling technique when compared to techniques such as Raman spectroscopy or EELS. Thus, it appears that combined analyses provide contradictory results and that amorphous

  11. Growth Rate of Calcite Steps as a Function of Aqueous Calcium-to-Carbonate Ratio: Independent Attachment and Detachment of Calcium and Carbonate Ions

    SciTech Connect

    Stack, Andrew G; Grantham, Ms. Meg

    2010-01-01

    Growth rates of monolayer-height steps on the {1014} calcite surface have been measured as a function of the aqueous calcium-to-carbonate ratio. The maximum growth rates of the two common crystallographic orientations were found to deviate from the ideal stoichiometric ratio of 1:1, and dissolution features were observed under supersaturated solutions containing high calcium-to-carbonate ratios. To explain these phenomena, a theory is applied that treats the rates of attachment and detachment of aqueous calcium and carbonate ions separately. The resultant attachment rate constants are 1-3 orders of magnitude smaller than the water exchange rate of the constituent aqueous ions, suggesting that ligand-exchange processes may directly drive attachment. The broader implication is that the saturation state alone is not adequate to fully describe the rates of the multiple, independent reactions that occur on mineral surfaces under these conditions.

  12. Calcium carbonate corrosivity in an Alaskan inland sea

    NASA Astrophysics Data System (ADS)

    Evans, W.; Mathis, J. T.; Cross, J. N.

    2014-01-01

    Ocean acidification is the hydrogen ion increase caused by the oceanic uptake of anthropogenic CO2, and is a focal point in marine biogeochemistry, in part, because this chemical reaction reduces calcium carbonate (CaCO3) saturation states (Ω) to levels that are corrosive (i.e., Ω ≤ 1) to shell-forming marine organisms. However, other processes can drive CaCO3 corrosivity; specifically, the addition of tidewater glacial melt. Carbonate system data collected in May and September from 2009 through 2012 in Prince William Sound (PWS), a semienclosed inland sea located on the south-central coast of Alaska and ringed with fjords containing tidewater glaciers, reveal the unique impact of glacial melt on CaCO3 corrosivity. Initial limited sampling was expanded in September 2011 to span large portions of the western and central sound, and included two fjords proximal to tidewater glaciers: Icy Bay and Columbia Bay. The observed conditions in these fjords affected CaCO3 corrosivity in the upper water column (< 50 m) in PWS in two ways: (1) as spring-time formation sites of mode water with near-corrosive Ω levels seen below the mixed layer over a portion of the sound, and (2) as point sources for surface plumes of glacial melt with corrosive Ω levels (Ω for aragonite and calcite down to 0.60 and 1.02, respectively) and carbon dioxide partial pressures (pCO2) well below atmospheric levels. CaCO3 corrosivity in glacial melt plumes is poorly reflected by pCO2 or pHT, indicating that either one of these carbonate parameters alone would fail to track Ω in PWS. The unique Ω and pCO2 conditions in the glacial melt plumes enhances atmospheric CO2 uptake, which, if not offset by mixing or primary productivity, would rapidly exacerbate CaCO3 corrosivity in a positive feedback. The cumulative effects of glacial melt and air-sea gas exchange are likely responsible for the seasonal reduction of Ω in PWS, making PWS highly sensitive to increasing atmospheric CO2 and amplified Ca

  13. Casein Phosphopeptide-Amorphous Calcium Phosphate Reduces Streptococcus mutans Biofilm Development on Glass Ionomer Cement and Disrupts Established Biofilms.

    PubMed

    Dashper, Stuart G; Catmull, Deanne V; Liu, Sze-Wei; Myroforidis, Helen; Zalizniak, Ilya; Palamara, Joseph E A; Huq, N Laila; Reynolds, Eric C

    2016-01-01

    Glass ionomer cements (GIC) are dental restorative materials that are suitable for modification to help prevent dental plaque (biofilm) formation. The aim of this study was to determine the effects of incorporating casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) into a GIC on the colonisation and establishment of Streptococcus mutans biofilms and the effects of aqueous CPP-ACP on established S mutans biofilms. S. mutans biofilms were either established in flow cells before a single ten min exposure to 1% w/v CPP-ACP treatment or cultured in static wells or flow cells with either GIC or GIC containing 3% w/w CPP-ACP as the substratum. The biofilms were then visualised using confocal laser scanning microscopy after BacLight LIVE/DEAD staining. A significant decrease in biovolume and average thickness of S. mutans biofilms was observed in both static and flow cell assays when 3% CPP-ACP was incorporated into the GIC substratum. A single ten min treatment with aqueous 1% CPP-ACP resulted in a 58% decrease in biofilm biomass and thickness of established S. mutans biofilms grown in a flow cell. The treatment also significantly altered the structure of these biofilms compared with controls. The incorporation of 3% CPP-ACP into GIC significantly reduced S. mutans biofilm development indicating another potential anticariogenic mechanism of this material. Additionally aqueous CPP-ACP disrupted established S. mutans biofilms. The use of CPP-ACP containing GIC combined with regular CPP-ACP treatment may lower S. mutans challenge. PMID:27589264

  14. Casein phosphopeptide-amorphous calcium phosphate incorporated into sugar confections inhibits the progression of enamel subsurface lesions in situ.

    PubMed

    Walker, G D; Cai, F; Shen, P; Adams, G G; Reynolds, C; Reynolds, E C

    2010-01-01

    Casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) has been demonstrated to exhibit anticariogenic activity in randomized, controlled clinical trials of sugar-free gum and a tooth cream. Two randomized, double-blind, crossover studies were conducted to investigate the potential of CPP-ACP added to hard candy confections to slow the progression of enamel subsurface lesions in an in situ model. The confections studied were: (1) control sugar (65% sucrose + 33% glucose syrup); (2) control sugar-free; (3) sugar + 0.5% (w/w) CPP-ACP; (4) sugar + 1.0% (w/w) CPP-ACP; (5) sugar-free + 0.5% (w/w) CPP-ACP. Participants (10 and 14 in study 1 and 2) wore a removable palatal appliance containing enamel half-slabs with subsurface lesions, except for meals and oral hygiene procedures, and consumed 1 confection 6 times a day for 10 days. The enamel half-slabs were inset to allow the development of plaque on the enamel surface. Participants rested for 1 week before crossing over to another confection. The appliances were stored in a humid container at 37 degrees C when not in the mouth. After each treatment period, the enamel half-slabs were removed, paired with their demineralized control half-slabs, embedded, sectioned and then analysed using transverse microradiography. In both studies consumption of the control sugar confection resulted in significant demineralization (progression) of the enamel subsurface lesions. However, consumption of the sugar confections containing CPP-ACP did not result in lesion progression, but in fact in significant remineralization (regression) of the lesions. Remineralization by consumption of the sugar + 1.0% CPP-ACP confection was significantly greater than that obtained with the sugar-free confection. PMID:20090326

  15. Amorphous calcium phosphate nanoparticles could function as a novel cancer therapeutic agent by employing a suitable targeted drug delivery platform

    PubMed Central

    2013-01-01

    Employment of nanovehicular system for delivering apoptogenic agent to cancer cells for inducing apoptosis has widely been investigated. Loading efficacy and controlled release of the agents are of the inseparable obstacles that hamper the efforts in reaching an efficacious targeted cancer therapy method. When the carrier itself is apoptogenic, then there is no need to load the carrier with apoptogenic agent and just delivering of the particle to the specific location matters. Hence, we hypothesize that amorphous calcium phosphate nanoparticle (ACPN) is a potent candidate for apoptosis induction, although encapsulation in liposome shell, and surface decoration with targeting ligand (TL), and cell-penetrating peptide (CPP) plays a pivotal role in the employment of this agent. It is well understood that elevation in cytosolic Ca2+ ([Ca2+]c) would result in the induction of apoptosis. ACPN has the potential to cause imbalance in this medium by elevating [Ca2+]c. Owning to the fact that the nanoparticles should be delivered into cytosol, it is necessary to trap them in a liposomal shell for evading endocytosis. It was demonstrated that employment of the trans-activator of transcription (TAT) as CPP eminently enhances the efficacy of endosomal escape; therefore, the platform is designed in a way that TAT is positioned on the surface of the liposome. Due to the fact that the apoptosis should be induced in sole cancer cells, Folate as TL is also attached on the surface of the liposome. This hypothesis heralds the new generation of chemotherapeutic agents and platforms which could have less side effect than the most common ones, in addition to other advantages they have. PMID:24172080

  16. In-Vitro Effect of Casein Phosphopeptide Amorphous Calcium Phosphate on Enamel Susceptibility to Staining by Tea during Bleaching Treatment

    PubMed Central

    Alaghemand, Homayoom; Hashemi Kamangar, Sedighe Sadat; Zarenegad, Nafiseh; Tabari, Negin; Khafri, Soraya

    2015-01-01

    Objectives: Bleached enamel is more susceptible to staining, and application of remineralizing agents may decrease enamel susceptibility to staining. This study sought to assess the effect of casein phosphopeptide amorphous calcium phosphate (CPP-ACP) on enamel susceptibility to staining during bleaching treatment. Materials and Methods: Forty central and lateral incisors and first premolar teeth were evaluated in four groups of 10. Group one specimens were subjected to in-office bleaching. Group two underwent in-office bleaching followed by surface treatment with CPP-ACP. Group three specimens received home bleaching and group four underwent home bleaching followed by CPP-ACP surface treatment. After each course of daily bleaching, specimens were immersed in tea solution. Home bleaching (15% carbamide peroxide) was performed for 14 days and in-office bleaching (40% hydrogen peroxide) was carried out in two sessions with an eight-day interval. The color of specimens was analyzed at baseline and post-intervention using Easy Shade Shade-Selection Device. Two-way ANOVA was used to evaluate the effects of bleaching type and surface treatment on color change. Then, the means were compared by Tukey’s HSD test (P=0.05). Results: The interaction effect of surface treatment and type of bleaching was not significant on any color parameter (P>0.05). Surface treatment had significant effects on ΔL (P=0.004). Type of bleaching had a significant effect on “b” parameter (P=0.00). The effect of bleaching type on ΔE was significant (P=0.00) but the effect of surface treatment was not (P=0.34). Conclusion: CPP-ACP had no significant effect on preventing enamel staining by tea during bleaching treatment. PMID:27123021

  17. Controlled degradation pattern of hydroxyapatite/calcium carbonate composite microspheres.

    PubMed

    Yang, Ning; Zhong, Qiwei; Zhou, Ying; Kundu, Subhas C; Yao, Juming; Cai, Yurong

    2016-06-01

    Hydroxyapatite (HAP) is widely used in clinic due to its good biocompatibility and osteoconductivity except for its slow degradation speed. In the present study, spherical calcium carbonate (CaCO3 ) is fabricated in the presence of silk protein sericin, which is transmuted into HAP microsphere in phosphate solution with the assistance of microwave irradiation. The effect of reaction conditions on the conversion of CaCO3 is investigated including reaction time, chemical composition of phosphate solution, and microwave power to get a series of HAP/CaCO3 composites. The degradation property of the composites is evaluated in vitro. Results show the degradation speed of the composite with higher HAP content is slower. The degradation rate of the composite could be changed effectively by modulating the proportion of HAP and CaCO3 . This work provides a feasible method for the preparation of spherical HAP/CaCO3 composite with controllable degradability. The composite thus obtained may be an ideal material for bone tissue engineering application. Microsc. Res. Tech. 79:518-524, 2016. © 2016 Wiley Periodicals, Inc. PMID:27037606

  18. Crystal growth of calcium carbonate in silk fibroin/sodium alginate hydrogel

    NASA Astrophysics Data System (ADS)

    Ming, Jinfa; Zuo, Baoqi

    2014-01-01

    As known, silk fibroin-like protein plays a pivotal role during the formation of calcium carbonate (CaCO3) crystals in the nacre sheets. Here, we have prepared silk fibroin/sodium alginate nanofiber hydrogels to serve as templates for calcium carbonate mineralization. In this experiment, we report an interesting finding of calcium carbonate crystal growth in the silk fibroin/sodium alginate nanofiber hydrogels by the vapor diffusion method. The experimental results indicate calcium carbonate crystals obtained from nanofiber hydrogels with different proportions of silk fibroin/sodium alginate are mixture of calcite and vaterite with unusual morphologies. Time-dependent growth study was carried out to investigate the crystallization process. It is believed that nanofiber hydrogels play an important role in the process of crystallization. This study would help in understanding the function of organic polymers in natural mineralization, and provide a novel pathway in the design and synthesis of new materials related unique morphology and structure.

  19. Synthesis of calcium carbonate nanocrystals and their potential application as vessels for drug delivery

    NASA Astrophysics Data System (ADS)

    Vergaro, Viviana; Carata, Elisabetta; Panzarini, Elisa; Baldassare, Francesca; Dini, Luciana; Ciccarella, Giuseppe

    2015-06-01

    Pure and stable calcium carbonate (CaCO3) nanocrystals were synthesized by spray drying method. We exploited the opportunity to use them as vessels for drug delivery studying the biocompatibility and the internalization in HeLa cells.

  20. Influence of the surfactant nature on the calcium carbonate synthesis in water-in-oil emulsion

    NASA Astrophysics Data System (ADS)

    Szcześ, Aleksandra

    2009-02-01

    Calcium carbonate has been precipitated from water-in-oil emulsions consisting of n-hexane/nonionic surfactant (Brij 30) and its mixture with cationic (DTAB) or anionic surfactant (SDS) to which calcium chloride and sodium carbonate were added. It was found that the surfactant kind and its amount can regulate the size, form and morphology of the precipitated particles. In case of nonionic surfactant the water/surfactant ratio is the most important parameter that allows to obtain small and regular calcium carbonate crystals. Addition of the DTAB results in different morphology of particles having the same crystal form, whereas addition of SDS changes the kind of emulsion from water-in-oil to oil-in-water. Moreover, light transmittance and backscattering light measurements have been used as a method to study the kinetics of calcium carbonate precipitation in emulsion systems.

  1. [Either calcium carbonate or sevelamer decreases urinary oxalate excretion in chronic renal failure patients].

    PubMed

    Caravaca, F; Ruiz, A B; Escola, J M; Hernández Gallego, R; Cerezo, I; Fernández, N; Barroso, S; Martín, M V

    2007-01-01

    The rate of oxalate absorbed from intestine is highly influenced by calcium intake in healthy subjects. It is unknown whether commonly used phosphate binders modify intestinal absorption and renal excretion of oxalate in chronic kidney disease (CKD) patients. This study aims to determine if calcium carbonate or sevelamer influences on urinary oxalate excretion. Twenty patients with CKD (stage 4 and 5 pre-dialysis) were included. Two treatment (1500 mg of calcium carbonate or 2400 mg of sevelamer), two-period (21 days each), crossover study with balanced assignment of the order of administration, and two washout periods were the main characteristics of this study design. Laboratory analyses in each phase included: serum creatinine, calcium, phosphorus, bicarbonate, total cholesterol, and 24 h urinary excretion of oxalate, creatinine, and urea. Creatinine clearance, protein catabolic rate (PNNA), total urinary oxalate excretion, and urinary oxalate / creatinine ratio were determined. Seventeen patients completed both treatment sequences. Total urinary oxalate excretion and urinary oxalate / creatinine ratios decreased significantly with respect to washout periods either after sevelamer or calcium carbonate treatment. The decrease in urinary oxalate excretion was greater after calcium carbonate (41.2+/-17.4%) than after sevelamer treatment (30.4+/-23.8%). There were not significant changes in renal function or PNNA values throughout the study periods. In conclusion, either calcium carbonate or sevelamer significantly reduces urinary oxalate excretion in CKD patients. Further studies will be needed to ascertain whether the type of phosphate binder influences on the accumulation of oxalate in CKD patients. PMID:17944584

  2. Calcium

    MedlinePlus

    ... body stores more than 99 percent of its calcium in the bones and teeth to help make and keep them ... in the foods you eat. Foods rich in calcium include Dairy products such as milk, cheese, and yogurt Leafy, green vegetables Fish with soft bones that you eat, such as canned sardines and ...

  3. Preparation of superior lubricious amorphous carbon films co-doped by silicon and aluminum

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoqiang; Hao, Junying; Yang, Jun; Zheng, Jianyun; Liang, Yongmin; Liu, Weimin

    2011-09-01

    Silicon (Si) and aluminum (Al) co-doped amorphous carbon films ((Si, Al)-C:H) were deposited on Si and stainless steel substrates by radio frequency (13.56 MHz) magnetron sputtering. The Al and Si were found to jointly regulate the hybridized carbon bonds. Mechanical properties of the films were detected by nano-indention and scratch tests. The nano-indention results revealed that all the samples exhibited good elastic recovery rate, among which the highest one was beyond 84%. Besides co-regulating the hybridizations of carbon, the co-doped Si and Al also had a common regulation on the mechanical and tribological properties. Especially, the film containing 1.6 at. % of Si and 0.9 at. % of Al showed a super-low friction (< 0.01) and a superior wear resistance in ambient air.

  4. Photovoltaic characteristics of Pd doped amorphous carbon film/SiO{sub 2}/Si

    SciTech Connect

    Ma Ming; Xue Qingzhong; Chen Huijuan; Zhou Xiaoyan; Xia Dan; Lv Cheng; Xie Jie

    2010-08-09

    The Pd doped amorphous carbon (a-C:Pd) films were deposited on n-Si substrates with or without a native SiO{sub 2} layer using magnetron sputtering. The photovoltaic characteristics of the a-C:Pd/SiO{sub 2}/Si and a-C:Pd/Si junctions were studied. It is found that under light illumination of 15 mW/cm{sup 2} at room temperature, the a-C:Pd/SiO{sub 2}/Si solar cell fabricated at 350 deg. C has a high power conversion efficiency of 4.7%, which is much better than the a-C/Si junctions reported before. The enhanced conversion efficiency is ascribed to the Pd doping and the increase in sp{sup 2}-bonded carbon clusters in the carbon film caused by the high temperature deposition.

  5. The influence of polyaspartate additive on the growth and morphology of calcium carbonate crystals

    NASA Astrophysics Data System (ADS)

    Gower, Laurie Anne

    The addition of low levels of polyaspartate to a supersaturated calcium carbonate (CaCOsb3) solution leads to unusual morphologies in the inorganic phase. Spherulitic vaterite aggregates with helical protrusions, and distorted calcite crystals that contain spiral pits, have been produced. The helical particles are coated with an inorganic membrane that appears to be responsible for the helical twist. The polymer also causes deposition of thin CaCOsb3 tablets and films on the glass substrate. Two distinct types of films are deposited; the first is a mosaic of calcite crystals, and the second is spherulitic vaterite. In situ observations of the crystallization reaction have determined that the thin-film morphology is a result of the phase separation of a hydrated CaCOsb3/polymer liquid-precursor, whereby accumulation of isotropic droplets creates a coating on the substrate, and subsequent dehydration and crystallization yields birefringent CaCOsb3 films. During the amorphous to crystalline transition, incremental growth steps lead to "transition bars" and sectored calcite tablets. This in vitro system was originally modeled after certain aspects of CaCOsb3 biomineralization, in which the soluble proteins extracted from biominerals tend to have high levels of aspartic acid residues. Based on the similarities between features exhibited by the products of this system and those in biominerals, an argument has been presented to suggest that this polymer-induced liquid-precursor (PILP) process is involved in the morphogenesis of CaCOsb3 biominerals. These features include the following: thin CaCOsb3 tablets that grow laterally; tablets that express unstable crystallographic faces; non-faceted single crystals with curved surfaces; spatially-delineated single crystals; sectored calcite tablets; hollow-shell spheres; calcium carbonate cements; and magnesium-bearing calcites. This work has demonstrated that a means of morphological control can be accomplished through non

  6. Structural properties of nitrogenated amorphous carbon films: Influence of deposition temperature and radiofrequency discharge power

    SciTech Connect

    Lazar, G.; Bouchet-Fabre, B.; Zellama, K.; Clin, M.; Ballutaud, D.; Godet, C.

    2008-10-01

    The structural properties of nitrogenated amorphous carbon deposited by radiofrequency magnetron sputtering of graphite in pure N{sub 2} plasma are investigated as a function of the substrate temperature and radiofrequency discharge power. The film composition is derived from x-ray photoemission spectroscopy, nuclear reaction analysis and elastic recoil detection measurements and the film microstructure is discussed using infrared, Raman, x-ray photoemission and near edge x-ray absorption fine structure spectroscopic results. At low deposition temperature and low radiofrequency power, the films are soft, porous, and easily contaminated with water vapor and other atmospheric components. The concentration of nitrogen in the films is very large for low deposition temperatures ({approx}33.6 at. % N at 150 deg. C) but decreases strongly when the synthesis temperature increases ({approx}15 at. % N at 450 deg. C). With increasing deposition temperature and discharge power values, the main observed effects in amorphous carbon nitride alloys are a loss of nitrogen atoms, a smaller hydrogen and oxygen contamination related to the film densification, an increased order of the aromatic sp{sup 2} phase, and a strong change in the nitrogen distribution within the carbon matrix. Structural changes are well correlated with modifications of the optical and transport properties.

  7. Substrate temperature influence on the trombogenicity in amorphous carbon nitride thin coatings

    NASA Astrophysics Data System (ADS)

    Galeano-Osorio, D. S.; Vargas, S.; López-Córdoba, L. M.; Ospina, R.; Restrepo-Parra, E.; Arango, P. J.

    2010-10-01

    Carbon nitride thin films were obtained through plasma assisted physical vapor deposition technique by pulsed arc, varying the substrate temperature and investigating the influence of this parameter on the films hemocompatibility. For obtaining approaches of blood compatibility, environmental scanning electron microscopy (ESEM) was used in order to study the platelets adherence and their morphology. Moreover, the elemental chemical composition was determined by using energy dispersive spectroscopy (EDS), finding C, N and O. The coatings hemocompatibility was evaluated by in vitro thrombogenicity test, whose results were correlated with the microstructure and roughness of the films obtained. During the films growth process, the substrate temperature was varied, obtaining coatings under different temperatures, room temperature ( Troom), 100 °C, 150 °C and 200 °C. Parameters as interelectrodic distance, voltage, work pressure and number of discharges, were remained constant. By EDS, carbon and nitrogen were found in the films. Visible Raman spectroscopy was used, and it revealed an amorphous lattice, with graphitic process as the substrate temperature was increased. However, at a critical temperature of 150 °C, this tendency was broken, and the film became more amorphous. This film showed the lowest roughness, 2 ± 1 nm. This last characteristic favored the films hemocompatibility. Also, it was demonstrated that the blood compatibility of carbon nitride films obtained were affected by the ID/ IG or sp 3/sp 2 ratio and not by the absolute sp 3 or sp 2 concentration.

  8. Pore fluid chemistry and spectral induced polarization signatures of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Wu, Y.; Hubbard, S. S.; Ajo Franklin, J. B.; Williams, K. H.

    2010-12-01

    Calcium carbonate (CaCO3) minerals are a key family of compounds that frequently precipitate during natural and engineered subsurface processes. They play important roles in elemental cycling within geosystems and can be utilized in the context of environmental remediation (such as metal sequestration through co-precipitation) and in geotechnical engineering (such as improving soil strength or decreasing rock permeability). Characterizing the spatial extent and temporal dynamics of carbonate mineral precipitation is critical for these studies. Our previous research has indicated the potential of geophysical methods, particularly spectral induced polarization (SIP) for tracking the onset and evolution of mineral precipitates, including calcite. Here, we experimentally document the significant role of pore fluid chemistry and surface charge structure on the SIP signature of calcium carbonates. Our column studies revealed that the SIP signature of calcium carbonate is dictated by surface charge structure that relies heavily on surface complexation properties, such as charge density and speciation. For calcium carbonate, the primary potential determining ions (PDIs) are calcium and carbonate ions and the SIP signatures of calcium carbonate are primarily controlled by the concentrations of these species. Our data show that calcium carbonates in thermodynamic equilibrium with pore fluid produce a negligible SIP response due to very small (if any) surface charges. In contrast, systems that are over saturated with respect to calcium carbonate (i.e., far from equilibrium) produce significant SIP responses, which is consistent with high surface charge densities shown by high zeta potential values in previous studies. Our studies reveal that a closed system that transitions from over-saturation to equilibrium conditions is accompanied by significant decrease of SIP signals (and vice-versa). The studies also show that the effect of pH on SIP signature of calcium carbonate is

  9. Influence of calcium carbonate and carbon nanotubes on the crystallization kinetics of polypropylene at high supercooling

    NASA Astrophysics Data System (ADS)

    Schawe, Jürgen E. K.

    2016-03-01

    Polymer fillers have been classified as active or inactive regarding their nucleation performance. Whereas an active filler significantly accelerates the crystallization process, an inactive filler has a significantly reduced influence on the crystallization kinetics. The majority of the studies of the filler influence on the crystallization process are performed at relatively low supercooling or at low cooling rates. In this paper, we use the Fast Scanning DSC to study the crystallization process of differently filled polypropylene (PP) in the temperature range between 120 °C and 0 °C. The inactive filler calcium carbonate reduces the crystallization rate of the α-phase at low supercooling (above 80 °C). Between 45 °C and 80 °C, calcium carbonate significantly accelerates the α-phase crystallization of PP. The mesophase crystallization is not affected by this filler. As an example of active filler, carbon nanotubes are used. Even with small filler content the α-phase crystallization of PP is significantly accelerated. Also in this case the mesophase crystallization is not significantly affected.

  10. High Calcium (~80mol%) Late Stage Carbonate in ALH84001

    NASA Astrophysics Data System (ADS)

    Gildea, K. J.; Holland, G.; Lyon, I. C.; Chatzitheodoridis, E.; Burgess, R.

    2006-03-01

    Brief petrological, chemical and textural description of previously undescribed high Ca late stage carbonate in Martian meteorite ALH84001. This carbonate surrounds Mg rich carbonates and rosette fragments.

  11. Phonon transport in amorphous carbon using Green-Kubo modal analysis

    NASA Astrophysics Data System (ADS)

    Lv, Wei; Henry, Asegun

    2016-05-01

    Amorphous carbon (a-C) is an important material often used in microelectronics. Using a recently developed approach, termed Green-Kubo modal analysis, we were able to calculate the thermal conductivity of a-C, which yielded excellent agreement with experiments, by employing a simple correction to the specific heat. The results show that the heat capacity substantially limits the thermal conductivity of a-C at room temperature and it is dominated by contributions from diffusons between 10 and 40 THz. Furthermore, the phonon relaxation times in a-C do not vary significantly with increasing temperature, which is quite unusual by comparison with the behavior observed for other materials.

  12. Strain-induced photoconductivity in thin films of Co doped amorphous carbon.

    PubMed

    Jiang, Y C; Gao, J

    2014-01-01

    Traditionally, strain effect was mainly considered in the materials with periodic lattice structure, and was thought to be very weak in amorphous semiconductors. Here, we investigate the effects of strain in films of cobalt-doped amorphous carbon (Co-C) grown on 0.7PbMg(1/3)Nb(2/3)O3-0.3PbTiO3 (PMN-PT) substrates. The electric transport properties of the Co-C films were effectively modulated by the piezoelectric substrates. Moreover, we observed, for the first time, strain-induced photoconductivity in such an amorphous semiconductor. Without strain, no photoconductivity was observed. When subjected to strain, the Co-C films exhibited significant photoconductivity under illumination by a 532-nm monochromatic light. A strain-modified photoconductivity theory was developed to elucidate the possible mechanism of this remarkable phenomenon. The good agreement between the theoretical and experimental results indicates that strain-induced photoconductivity may derive from modulation of the band structure via the strain effect. PMID:25338641

  13. Strain-induced photoconductivity in thin films of Co doped amorphous carbon

    PubMed Central

    Jiang, Y. C.; Gao, J.

    2014-01-01

    Traditionally, strain effect was mainly considered in the materials with periodic lattice structure, and was thought to be very weak in amorphous semiconductors. Here, we investigate the effects of strain in films of cobalt-doped amorphous carbon (Co-C) grown on 0.7PbMg1/3Nb2/3O3-0.3PbTiO3 (PMN-PT) substrates. The electric transport properties of the Co-C films were effectively modulated by the piezoelectric substrates. Moreover, we observed, for the first time, strain-induced photoconductivity in such an amorphous semiconductor. Without strain, no photoconductivity was observed. When subjected to strain, the Co-C films exhibited significant photoconductivity under illumination by a 532-nm monochromatic light. A strain-modified photoconductivity theory was developed to elucidate the possible mechanism of this remarkable phenomenon. The good agreement between the theoretical and experimental results indicates that strain-induced photoconductivity may derive from modulation of the band structure via the strain effect. PMID:25338641

  14. Precipitation of Co(2+) carbonates from aqueous solution: insights on the amorphous to crystalline transformation.

    NASA Astrophysics Data System (ADS)

    González-López, Jorge; Fernández-González, Ángeles; Jiménez, Amalia

    2016-04-01

    Cobalt is toxic metal that is present only as a trace in the Earth crust. However, Co might concentrate on specific areas due to both natural and anthropogenic factors and thus, soils and groundwater can be contaminated. It is from this perspective that we are interested in the precipitation of cobalt carbonates, since co-precipitation with minerals phases is a well-known method for metal immobilization in the environment. In particular, the carbonates are widely used due to its reactivity and natural abundance. In order to evaluate the cobalt carbonate precipitation at room temperature, a simple experimental work was carried out in this work. The precipitation occurred via reaction of two common salts: 0.05M of CoCl2 and 0.05M of Na2CO3 in aqueous solution. After reaction, the precipitated solid was kept in the remaining water at 25 oC and under constant stirring for different aging times of 5 min, 1 and 5 hours, 1, 2, 4, 7, 30 and 60 days. In addition to the aging and precipitation experiments, we carried out experiments to determine the solubility of the solids. In these experiments each precipitate was dissolved in Milli-Q water until equilibrium was reached and then the aqueous solution was analyzed regarding Co2+ and total alkalinity. Furthermore, acid solution calorimetry of the products were attained. Finally, we modeled the results using the PHREEQC code. Solid and aqueous phase identification and characterization have been extensively reported in a previous work (González-López et al., 2015). The main results of our investigation were the initial precipitation of an amorphous cobalt carbonate that evolve towards a poorly crystalline cobalt hydroxide carbonate with aging treatment. Solubility of both phases have been calculated under two different approaches: precipitation and dissolution. Values of solubility from each approach were obtained with a general error due to differences in experiment conditions, for instance, ionic strength, temperature and

  15. Ultra-Small-Angle X-ray Scattering – X-ray Photon Correlation Spectroscopy Studies of Incipient Structural Changes in Amorphous Calcium Phosphate Based Dental Composites

    PubMed Central

    Zhang, F.; Allen, A.J.; Levine, L.E.; Espinal, L.; Antonucci, J.M.; Skrtic, D.; O’Donnell, J.N.R.; Ilavsky, J.

    2012-01-01

    The local structural changes in amorphous calcium phosphate (ACP) based dental composites were studied under isothermal conditions using both static, bulk measurement techniques and a recently developed methodology based on combined ultra-small angle X-ray scattering – X-ray photon correlation spectroscopy (USAXS-XPCS), which permits a dynamic approach. While results from conventional bulk measurements do not show clear signs of structural change, USAXS-XPCS results reveal unambiguous evidence for local structural variations on a similar time scale to that of water loss in the ACP fillers. A thermal-expansion based simulation indicates that thermal behavior alone does not account for the observed dynamics. Together, these results suggest that changes in the water content of ACP affect the composite morphology due to changes in ACP structure that occur without an amorphous-to-crystalline conversion. It is also noted that biomedical materials research could benefit greatly from USAXS-XPCS, a dynamic approach. PMID:22374649

  16. Carbonate-coordinated metal complexes precede the formation of liquid amorphous mineral emulsions of divalent metal carbonates.

    PubMed

    Wolf, Stephan E; Müller, Lars; Barrea, Raul; Kampf, Christopher J; Leiterer, Jork; Panne, Ulrich; Hoffmann, Thorsten; Emmerling, Franziska; Tremel, Wolfgang

    2011-03-01

    During the mineralisation of metal carbonates MCO3 (M=Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed. PMID:21218241

  17. Calcium

    MedlinePlus

    ... milligrams) of calcium each day. Get it from: Dairy products. Low-fat milk, yogurt, cheese, and cottage ... lactase that helps digest the sugar (lactose) in dairy products, and may have gas, bloating, cramps, or ...

  18. Sulfur Cycling Mediates Calcium Carbonate Geochemistry in Modern Marine Stromatolites

    NASA Technical Reports Server (NTRS)

    Visscher, P. T.; Hoeft, S. E.; Bebout, B. M.; Reid, R. P.

    2004-01-01

    Modem marine stromatolites forming in Highborne Cay, Exumas (Bahamas), contain microbial mats dominated by Schizothrix. Although saturating concentrations of Ca2+ and CO32- exist, microbes mediate CaCO3 precipitation. Cyanobacterial photosynthesis in these stromatolites aids calcium carbonate precipitation by removal of HS+ through CO2 use. Photorespiration and exopolymer production predominantly by oxygenic phototrophs fuel heterotrophic activity: aerobic respiration (approximately 60 umol/sq cm.h) and sulfate reduction (SR; 1.2 umol SO42-/sq cm.h) are the dominant C- consuming processes. Aerobic microbial respiration and the combination of SR and H2S oxidation both facilitate CaCO3 dissolution through H+ production. Aerobic respiration consumes much more C on an hourly basis, but duel fluctuating O2 and H2 depth profiles indicate that overall, SR consumes only slightly less (0.2-0.5) of the primary production. Moreover, due to low O2 concentrations when SR rates are peaking, reoxidation of the H2S formed is incomplete: both thiosulfate and polythionates are formed. The process of complete H2S oxidation yields H+. However, due to a low O2 concentration late in the day and relatively high O2 concentrations early in the following morning, a two-stage oxidation takes place: first, polythionates are formed from H2S, creating alkalinity which coincides with CaCO3 precipitation; secondly, oxidation of polythionates to sulfate yields acidity, resulting in dissolution, etc. Vertical profiles confirmed that the pH peaked late in the afternoon (greater than 8.8) and had the lowest values (less than 7.4) early in the morning. Thus, the effect of this S-cycling through alkalinity production, followed by acidification during H2S oxidation, results in a six times stronger fluctuation in acidity than photosynthesis plus aerobic respiration accomplish. This implies that anaerobic processes play a pivotal role in stromatolite formation.

  19. Tribocharging phenomena in hard disk amorphous carbon coatings with and without perfluoropolyether lubricants

    SciTech Connect

    van den Oetelaar, Ronald J.A.; Xu, Lei; Ogletree, D. Frank; Salmeron, Miquel; Tang, Hung; Gui, Jing

    2000-08-01

    Scanning polarization force microscopy was used to study changes in surface potential (tribocharging) caused by the contact between a tungsten carbide tip and the amorphous carbon coating of a hard disk,both when bare and when covered with Zdol-TX lubricant. The surface potential change produced by tip contact decays with time at a rate that is strongly dependent on lubricant coverage, and on the presence of oxygen and water vapor in the environment. Two different charging mechanisms are proposed. One involves chemical modification of the surface by removal of oxygen bound to the surface. This gives rise to a potential change that decays with time. Another mechanism involves trapping of charge in states within the energy gap of the insulating carbon film. The potential change due to this trapped charge does not decay over periods much greater than 1 hour.

  20. LETTER TO THE EDITOR: A new approach to modelling tetrahedral amorphous carbon

    NASA Astrophysics Data System (ADS)

    Walters, J. K.; Gilkes, K. W. R.; Wicks, J. D.; Newport, R. J.

    1997-08-01

    We have generated a new model for the structure of tetrahedral amorphous carbon using a modified reverse Monte Carlo modelling method. The novel feature of this approach is the definition of three different types of carbon atom, corresponding to tetrahedral, planar and linear bonding conformations. The particular strengths of the method are the large model size (3000 atoms), that all the possible arrangements of 0953-8984/9/34/001/img7 and 0953-8984/9/34/001/img8 bonds are allowed, and that no interatomic potential is required. For the first time we have determined the distribution of 0953-8984/9/34/001/img8 bonded sites within the predominantly disordered tetrahedral structure, and we find that they form polymer-like chains and small clusters which connect the 0953-8984/9/34/001/img7 bonded regions.

  1. Hydrogen softening and optical transparency in Si-incorporated hydrogenated amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Abbas, G. A.; Papakonstantinou, P.; McLaughlin, J. A.; Weijers-Dall, T. D. M.; Elliman, R. G.; Filik, J.

    2005-11-01

    High-resolution x-ray reflectivity (XRR) and heavy-ion elastic recoil detection were employed to study the role of hydrogen on the softening behavior observed in Si-incorporated hydrogenated amorphous carbon (Si-a-C:H) films synthesized by plasma-enhanced chemical-vapor deposition using tetramethylsilane (TMS) precursor in C2H2/Ar plasma. An enhancement of the optical band gap and a massive reduction in the density of the films prepared at high TMS flow rate were revealed, respectively, by spectroscopic ellipsometry and XRR analysis with the development of a double critical angle. A hydrogenation process was responsible for a rise in the density of voids and an associated reduction in the connectivity of the carbon network and the release of its residual stress.

  2. AFM investigation on surface evolution of amorphous carbon during ion-beam-assisted deposition

    NASA Astrophysics Data System (ADS)

    Zhu, X. D.; Ding, F.; Naramoto, H.; Narumi, K.

    2006-11-01

    Hydrogen-free amorphous carbons (a-C) have been prepared on mirror-polished Si(1 1 1) wafers through thermally evaporated C 60 with simultaneous bombardments of Ne + ions. The time evolution of film surfaces has been characterized by atomic force microscopy (AFM) at two temperatures of 400 and 700 °C, respectively. Based on the topography images and the root-mean-square (rms) roughness analysis, it is found that the a-C surfaces present roughening growth at the initial stage. With increasing growth time, the cooperative nucleation of the islands and pits appears on the surfaces, suggesting three-dimensional growth, and then they continue to evolve to irregular mounds at 400 °C, and elongated mounds at 700 °C. At the steady growth stage, these surfaces further develop to the structures of bamboo joints and ripples corresponding to these two temperatures, respectively. It is believed that besides ion sputtering effect, the chemical bonding configurations in the amorphous carbon films should be taken into considerations for elucidating the surface evolutions.

  3. Formation of Ultrananocrystalline Diamond/Amorphous Carbon Composite Films in Vacuum Using Coaxial Arc Plasma Gun

    NASA Astrophysics Data System (ADS)

    Hanada, Kenji; Yoshida, Tomohiro; Nakagawa, You; Yoshitake, Tsuyoshi

    2010-12-01

    Ultrananocrystalline diamond (UNCD)/nonhydrogenated amorphous carbon (a-C) composite films were grown in vacuum using a coaxial arc plasma gun. From the X-ray diffraction measurement, the UNCD crystallite size was estimated to be 1.6 nm. This size is dramatically reduced from that (2.3 nm) of UNCD/hydrogenated amorphous carbon (a-C:H) composite films grown in a hydrogen atmosphere. The sp3/(sp3 + sp2) value, which was estimated from the X-ray photoemission spectrum, was also reduced to be 41%. A reason for it might be the reduction in the UNCD crystallite size. From the near-edge X-ray absorption fine-structure (NEXAFS) spectrum, it was found that the π*C=C and π*C≡C bonds are preferentially formed instead of the σ*C-H bonds in the UNCD/a-C:H films. Since the extremely small UNCD crystallites (1.6 nm) correspond to the nuclei of diamond, we consider that UNCD crystallite formation should be due predominantly to nucleation. The supersaturated condition required for nucleation is expected to be realized in the deposition using the coaxial arc plasma gun.

  4. Probing the intrinsic failure mechanism of fluorinated amorphous carbon film based on the first-principles calculations

    PubMed Central

    Zhang, Ren-hui; Wang, Li-ping; Lu, Zhi-bin

    2015-01-01

    Fluorinated amorphous carbon films exhibit superlow friction under vacuum, but are prone to catastrophic failure. Thus far, the intrinsic failure mechanism remains unclear. A prevailing view is that the failure of amorphous carbon film results from the plastic deformation of substrates or strong adhesion between two contacted surfaces. In this paper, using first-principles and molecular dynamics methodology, combining with compressive stress-strain relation, we firstly demonstrate that the plastic deformation induces graphitization resulting in strong adhesion between two contacted surfaces under vacuum, which directly corresponds to the cause of the failure of the films. In addition, sliding contact experiments are conducted to study tribological properties of iron and fluorinated amorphous carbon surfaces under vacuum. The results show that the failure of the film is directly attributed to strong adhesion resulting from high degree of graphitization of the film, which are consistent with the calculated results. PMID:25803202

  5. Characterization of amorphous carbon films as total-reflection mirrors for XUV free-electron lasers

    NASA Astrophysics Data System (ADS)

    Jacobi, Sandra; Steeg, Barbara; Wiesmann, Jorg; Stormer, Michael; Feldhaus, Josef; Bormann, R.'diger; Michaelsen, Carsten

    2002-12-01

    As part of the TESLA (TeV-Energy Superconducting Linear Accelerator) project a free electron laser (FEL) in the XUV (Extreme Ultra-Violet, (6-200 eV)) and X-ray (0.5-15 keV) range is being developed at DESY (Deutsches Elektronen Synchrotron, Hamburg). At the TESLA Test Facility (TTF) a prototype FEL has recently demonstrated maximum light amplification in the range of 80 nm to 120 nm. It is expected that the FEL will provide intense, sub-picosecond radiation pulses with photon energies up to 200 eV in the next development stage. In a joint project between DESY and GKSS, thin film optical elements with very high radiation stability, as required for FEL applications, are currently being developed. Sputter-deposited amorphous carbon coatings have been prepared for use as total reflection X-ray mirrors. The optical characterization of the mirrors has been carried out using the soft X-ray reflectometer at HASYLAB (Hamburger Synchrotronstrahlungslabor) beamline G1. The reflectivity of the carbon films at 2 deg incidence angle is close to the theoretical reflectivity of 95.6 %, demonstrating the high quality of the coatings. For comparison, layers produced by different methods (e.g. Chemical vapor deposition, Pulsed laser deposition) have been characterized as well. Annealing experiments have been performed to evaluate the thermal stability of the amorphous carbon films. Further investigations concerning the radiation stability of the X-ray mirrors have also been conducted. The mirrors were irradiated in the FELIS (Free Electron Laser-Interaction with Solids) experiment at the TTF-FEL. Microscopic investigations demonstrate that the carbon mirrors are fairly stable.

  6. Structural changes of hydrogenated amorphous carbon films deposited on steel rods

    NASA Astrophysics Data System (ADS)

    Choi, Junho; Hatta, Tetsuya

    2015-12-01

    In this study, hydrogenated amorphous carbon (a-C:H) films were deposited on steel rods of various radii by using bipolar-type plasma based ion implantation and deposition, and the film structure and mechanical properties have been investigated. Furthermore, the behavior of plasma surrounding the steel rods (i.e., flux and energy of incident ions and electrons) was investigated using the particle-in-cell Monte Carlo collision (PIC-MCC) method to examine the mechanism behind the structural changes of the a-C:H films. Three kinds of amorphous carbon films with different microstructures were prepared by changing the negative pulse voltages from -1 kV to -5 kV: one polymer-like carbon film and two diamond-like carbon films that possess the maximum FWHM(G) (full width at half maximum of Raman G-peak) and maximum hardness. The structure of the a-C:H films was evaluated through Raman spectroscopy, and the hardness of the films was measured using nanoindentation. It was found that the structures of a-C:H films deposited on the steel-rod surfaces are quite different from those on flat surfaces, and the film structures are directly affected by the curvature of the rod. It was also determined from the plasma simulation that the incident electron flux and ion flux become more intense as the curvature increases, resulting in the structural changes of the a-C:H films due to hydrogen evolution and thermal relaxation in the films.

  7. Fluctuation microscopy studies of medium-range ordering in amorphous diamond-like carbon films.

    SciTech Connect

    Chen, X.; Sullivan, J. P.; Friedmann, T. A.; Gibson, J. M.; Cedarville Univ.; SNL

    2004-04-12

    In this letter, we report fluctuation microscopy studies of medium-range ordering in amorphous diamond-like carbon films and the effect of annealing on this ordering. Annealed and unannealed diamond-like carbon films have almost identical short-range order. Our fluctuation microscopy results, however, indicate the presence of medium range order or clustering in the films on a lateral length scale that exceeds 1 nm. Within the clustered regions, the dominant local ordering appears to be diamond-like, and graphite-like ordering is not observed. Thermal annealing up to 600 {sup o}C leads to an increase in diamond-like clustering with no onset of graphite-like clustering. However, after high temperature annealing up to 1000 {sup o}C, graphite-like clustering becomes apparent as a result of the conversion of diamond-like carbon to graphite-like carbon. The results on the as-deposited films and films annealed up to 600 {sup o}C suggest that a spontaneous medium range ordering process occurs in diamond-like carbon films during and subsequent to film growth, and this may play an important role in stress relaxation.

  8. Preparation of pure calcium carbonate by mineral carbonation using industrial byproduct FGD gypsum

    NASA Astrophysics Data System (ADS)

    Song, K.; Kim, W.; Bang, J. H.; Park, S.; Jeon, C. W.

    2015-12-01

    Mineral carbonation is one of the geological approaches for the sequestration of anthropogenic CO2 gas. Its concept is based on the natural weathering processes in which silicate minerals containing divalent cations such as Ca or Mg are carbonated to CaCO3 or MgCO3 in the reaction with CO2gas. Raw materials for the mineral carbonation have been extended to various industrial solid wastes such as steel slag, ashes, or FGD (flue gas desulfurization) gypsum which are rich in divalent cations. These materials have economic advantages when they are produced in CO2 emission sites. Flue gas desulfurization (FGD) gypsum is such a byproduct obtained in at coal-fired power plants. Recently, we carried out a research on the direct mineral carbonation of FGD gypsum for CO2sequestration. It showed high carbonation reactivity under ambient conditions and the process can be described as follows: CaSO4·2H2O + CO2(g) + 2NH4OH(aq) → CaCO3(s) + (NH4)2SO4(aq) (1) At the early stage of the process, calcium carbonate (CaCO3) exists as a dissolved ion pair during the induction period. High-purity CaCO3 could be precipitated from dissolved calcium carbonate solution extracted during the induction period. The effect of experimental parameters on pure CaCO3 was evaluated: CO2 flow rate (1-3 L/min), ammonia content (4-12%), and solid-to-liquid (S/L) ratio (5-300 g/L). FE-SEM (field-emission scanning electron microscopy) and XRD (X-ray diffraction) study revealed that the precipitated CaCO3 was round-shaped vaterite crystals. The induction time was inversely proportional to the CO2 flow rate and the yield for pure CaCO3 increased with the ammonia content. The formation efficiency for pure CaCO3 decreased with S/L (solid/liquid) ratio. It was 90% (mol/mol) when the S/L ratio was 5 g/L. However, S/L ratio didn't affect the maximum solubility limit of dissolved CaCO3.

  9. Effects of calcium carbonate and hydroxyapatite on zinc and iron retention in postmenopausal women

    SciTech Connect

    Dawson-Hughes, B.; Seligson, F.H.; Hughes, V.A.

    1986-07-01

    We measured the effect of calcium carbonate and hydroxyapatite on whole-body retention of zinc-65 in 11 and iron-59 in 13 healthy, postmenopausal women. In a single-blind, controlled, crossover study, each subject, on three occasions, ingested a standard test meal supplemented with iron-59 or zinc-65 and capsules containing placebo or 500 mg elemental calcium as calcium carbonate or hydroxyapatite. Whole-body countings were performed prior to, 30 min after, and 2 wk after each meal. Mean (SEM) zinc retention was 18.1 +/- 1.0% with placebo (control) and did not vary significantly with calcium carbonate (110.0 +/- 8.6% of control) or hydroxyapatite (106.0 +/- 7.9% of control). Iron retention, 6.3 +/- 2.0% with placebo, was significantly reduced with both calcium carbonate (43.3 +/- 8.8% of control, p = 0.002) and hydroxyapatite (45.9 +/- 10.0% of control, p = 0.003). Iron absorption may be significantly reduced when calcium supplements are taken with meals.

  10. pH control in biological systems using calcium carbonate.

    PubMed

    Salek, S S; van Turnhout, A G; Kleerebezem, R; van Loosdrecht, M C M

    2015-05-01

    Due to its abundance, calcium carbonate (CaCO3) has high potentials as a source of alkalinity for biotechnological applications. The application of CaCO3 in biological systems as neutralizing agent is, however, limited due to potential difficulties in controlling the pH. The objective of the present study was to determine the dominant processes that control the pH in an acid-forming microbial process in the presence of CaCO3. To achieve that, a mathematical model was made with a minimum set of kinetically controlled and equilibrium reactions that was able to reproduce the experimental data of a batch fermentation experiment using finely powdered CaCO3. In the model, thermodynamic equilibrium was assumed for all speciation, complexation and precipitation reactions whereas, rate limited reactions were included for the biological fatty acid production, the mass transfer of CO2 from the liquid phase to the gas phase and the convective transport of CO2 out of the gas phase. The estimated pH-pattern strongly resembled the measured pH, suggesting that the chosen set of kinetically controlled and equilibrium reactions were establishing the experimental pH. A detailed analysis of the reaction system with the aid of the model revealed that the pH establishment was most sensitive to four factors: the mass transfer rate of CO2 to the gas phase, the biological acid production rate, the partial pressure of CO2 and the Ca(+2) concentration in the solution. Individual influences of these factors on the pH were investigated by extrapolating the model to a continuously stirred-tank reactor (CSTR) case. This case study indicates how the pH of a commonly used continuous biotechnological process could be manipulated and adjusted by altering these four factors. Achieving a better insight of the processes controlling the pH of a biological system using CaCO3 as its neutralizing agent can result in broader applications of CaCO3 in biotechnological industries. PMID:25425281

  11. The effect of pigeon yolk sac fluid on the growth behavior of calcium carbonate crystals.

    PubMed

    Song, Juan; Cheng, Haixia; Shen, Xinyu; Tong, Hua

    2015-03-01

    Previous experiments have proved that thermodynamically unstable calcium carbonate vaterite can exist for long periods in the yolk sac of a pigeon embryo. The aim of this article was to demonstrate the effect of in vitro mineralization of yolk sac fluid on calcium carbonate by direct precipitation. Experiments were conducted using pigeon yolk sac fluid and using lecithin extracted from pigeon yolk sac fluid as a control to investigate the regulating effects of the organic components in the embryo on the formation of the calcium carbonate precipitate. Multiple characterization methods were employed to study the various morphological patterns, sizes, crystal growth, and crystal phase transformations of the calcium carbonate precipitates as regulated by the yolk sac fluid extracted at different stages of incubation. The experimental results demonstrate that as the incubation proceeds towards the later stages, the composition and environmental features of the yolk sac fluid become more favorable for the formation of relatively unstable calcium carbonate phases with high energies of the vaterite state. The experiments conducted with extracted lecithin as the template for crystal growth yielded similar results. A large amount of organic molecules with polar functional groups carried by the yolk sac fluid have strong effects and can both initially induce the crystallization and regulate the aggregation of calcium carbonate. Furthermore, this regulation process is found to be closely related to the lecithin contained in yolk sac fluid. These observations confirm the changes in yolk sac fluid composition during incubation have significant effects on the production of vaterite, which implicates the calcium transport during embryo growth. PMID:25681477

  12. Effect of acid rain on calcium carbonate saturation in the Albemarle sound of North Carolina

    SciTech Connect

    Rudolph, K.A.; Burgess, S.K.; Willey, J.D.; Kieber, R.J.

    1996-10-01

    The effects of acidic rainwater additions on calcium carbonate solubility and alkalinity in the poorly buffered, biologically active and commercially important waters of the Albemarle Sound, NC are reported. Samples collected monthly at four sites were analyzed for salinity, pK total alkalinity, and calcium concentrations. Five percent and 10% dilutions of sulfuric acid at pH 4, mimicking acid rain additions, were added and total alkalinity and calcium concentrations again determined. The addition of acid decreased the alkalinity in the Albemarle samples by as much as 15%, although the magnitude of the impact depended both on site and season. The effects of acid additions on dissolved calcium concentrations were more variable,. and also displayed a site and season dependency. Calcium concentrations, alkalinity, and pH values were also determined during controlled laboratory experiments, where 25 mg/L Callinectes sapidus shells were added to Albemarle Sound water. All three analytes increased significantly upon acid additions relative to controls.

  13. Cooling rate threshold in transformation of C_60 fullerene to amorphous diamond and highly disordered carbon in SCARQ experiments

    NASA Astrophysics Data System (ADS)

    Homae, Tomotaka; Okamoto, Atsushi; Nakamura, Kazutaka; Ken-Ichi, Kondo; Yoshida, Masatake; Hirabayashi, Keiji; Niwase, Keisuke

    2001-06-01

    Synthesis of amorphous diamond from C_60 fullerene by Shock compression and rapid quenching (SCARQ) technique was reported previously (Hirai et. al., Appl. Phys. Lett. 64, 1797 (1994)). In this paper, we report the condition for the formation of amorphous diamond. When the initial thickness was less than 10 μm, the recovered sample showed broad photoluminescence (PL) and cathodeluminescence (CL) spectra but no Raman peaks. These observations indicate that the sample was amorphous diamond. In the case of 20-μm thick sample, the recovered sample was disordered carbon as it gave G and D Raman peaks and PL spectrum. However, it gave CL spectrum similar to amorphous diamond, which is not normally observed for normal disordered carbon. The cooling rate related to the initial thickness of the sample was estimated by numerically calculated temperature changes of the sample on the basis of Fourier's law for conduction heat transfer. The threshold of cooling rate between amorphous diamond and disordered carbon was determined. The details of the transformation processes of C_60 fullerene will be discussed.

  14. Effects of functional groups and soluble matrices in fish otolith on calcium carbonate mineralization.

    PubMed

    Ren, Dongni; Li, Zhuo; Gao, Yonghua; Feng, Qingling

    2010-10-01

    Calcium carbonate mineralization is significantly influenced by organic matrices in vivo. The effect mainly relies on functional groups in proteins. In order to study the influence of functional groups on calcium carbonate mineralization, -OH, -NH2 and -COOH groups were grafted onto single crystal silicon chips, and such modified chips were used as substrates in in vitro mineralization experiments. An x-ray photoelectron spectroscopy (XPS) test was conducted to examine the grafting efficiency, and the three groups were successfully grafted. Calcium carbonate mineralization on a modified silicon substrate was examined by a scanning electron microscope (SEM) and x-ray diffraction (XRD), and the results showed that the effects of -OH, -NH2 and -COOH groups were quite different. Furthermore, a water-soluble protein matrix (WSM) and an acid-soluble protein matrix (ASM) extracted from fish otolith were adsorbed onto the -COOH-modified silicon substrate, and the effects of the protein matrices on calcium carbonate mineralization were studied. The results showed that both WSM and ASM of lapillus could mediate aragonite crystallization, but the size and morphology of the formed crystals were different. The WSM and ASM of asteriscus adsorbed on the silicon substrate had little effect on calcium carbonate mineralization; almost all the crystals were calcite, while both asteriscus WSM and ASM in solution could mediate vaterite crystals, and the morphologies of vaterite crystal aggregates were different. PMID:20844320

  15. Recovery of calcium carbonate from steelmaking slag and utilization for acid mine drainage pre-treatment.

    PubMed

    Mulopo, J; Mashego, M; Zvimba, J N

    2012-01-01

    The conversion of steelmaking slag (a waste product of the steelmaking process) to calcium carbonate (CaCO(3)) was tested using hydrochloric acid, ammonium hydroxide and carbon dioxide via a pH-swing process. Batch reactors were used to assess the technical feasibility of calcium carbonate recovery and its use for pre-treatment of acid mine drainage (AMD) from coal mines. The effects of key process parameters, such as the amount of acid (HCl/calcium molar ratio), the pH and the CO(2) flow rate were considered. It was observed that calcium extraction from steelmaking slag significantly increased with an increase in the amount of hydrochloric acid. The CO(2) flow rate also had a positive effect on the carbonation reaction rate but did not affect the morphology of the calcium carbonate produced for values less than 2 L/min. The CaCO(3) recovered from the bench scale batch reactor demonstrated effective neutralization ability during AMD pre-treatment compared with the commercial laboratory grade CaCO(3). PMID:22643421

  16. Ubiquitylation Functions in the Calcium Carbonate Biomineralization in the Extracellular Matrix

    PubMed Central

    Fang, Dong; Pan, Cong; Lin, Huijuan; Lin, Ya; Xu, Guangrui; Zhang, Guiyou; Wang, Hongzhong; Xie, Liping; Zhang, Rongqing

    2012-01-01

    Mollusks shell formation is mediated by matrix proteins and many of these proteins have been identified and characterized. However, the mechanisms of protein control remain unknown. Here, we report the ubiquitylation of matrix proteins in the prismatic layer of the pearl oyster, Pinctada fucata. The presence of ubiquitylated proteins in the prismatic layer of the shell was detected with a combination of western blot and immunogold assays. The coupled ubiquitins were separated and identified by Edman degradation and liquid chromatography/mass spectrometry (LC/MS). Antibody injection in vivo resulted in large amounts of calcium carbonate randomly accumulating on the surface of the nacreous layer. These ubiquitylated proteins could bind to specific faces of calcite and aragonite, which are the two main mineral components of the shell. In the in vitro calcium carbonate crystallization assay, they could reduce the rate of calcium carbonate precipitation and induce the calcite formation. Furthermore, when the attached ubiquitins were removed, the functions of the EDTA-soluble matrix of the prismatic layer were changed. Their potency to inhibit precipitation of calcium carbonate was decreased and their influence on the morphology of calcium carbonate crystals was changed. Taken together, ubiquitylation is involved in shell formation. Although the ubiquitylation is supposed to be involved in every aspect of biophysical processes, our work connected the biomineralization-related proteins and the ubiquitylation mechanism in the extracellular matrix for the first time. This would promote our understanding of the shell biomineralization and the ubiquitylation processes. PMID:22558208

  17. Computational investigation of the mechanical and tribological responses of amorphous carbon nanoparticles

    NASA Astrophysics Data System (ADS)

    Bucholz, Eric W.; Sinnott, Susan B.

    2013-02-01

    Nanoparticles are a class of materials that have seen increasing use as friction and wear reducers in tribological applications. Amorphous carbon (a-C) films have been the subject of significant scientific and industrial interest for use as solid-state lubricants. Here, we present classical molecular dynamics simulations to investigate the mechanical and tribological responses of a-C nanoparticles that are subjected to external forces between hydrogen-terminated diamond surfaces. Over the range of a-C nanoparticle diameters (2-5 nm) and hydrogenation (0%-50%) considered, the simulations predict a consistent mechanical response where each nanoparticle is highly elastic. The simulations predict that the transition from elastic to plastic response is directly related to an increase in the percentage of carbon-carbon crosslinking within the individual nanoparticles. Contrarily, the simulations also predict that the tribological response is noticeably impacted by changes in diameter and hydrogenation. This is because during friction, hydrogen passivates the unsaturated carbon atoms near the nanoparticle's surface, which prevents interfacial bond formation and allows the nanoparticle to roll within the interface. From these findings, it is demonstrated that a-C nanoparticles are able to provide good tribological performance only when sufficient chemical passivation of the nanoparticles is maintained.

  18. CALCIUM HYDROXIDE AND CALCIUM CARBONATE PARTICLE SIZE EFFECTS ON REACTIVITY WITH SULFUR DIOXIDE

    EPA Science Inventory

    The paper reports results of measurements of the effect of in situ calcium-based sorbent particle size upon reactivity with 3000 ppm SO2 in an 1100 c drop-tube furnace, using on-line collection of the reacted sorbent with a particle cascade impactor. Significant agglomeration occ...

  19. A calcium oxide sorbent process for bulk separation of carbon dioxide

    SciTech Connect

    Harrison, D.P.; Han, C.

    1994-10-01

    In this experimental investigation, a laboratory-scale fixed-bed reactor containing a calcium-based sorbent is being used to study the feasibility of combining CO{sub 2} removal with the water gas shift reaction. The sorptive properties of the calcium oxide sorbent were studied as a function of carbonation temperature and pressure, synthesis gas composition, reactor space velocity, and sorbent composition and properties.

  20. Carbonate-coordinated metal complexes precede the formation of liquid amorphous mineral emulsions of divalent metal carbonates

    NASA Astrophysics Data System (ADS)

    Wolf, Stephan E.; Müller, Lars; Barrea, Raul; Kampf, Christopher J.; Leiterer, Jork; Panne, Ulrich; Hoffmann, Thorsten; Emmerling, Franziska; Tremel, Wolfgang

    2011-03-01

    During the mineralisation of metal carbonates MCO3 (M = Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed.During the mineralisation of metal carbonates MCO3 (M = Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed. Electronic supplementary information (ESI) available: (S1 and S5) TEM at higher magnifications and of crystallizations conducted at pH = 6.0, 9.0 and 11.3; (S2) sketch of a spreading liquid particle on a TEM grid; (S3) wide-angle scattering of BaCO3 and CdCO3; (S4 and S6-S9) ESI-MS spectra of a solution of carbon dioxide and of bicarbonates of Sr, Ba, Pb, Mn and Cd. See DOI: 10.1039/c0nr00761g

  1. Distribution and speciation of gold in biogenic and abiogenic calcium carbonates - Implications for the formation of gold anomalous calcrete

    NASA Astrophysics Data System (ADS)

    Reith, Frank; Etschmann, Barbara; Dart, Robert C.; Brewe, Dale L.; Vogt, Stefan; Schmidt Mumm, Andreas; Brugger, Joël

    2011-04-01

    Calcrete (pedogenic Ca carbonate) is an important sampling medium for geochemical gold (Au) exploration in semi-arid and arid regions of Australia, because it is widespread, easy to sample and calcium (Ca) shows a strong positive correlation with Au, but not with base metals, in calcrete overlying buried Au mineralization. In this study we show that the formation of Au-anomalous calcrete can be biomediated through the activity of resident microorganisms, and may not simply be the result of passive nucleation on inactive cells or evapotransporative processes. Calcified microfossils are highly abundant in calcrete from the Barns Au-prospect in South Australia. These microfossils are morphological analogues of calcified cells and biofilms formed in laboratory experiments conducted with active bacterial cultures enriched from Au-anomalous calcareous sand from the Barns prospect. Calcium carbonates precipitated by these cultures consisted mostly of calcite, which is the main carbonate mineral in calcrete. Synchrotron micro-X-ray fluorescence (S-μXRF) mapping was used to assess the distribution of Au, Zn, Ca and other metals in Ca carbonates precipitated by active bacterial cultures. On a μm-scale the distribution of Au was heterogeneous in these Ca carbonates and differed from base metal distribution, thus mimicking the spatial separation of these metals observed in calcrete. The speciation of Au in Ca carbonates precipitated by active bacteria was measured using micro-X-ray absorption near edge structure spectroscopy (μ-XANES) and resembled that observed in Au-anomalous calcrete closely. While metallic Au was observed in Au 'hotpots', ionic Au was detected in the halo surrounding the 'hotspot'. In contrast, the precipitates produced in the presence of dead bacterial cells or by raising solution pH or pCO 2, i.e., hydroxylapatite, portlandite and vaterite, respectively, did not reflect the mineralogy of calcrete. Gold distribution and speciation in vaterite, formed

  2. Correlation between substrate bias, growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Liu, Aiping; Zhu, Jiaqi; Han, Jiecai; Wu, Huaping; Jia, Zechun

    2007-09-01

    We investigate the growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon (ta-C:P) films which are deposited at different substrate biases by filtered cathodic vacuum arc technique with PH 3 as the dopant source. The films are characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, Raman spectroscopy, residual stress measurement, UV/VIS/NIR absorption spectroscopy and temperature-dependent conductivity measurement. The atomic fraction of phosphorus in the films as a function of substrate bias is obtained by XPS analysis. The optimum bias for phosphorus incorporation is about -80 V. Raman spectra show that the amorphous structures of all samples with atomic-scaled smooth surface are not remarkably changed when PH 3 is implanted, but some small graphitic crystallites are formed. Moreover, phosphorus impurities and higher-energetic impinging ions are favorable for the clustering of sp 2 sites dispersed in sp 3 skeleton and increase the level of structural ordering for ta-C:P films, which further releases the compressive stress and enhances the conductivity of the films. Our analysis establishes an interrelationship between microstructure, stress state, electrical properties, and substrate bias, which helps to understand the deposition mechanism of ta-C:P films.

  3. Carbon-assisted growth and high visible-light optical reflectivity of amorphous silicon oxynitride nanowires

    PubMed Central

    2011-01-01

    Large amounts of amorphous silicon oxynitride nanowires have been synthesized on silicon wafer through carbon-assisted vapor-solid growth avoiding the contamination from metallic catalysts. These nanowires have the length of up to 100 μm, with a diameter ranging from 50 to 150 nm. Around 3-nm-sized nanostructures are observed to be homogeneously distributed within a nanowire cross-section matrix. The unique configuration might determine the growth of ternary amorphous structure and its special splitting behavior. Optical properties of the nanowires have also been investigated. The obtained nanowires were attractive for their exceptional whiteness, perceived brightness, and optical brilliance. These nanowires display greatly enhanced reflection over the whole visible wavelength, with more than 80% of light reflected on most of the wavelength ranging from 400 to 700 nm and the lowest reflectivity exceeding 70%, exhibiting performance superior to that of the reported white beetle. Intense visible photoluminescence is also observed over a broad spectrum ranging from 320 to 500 nm with two shoulders centered at around 444 and 468 nm, respectively. PMID:21787429

  4. The Infrared Spectra and Absorption Intensities of Amorphous Ices: Methane and Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Gerakines, Perry A.; Hudson, Reggie L.; Loeffler, Mark J.

    2015-11-01

    Our research group is carrying out new IR measurements of icy solids relevant to the outer solar system and the interstellar medium, with an emphasis on amorphous and crystalline ices below ~70 K. Our goal is to add to the relatively meager literature on this subject and to provide electronic versions of state-of-the-art data, since the abundances of such molecules cannot be deduced without accurate reference spectra and IR band strengths. In the past year, we have focused on two of the simplest and most abundant components of icy bodies in the solar system - methane (CH4) and carbon dioxide (CO2). Infrared spectra from ˜ 4500 to 500 cm-1 have been measured for each of these molecules in μm-thick films at temperatures from 10 to 70 K. All known amorphous and crystalline phases have been reproduced and, for some, presented for the first time. We also report measurements of the index of refraction at 670 nm and the mass densities for each ice phase. Comparisons are made to earlier work where possible. Electronic versions of our new results are available at http://science.gsfc.nasa.gov/691/cosmicice/ constants.html.

  5. Wetting and spreading of long-chain ZDOL polymer nanodroplet on graphene-coated amorphous carbon

    NASA Astrophysics Data System (ADS)

    Sorkin, V.; Zhang, Y. W.

    2014-12-01

    Wetting transparency/translucency/opacity of graphene recently has attracted great interest. The underlying mechanisms and physics for simple liquid droplets containing small molecules on graphene coated crystalline substrates have been studied extensively. However, the behavior of more complicated polymeric droplets on graphene coated amorphous substrates has not been explored. In this work, we perform molecular dynamics simulations to examine the wetting of long-chain ZDOL polymeric droplet on graphene coated amorphous hydrogenated diamond-like carbon or DLCH. We find that at room temperature, the droplet adopts a nearly spherical cap shape with no protruding foot on bare DLCH, and a complex multi-layered structure is formed at the droplet-substrate interface. With addition of graphene layers, externally, the height of the droplet decreases and the protruding foot at the droplet edge appears and grows in size; while internally, the complex multi-layered structure near the droplet-substrate interface remains, but the density distribution for the formed layers becomes increasingly non-uniform. A steady state of the droplet is attained when the number of graphene layers reaches three. These changes can be explained by the interactions between the droplet and substrate across the number of graphene layers. Therefore, it is concluded that the graphene monolayer and bilayer are translucent, while trilayer and above are opaque from the wetting point of view.

  6. Interfacial interaction in a composite based on multi-walled carbon nanotubes and amorphous tin oxide

    NASA Astrophysics Data System (ADS)

    Nesov, S. N.; Bolotov, V. V.; Korusenko, P. M.; Povoroznyuk, S. N.; Vilkov, O. Yu.

    2016-05-01

    The specific features of changes in the electronic structure of multi-walled carbon nanotubes (MWCNTs) due to the interaction with an amorphous tin oxide in the SnO x /MWCNT composite formed by magnetron sputtering have been investigated using X-ray spectroscopy. It has been shown that the formation of chemical bonds responsible for significant changes in the local and electronic structures of the outer layers of MWCNTs occurs at the boundaries of the "amorphous oxide/MWCNT" contacts. The vacuum annealing of the composite leads to the disturbance of the chemical interaction at interfaces of the composite and to a partial recovery of the local structure of the outer layers of MWCNTs. A decrease in the amount of oxygen in the tin oxide under vacuum annealing conditions causes an increase in the number of unpaired Sn 5 s electrons, which, in turn, enhances the charge transfer through the interfaces in the composite and leads to a splitting of the π*-subsystem of the outer layers of MWCNTs.

  7. Calcium Carbonate Formation by Synechococcus sp. Strain PCC 8806 and Synechococcus sp. Strain PCC 8807

    SciTech Connect

    Lee, Brady D.; William A. Apel; Michelle R. Walton

    2006-12-01

    Precipitation of CaCO3 catalyzed by the growth and physiology of cyanobacteria in the Genus Synechococcus represents a potential mechanism for sequestration of CO2 produced during the burning of coal for power generation. Microcosm experiments were performed in which Synechococcus sp. strain PCC 8806 and Synechococcus sp. strain PCC 8807 were tested for their ability to calcify when exposed to a fixed calcium concentration of 3.4 mM and bicarbonate concentrations of 0.5, 1.25 and 2.5 mM. Disappearance of soluble calcium was used as an indicator of CaCO3 formation; results from metabolically active microcosms were compared to controls with no cells or no carbonate added. Synechococcus sp. strain PCC 8806 removed calcium continuously over the duration of the experiment with approximately 18.6 mg of calcium in the solid phase. Calcium removal occurred over a two-day time period when Synechococcus sp. strain PCC 8807 was tested and only 8.9 mg of calcium was removed in the solid phase. The ability of the cyanobacteria to create an alkaline growth environment appeared to be the primary factor responsible for CaCO3 precipitation in these experiments. Removal of inorganic carbon by fixation into biomass was insignificant compared to the mass of inorganic carbon removed by incorporation into the growing CaCO3 solid.

  8. Effect of tetrahedral amorphous carbon coating on the resistivity and wear of single-walled carbon nanotube network

    NASA Astrophysics Data System (ADS)

    Iyer, Ajai; Kaskela, Antti; Novikov, Serguei; Etula, Jarkko; Liu, Xuwen; Kauppinen, Esko I.; Koskinen, Jari

    2016-05-01

    Single walled carbon nanotube networks (SWCNTNs) were coated by tetrahedral amorphous carbon (ta-C) to improve the mechanical wear properties of the composite film. The ta-C deposition was performed by using pulsed filtered cathodic vacuum arc method resulting in the generation of C+ ions in the energy range of 40-60 eV which coalesce to form a ta-C film. The primary disadvantage of this process is a significant increase in the electrical resistance of the SWCNTN post coating. The increase in the SWCNTN resistance is attributed primarily to the intrinsic stress of the ta-C coating which affects the inter-bundle junction resistance between the SWCNTN bundles. E-beam evaporated carbon was deposited on the SWCNTNs prior to the ta-C deposition in order to protect the SWCNTN from the intrinsic stress of the ta-C film. The causes of changes in electrical resistance and the effect of evaporated carbon thickness on the changes in electrical resistance and mechanical wear properties have been studied.

  9. Rapid thermal annealing of Amorphous Hydrogenated Carbon (a-C:H) films

    NASA Technical Reports Server (NTRS)

    Alterovitz, Samuel A.; Pouch, John J.; Warner, Joseph D.

    1987-01-01

    Amorphous hydrogenated carbon (a-C:H) films were deposited on silicon and quartz substrates by a 30 kHz plasma discharge technique using methane. Rapid thermal processing of the films was accomplished in nitrogen gas using tungsten halogen light. The rapid thermal processing was done at several fixed temperatures (up to 600 C), as a function of time (up to 1800 sec). The films were characterized by optical absorption and by ellipsometry in the near UV and the visible. The bandgap, estimated from extrapolation of the linear part of a Tauc plot, decreases both with the annealing temperature and the annealing time, with the temperature dependence being the dominating factor. The density of states parameter increases up to 25 percent and the refractive index changes up to 20 percent with temperature increase. Possible explanations of the mechanisms involved in these processes are discussed.

  10. Released Plasmonic Electric Field of Ultrathin Tetrahedral-Amorphous-Carbon Films Coated Ag Nanoparticles for SERS

    PubMed Central

    Liu, Fanxin; Tang, Chaojun; Zhan, Peng; Chen, Zhuo; Ma, Hongtao; Wang, Zhenlin

    2014-01-01

    We have demonstrated the plasmonic characteristics of an ultrathin tetrahedral amorphous carbon (ta-C) film coated with Ag nanoparticles. The simulation result shows that, under resonant and non-resonant excitations, the strongest plasmonic electric field of 1 nm ta-C coated Ag nanoparticle is not trapped within the ta-C layer but is released to its outside surface, while leaving the weaker electric field inside ta-C layer. Moreover, this outside plasmonic field shows higher intensity than that of uncoated Ag nanoparticle, which is closely dependent on the excitation wavelength and size of Ag particles. These observations are supported by the SERS measurements. We expect that the ability for ultrathin ta-C coated Ag nanoparticles as the SERS substrates to detect low concentrations of target biomolecules opens the door to the applications where it can be used as a detection tool for integrated, on-chip devices. PMID:24675437

  11. Synergistic etch rates during low-energetic plasma etching of hydrogenated amorphous carbon

    SciTech Connect

    Hansen, T. A. R.; Weber, J. W.; Colsters, P. G. J.; Mestrom, D. M. H. G.; Sanden, M. C. M. van de; Engeln, R.

    2012-07-01

    The etch mechanisms of hydrogenated amorphous carbon thin films in low-energetic (<2 eV) high flux plasmas are investigated with spectroscopic ellipsometry. The results indicate a synergistic effect for the etch rate between argon ions and atomic hydrogen, even at these extremely low kinetic energies. Ion-assisted chemical sputtering is the primary etch mechanism in both Ar/H{sub 2} and pure H{sub 2} plasmas, although a contribution of swift chemical sputtering to the total etch rate is not excluded. Furthermore, ions determine to a large extent the surface morphology during plasma etching. A high influx of ions enhances the etch rate and limits the surface roughness, whereas a low ion flux promotes graphitization and leads to a large surface roughness (up to 60 nm).

  12. Mechanism of wiggling enhancement due to HBr gas addition during amorphous carbon etching

    NASA Astrophysics Data System (ADS)

    Kofuji, Naoyuki; Ishimura, Hiroaki; Kobayashi, Hitoshi; Une, Satoshi

    2015-06-01

    The effect of gas chemistry during etching of an amorphous carbon layer (ACL) on wiggling has been investigated, focusing especially on the changes in residual stress. Although the HBr gas addition reduces critical dimension loss, it enhances the surface stress and therefore increases wiggling. Attenuated total reflectance Fourier transform infrared spectroscopy revealed that the increase in surface stress was caused by hydrogenation of the ACL surface with hydrogen radicals. Three-dimensional (3D) nonlinear finite element method analysis confirmed that the increase in surface stress is large enough to cause the wiggling. These results also suggest that etching with hydrogen compound gases using an ACL mask has high potential to cause the wiggling.

  13. Amorphous Vanadium Oxide/Carbon Composite Positive Electrode for Rechargeable Aluminum Battery.

    PubMed

    Chiku, Masanobu; Takeda, Hiroki; Matsumura, Shota; Higuchi, Eiji; Inoue, Hiroshi

    2015-11-11

    Amorphous vanadium oxide/carbon composite (V2O5/C) was first applied to the positive electrode active material for rechargeable aluminum batteries. Electrochemical properties of V2O5/C were investigated by cyclic voltammetry and charge-discharge tests. Reversible reduction/oxidation peaks were observed for the V2O5/C electrode and the rechargeable aluminum cell showed the maximum discharge capacity over 200 mAh g(-1) in the first discharging. The XPS analyses after discharging and the following charging exhibited that the redox of vanadium ion in the V2O5/C active material occurred during discharging and charging, and the average valence of V changed between 4.14 and 4.85. PMID:26489385

  14. Investigation of the microstructure, mechanical properties and thermal stability of nanocomposite coatings based on amorphous carbon

    NASA Astrophysics Data System (ADS)

    Andreev, A. V.; Litovchenko, I. Y.; Korotaev, A. D.; Borisov, D. P.

    2015-10-01

    The Ti-C-Ni-Cr and Ti-C-Ni-Cr-Al-Si nanocomposite coatings based on amorphous carbon and the nanosized particles were synthesized by magnetron method. The results of the microstructure features and mechanical properties investigations of these coatings are presented. The thermal stability of microstructure and properties of these coatings at tempering up to 900°C were investigated. These coatings have a high (11-18 GPa) hardness, low (μ < 0.2) the coefficient of friction and high thermal stability of the microstructure and properties up to 700°C. The features of elastically stressed state of nanosized particles in these coatings were founded. A high local internal stresses in the TiC nanoscale particles do not observed.

  15. Nanoelectromechanical digital logic circuits using curved cantilever switches with amorphous-carbon-coated contacts

    NASA Astrophysics Data System (ADS)

    Ayala, Christopher L.; Grogg, Daniel; Bazigos, Antonios; Bleiker, Simon J.; Fernandez-Bolaños, Montserrat; Niklaus, Frank; Hagleitner, Christoph

    2015-11-01

    Nanoelectromechanical (NEM) switches have the potential to complement or replace traditional CMOS transistors in the area of ultra-low-power digital electronics. This paper reports the demonstration of prototype circuits including the first 3-stage ring oscillator built using cell-level digital logic elements based on curved NEM switches. The ring oscillator core occupies an area of 30 μm × 10 μm using 6 NEM switches. Each NEM switch device has a footprint of 5 μm × 3 μm, an air gap of 60 μm and is coated with amorphous carbon (a-C) for reliable operation. The ring oscillator operates at a frequency of 6.7 MHz, and confirms the simulated inverter propagation delay of 25 ns. The successful fabrication and measurement of this demonstrator are key milestones on the way towards an optimized, scaled technology with sub-nanosecond switching times, lower operating voltages and VLSI implementation.

  16. Tetrahedral Amorphous Carbon (ta-C) Ultra Thin Films for Slider Overcoat Application

    NASA Astrophysics Data System (ADS)

    Shi, X.; Hu, Y. H.; Hu, L.

    Tetrahedral Amorphous Carbon (ta-C) thin film by using Filtered Cathodic Vacuum Arc (FCVA) technique has proven to be wear-resistive and corrosion resistant for a wide range of electrical, optical, and mechanical applications. Many investigations have shown that the ta-C film prepared by the FCVA technique can provide a superior ultra thin overcoat for the sliders and media compared to ECR-CVD and IBD coating technology. The ta-C film excels in terms of the film density, hardness, surface roughness and corrosion resistance. Nanofilm Technology International (NTI) has successfully developed and commercialized the FCVA coating system (FS series) for the slider overcoat application, which provides a good quality film with a high hardness (~50 GPa), low stress (2~3 GPa), low macro-particle density (~1/cm2 for particles > 0.3 μm), good uniformity (< 4%$ in 8 inch coating area) and high production repeatability (< 5%).

  17. Platinum containing amorphous hydrogenated carbon (a-C:H/Pt) thin films as selective solar absorbers

    NASA Astrophysics Data System (ADS)

    Lan, Yung-Hsiang; Brahma, Sanjaya; Tzeng, Y. H.; Ting, Jyh-Ming

    2014-10-01

    We have investigated a double-cermet structured thin film in which an a-C:H thin film was used as an anti-reflective (AR) layer and two platinum-containing amorphous hydrogenated carbon (a-C:H/Pt) thin films were used as the double cermet layers. A reactive co-sputter deposition method was used to prepare both the anti-reflective and cermet layers. Effects of the target power and heat treatment were studied. The obtained films were characterized using X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy. The optical absorptance and emittance of the as deposited and annealed films were determined using UV-vis-NIR spectroscopy. We show that the optical absorptance of the resulting double-cermet structured thin film is as high as 96% and remains to be 91% after heat treatment at 400 °C, indicating the thermal stability of the film.

  18. Amorphous carbon film growth on Si: Correlation between stress and generation of defects into the substrate

    SciTech Connect

    Brusa, R.S.; Macchi, C.; Mariazzi, S.; Karwasz, G.P.; Laidani, N.; Bartali, R.; Anderle, M.

    2005-05-30

    Amorphous carbon films of several thicknesses were prepared by graphite sputtering on crystalline silicon substrate. The samples were depth profiled with positron annihilation spectroscopy for open-volume measurements and characterized for their residual internal stress. It was found that after film growth the substrate presents vacancy-like defects decorated by oxygen in a layer extending in the substrate by several tens of nanometers beyond the film/Si interface. The width of the defected layer and the decoration of vacancy-like defects are directly and inversely proportional to the measured intensity of the residual stress, respectively. These findings indicate the existence of a relaxation mechanism of the stress in the films that involves deeply the substrate. The decorated vacancy-like defects are suggested to be bounded to dislocations induced in the substrate by the stress relaxation.

  19. Abnormal humidity-dependent electrical properties of amorphous carbon/silicon heterojunctions

    SciTech Connect

    Gao Xili; Zhang Xiaozhong; Wan Caihua; Zhang Xin; Wu Lihua; Tan Xinyu

    2010-11-22

    Amorphous carbon (a-C) film/n-Si heterojunctions have been fabricated by pulse laser deposition, and their current-voltage characteristics have been investigated. The results show that the atmosphere relative humidity (RH) has a significant effect on the reverse bias I-V characteristics of the heterojunctions. For the low bias voltages, the resistance of the a-C/Si heterojunction decreases with the increase of the RH. However, when the applied voltage is greater than a threshold, the resistance of the a-C/Si heterojunctions increases with the increase of the RH. This humidity-dependent phenomenon is attributed to the charge transfer from the absorbed H{sub 2}O molecular to a-C film.

  20. Aurum and Platinum as Metal Contact to Amorphous Carbon Thin Films

    NASA Astrophysics Data System (ADS)

    Mohamad, F.; Suriani, A. B.; Noor, U. M.; Rusop, M.

    2010-07-01

    Amorphous carbon (a-C) thin films have been deposited on quartz substrates at different deposition temperatures ranging from 700 °C-800 °C. The objective of this work is to investigate several electrical contacts on a-C thin films and to find the suitable method to fabricate ohmic contact on a-C thin films that prepared from a natural product, camphor (C10H16O). The a-C thin films were prepared with a simple thermal CVD method. In this study, Aurum (Au) and Platinum (Pt) were selected as the metal contact to a-C thin films. I-V characteristics measurement was carried out to study the contact between metal and a-C thin films. It was found that increasing deposition temperature also contributes to the variation I-V characteristics of a-C thin films.

  1. Effect of air post contamination on mechanical properties of amorphous carbon nitride thin films

    NASA Astrophysics Data System (ADS)

    Lejeune, M.; Benlahsen, M.; Lemoine, P.

    2005-08-01

    We report in this study the mechanical, structural and compositional characteristics of amorphous carbon nitride films (a-CN x) deposited on Si(100) using RF magnetron sputtering of graphite targets in pure nitrogen and under different RF powers. The properties of the films were determined in their as deposited state using nuclear reaction analysis (NRA), elastic recoil detection (ERDA), infrared (IR) absorption and Raman spectroscopy. The mechanical properties were obtained combining nanoindentation and residual stress measurements. The presence of various types of C-N bonds, as well as the post-deposition contamination of the deposited films by oxygen and water (voids) is revealed. The measured hardness and Young modulus were 0.9-2.03 and 23-27 GPa, respectively. These results have been analysed in term of the matrix flexibility which results from the nitrogen content and the porous character of the films, which can affect deeply the estimation of the physical-mechanical properties of the films.

  2. Highly photoconductive amorphous carbon nitride films prepared by cyclic nitrogen radical sputtering

    SciTech Connect

    Katsuno, T.; Nitta, S.; Habuchi, H.; Stolojan, V.; Silva, S.R.P.

    2004-10-04

    We report on the growth of amorphous carbon nitride films (a-CN{sub x}) showing the highest conductivity to date. The films were prepared using a layer-by-layer method (a-CN{sub x}:LL), by the cyclical nitrogen radical sputtering of a graphite radical, alternated with a brief hydrogen etch. The photosensitivity S of these films is 10{sup 5}, defined as the ratio of the photoconductivity {sigma}{sub p} to the dark conductivity {sigma}{sub d} and is the highest value reported thus far. We believe that the carriers generated by the monochromatic light (photon energy 6.2 eV) in the a-CN{sub x}:LL films are primarily electrons, with the photoconductivity shown to increase with substrate deposition temperature.

  3. Understanding the catalyst-free transformation of amorphous carbon into graphene by current-induced annealing

    PubMed Central

    Barreiro, Amelia; Börrnert, Felix; Avdoshenko, Stanislav M.; Rellinghaus, Bernd; Cuniberti, Gianaurelio; Rümmeli, Mark H.; Vandersypen, Lieven M. K.

    2013-01-01

    We shed light on the catalyst-free growth of graphene from amorphous carbon (a–C) by current-induced annealing by witnessing the mechanism both with in-situ transmission electron microscopy and with molecular dynamics simulations. Both in experiment and in simulation, we observe that small a–C clusters on top of a graphene substrate rearrange and crystallize into graphene patches. The process is aided by the high temperatures involved and by the van der Waals interactions with the substrate. Furthermore, in the presence of a–C, graphene can grow from the borders of holes and form a seamless graphene sheet, a novel finding that has not been reported before and that is reproduced by the simulations as well. These findings open up new avenues for bottom-up engineering of graphene-based devices.

  4. Far-infrared absorption measurements of graphite, amorphous carbon, and silicon carbide

    NASA Astrophysics Data System (ADS)

    Tanabe, T.; Nakada, Y.; Kamijo, F.; Sakata, A.

    The mass absorption coefficients of graphite (G), amorphous-carbon (AC), and SiC grains at 25-250 microns are determined experimentally at room temperature and applied to the interpretation of published IR observations of IRC+10216. Absorption measurements are obtained using a single-beam grating spectrometer with a Goley-cell detector by a polyethylene-powder-tablet technique. The results are presented in a table and graphs. The mass absorption constants (in sq cm/g) are calculated as 642 for G, 281 for AC produced in Ar, 93.9 for AC produced in H2, and 19.6 for SiC; power-law relationships to wavelength, with indices of -2.18, 0.60, -0.59, and -1.37 (respectively) are established. AC is found to be the most likely constituent of the IRC+10216 dust cloud, permitting the dust mass to be estimated as 0.0001 solar mass.

  5. Immobilization of Pseudomonas sp. DG17 onto sodium alginate–attapulgite–calcium carbonate

    PubMed Central

    Wang, Hong Qi; Hua, Fei; Zhao, Yi Cun; Li, Yi; Wang, Xuan

    2014-01-01

    A strain of Pseudomonas sp. DG17, capable of degrading crude oil, was immobilized in sodium alginate–attapulgite–calcium carbonate for biodegradation of crude oil contaminated soil. In this work, proportion of independent variables, the laboratory immobilization parameters, the micromorphology and internal structure of the immobilized granule, as well as the crude oil biodegradation by sodium alginate–attapulgite–calcium carbonate immobilized cells and sodium alginate–attapulgite immobilized cells were studied to build the optimal immobilization carrier and granule-forming method. The results showed that the optimal concentrations of sodium alginate–attapulgite–calcium carbonate and calcium chloride were 2.5%–3.5%, 0.5%–1%, 3%–7% and 2%–4%, respectively. Meanwhile, the optimal bath temperature, embedding cell amount, reaction time and multiplication time were 50–60 °C, 2%, 18 h and 48 h, respectively. Moreover, biodegradation was enhanced by immobilized cells with a total petroleum hydrocarbon removal ranging from 33.56% ± 3.84% to 56.82% ± 3.26% after 20 days. The SEM results indicated that adding calcium carbonate was helpful to form internal honeycomb-like pores in the immobilized granules. PMID:26019567

  6. The influence of electron discharge and magnetic field on calcium carbonate (CaCO3) precipitation

    NASA Astrophysics Data System (ADS)

    Putro, Triswantoro; Endarko

    2016-04-01

    The influences of electron discharge and magnetic field on calcium carbonate (CaCO3) precipitation in water have been successfully investigated. The study used three pairs of magnetic field 0.1 T whilst the electron discharge was generated from television flyback transformer type BW00607 and stainless steel SUS 304 as an electrode. The water sample with an initial condition of 230 mg/L placed in the reactor with flow rate 375 mL/minutes, result showed that the electron discharge can be reduced contain of calcium carbonate the water sample around 17.39% within 2 hours. Meanwhile for the same long period of treatment and flow rate, around 56.69% from initial condition of 520 mg/L of calcium carbonate in the water sample can be achieved by three pairs of magnetic field 0.1 T. When the combination of three pairs of magnetic field 0.1 T and the electron discharge used for treatment, the result showed that the combination of electron discharge and magnetic field methods can be used to precipitate calcium carbonate in the water sample 300 mg/L around 76.66% for 2 hours of treatment. The study then investigated the influence of the polar position of the magnetic field on calcium carbonate precipitation. Two positions of magnetic field were tested namely the system with alternated polar magnetics and the system without inversion of the polar magnetics. The influence of the polar position showed that the percentage reduction in levels of calcium carbonate in the water sample (360 mg/L) is significant different. Result showed that the system without inversion of the polar magnetics is generally lower than the system with alternated polar magnetics, with reduction level at 30.55 and 57.69%, respectively.

  7. Amorphous Molybdenum Sulfide on Graphene-Carbon Nanotube Hybrids as Highly Active Hydrogen Evolution Reaction Catalysts.

    PubMed

    Pham, Kien-Cuong; Chang, Yung-Huang; McPhail, David S; Mattevi, Cecilia; Wee, Andrew T S; Chua, Daniel H C

    2016-03-01

    In this study, we report on the deposition of amorphous molybdenum sulfide (MoSx, with x ≈ 3) on a high specific surface area conductive support of Graphene-Carbon Nanotube hybrids (GCNT) as the Hydrogen Evolution Reaction (HER) catalysts. We found that the high surface area GCNT electrode could support the deposition of MoSx at much higher loadings compared with simple porous carbon paper or flat graphite paper. The morphological study showed that MoSx was successfully deposited on and was in good contact with the GCNT support. Other physical characterization techniques suggested the amorphous nature of the deposited MoSx. With a typical catalyst loading of 3 mg cm(-2), an overpotential of 141 mV was required to obtain a current density of 10 mA cm(-2). A Tafel slope of 41 mV decade(-1) was demonstrated. Both measures placed the MoSx-deposited GCNT electrode among the best performing molybdenum sulfide-based HER catalysts reported to date. The electrode showed a good stability with only a 25 mV increase in overpotential required for a current density of 10 mA cm(-2), after undergoing 500 potential sweeps with vigorous bubbling present. The current density obtained at -0.5 V vs SHE (Standard Hydrogen Electrode potential) decreased less than 10% after the stability test. The deposition of MoSx on high specific surface area conductive electrodes demonstrated to be an efficient method to maximize the catalytic performance toward HER. PMID:26864503

  8. Multiscale simulation of thermal disruption in resistance switching process in amorphous carbon

    NASA Astrophysics Data System (ADS)

    Popov, A. M.; Shumkin, G. N.; Nikishin, N. G.

    2015-09-01

    The switching of material atomic structure and electric conductivity is used in novel technologies of making memory on the base of phase change. The possibility of making memory on the base of amorphous carbon is shown in experiment [1]. Present work is directed to simulation of experimentally observed effects. Ab initio quantum calculations were used for simulation of atomic structure changes in amorphous carbon [2]. These simulations showed that the resistance change is connected with thermally induced effects. The temperature was supposed to be the function of time. In present paper we propose a new multiscale, self-consistent model which combines three levels of simulation scales and takes into account the space and time dependencies of the temperature. On the first level of quantum molecular dynamic we provide the calculations of phase change in atomic structure with space and time dependence of the temperature. Nose-Hover thermostats are used for MD simulations to reproduce space dependency of the temperature. It is shown that atomic structure is localized near graphitic layers in conducting dot. Structure parameter is used then on the next levels of the modeling. Modified Ehrenfest Molecular Dynamics is used on the second level. Switching evolution of electronic subsystem is obtained. In macroscopic scale level the heat conductivity equation for continuous media is used for calculation space-time dependence of the temperature. Joule heat source depends on structure parameter and electric conductivity profiles obtained on previous levels of modeling. Iterative procedure is self-consistently repeated combining three levels of simulation. Space localization of Joule heat source leads to the thermal disruption. Obtained results allow us to explain S-form of the Volt-Ampere characteristic observed in experiment. Simulations were performed on IBM Blue Gene/P supercomputer at Moscow State University.

  9. Micromachining of large area amorphous carbon membranes prepared by filtered cathodic vacuum arc technique

    NASA Astrophysics Data System (ADS)

    Liujiang, Yu; Tay, B. K.; Sheeja, D.; Fu, Y. Q.; Miao, J. M.

    2004-02-01

    Currently, there is a strong drive to make micro-electro-mechanical system (MEMS) devices from higher performance materials such as diamond-like carbon or amorphous carbon (a-C) films, due to their excellent tribological properties, low-stiction (hydrophobic) surfaces, chemical inertness and high elastic modulus, compared to that of Si. The hydrogen free a-C films prepared, by Nanyang Technological University's (NTUs) patented filtered cathodic vacuum arc (FCVA) technique, at 100 eV exhibits high fraction of tetrahedral (sp 3 bonded) carbon atoms. These films exhibit relatively high hardness, stiffness and wear resistance in addition to low friction and stiction behaviour. However, the primary problem lies in the large intrinsic compressive stress induced during the deposition process. By making use of high substrate pulse bias, we have successfully produced low stress, thick a-C films. The films were then characterised using different equipments to evaluate the stress, microstructure and morphological roughness. Large area a-C membranes, of 2 mm×2 mm in size, have also been fabricated using the low stress, thick film deposited by the above method.

  10. Excellent wear life of silicon nitride/tetrahedral amorphous carbon bilayer overcoat on functional tape heads

    NASA Astrophysics Data System (ADS)

    Yeo, Reuben J.; Dwivedi, Neeraj; Tripathy, S.; Bhatia, C. S.

    2015-03-01

    Developing ultrathin and highly wear-resistant overcoats for magnetic tape heads is one of the current research areas of interest, because of its potential to delay pole tip recession and increase the operational lifetime of high areal density tape drives. Using optimized process conditions and an appropriate overcoat design, we report on the development of a ˜20 nm thick silicon nitride/tetrahedral amorphous carbon (Si/SiNx/ta-C) bilayer overcoat, where the ta-C film was deposited by a filtered cathodic vacuum arc process. The bilayer overcoat deposited on a functional tape head survived 40-50 × 106 m of testing with commercial tape media under standard industrial testing conditions. The excellent wear resistance of the overcoat was attributed to the generation of high (˜72%) sp3 carbon content and the formation of strong interfacial bonds, such as Si-C, C=N, nitrile, and (Al, Ti)N at the interfaces, as confirmed by various spectroscopic techniques. This study demonstrates the pivotal role of high sp3 carbon bonding combined with enhanced interfacial bonding in developing an ultrathin yet durable protective overcoat for magnetic tape heads.

  11. Crystallization effects and diamond formation in amorphous carbon films under low energy ion beam irradiation

    NASA Astrophysics Data System (ADS)

    Patsalas, P.; Logothetidis, S.

    2001-05-01

    The crystallization effects occurring in various types of amorphous carbon (a-C) thin films with different structure and bonding induced by post-growth low energy (<1.5 keV) Ar + ion beam irradiation are presented. Detailed X-ray diffraction (XRD) measurements were used to identify several allotropic forms of carbon such as graphite and diamond as well as SiC detected in a-C films after ion irradiation. The diamond and SiC nucleation occurs close to the a-C/Si interface, beyond the ion penetration depth suggesting a non-direct nucleation mechanism. The relative content, grain size, distribution and orientation of each particular crystalline phase in the films depend strongly on the microstructural characteristics of the as-grown films. We also consider the effects of ion energy and fluence and substrate material on the crystallization process in an effort to get a deeper insight of the fundamental mechanisms occurring during the interaction of various carbon materials with low energy ion beams.

  12. Electrical and Electrochemical Properties of Nitrogen-Containing Tetrahedral Amorphous Carbon (ta-C) Thin Films

    NASA Astrophysics Data System (ADS)

    Yang, Xingyi

    Tetrahedral amorphous carbon (ta-C) is a diamond-like carbon (DLC) material comprised of a mixture of sp2 (˜40%) and sp3-bonded (˜60%) carbon domains. The physicochemical structure and electrochemical properties depend strongly on the sp2/sp3 bonding ratio as well as the incorporation of impurities, such as hydrogen or nitrogen. The ability to grow ta-C films at lower temperatures (25-100 °C) on a wider variety of substrates is a potential advantage of these materials as compared with diamond films. In this project, the basic structural and electrochemical properties of nitrogen-incorporated ta-C thin films will be discussed. The major goal of this work was to determine if the ta-C:N films exhibit electrochemical properties more closely aligned with those of boron-doped diamond (sp 3 carbon) or glassy carbon (amorphous sp2 carbon). Much like diamond, ta-C:N thin-film electrodes are characterized by a low background voltammetric current, a wide working potential window, relatively rapid electron-transfer kinetics for aqueous redox systems, such as Fe(CN) 6-3/-4 and Ru(NH3)6+3/+2 , and weak adsorption of polar molecules from solution. For example, negligible adsorption of methylene blue was found on the ta-C:N films in contrast to glassy carbon; a surface on which this molecule strongly adsorbs. The film microstructure was studied with x-ray photoelectron microscopy (XPS), visible Raman spectroscopy and electron-energy loss spectroscopy (EELS); all of which revealed the sp2-bonded carbon content increased with increasing nitrogen. The electrical properties of ta-C:N films were studied by four-point probe resistance measurement and conductive-probe AFM (CP-AFM). The incorporation of nitrogen into ta-C films increased the electrical conductivity primarily by increasing the sp2-bonded carbon content. CP-AFM showed the distribution of the conductive sp2-carbon on the film surface was not uniform. These films have potential to be used in field emission area. The

  13. Effects of Phosphorus and Carbon Contents on Amorphous Forming Ability in Fe-based Amorphous Alloys Used for Thermal Spray Coatings

    NASA Astrophysics Data System (ADS)

    Do, Jeonghyeon; Jung, Seungmun; Lee, Hyuk-Joong; Lee, Byeong-Joo; Cha, Gil-up; Jo, Chang Yong; Lee, Sunghak

    2013-06-01

    Cost-effective Fe-based amorphous alloys used for thermal spray coatings were developed by varying contents of P and C, and their microstructure, hardness, and corrosion resistance were analyzed. In order to achieve chemical compositions having high amorphous forming ability, thermodynamically calculated phase diagrams of Fe-Al-P-C-B five-component system were used, from which compositions of super-cooled liquid having the lowest driving force of formation of crystalline phases were obtained. The thermodynamic calculation results showed that only phases of Fe3P and Fe3C were formed in the Fe78Al2P(18.3- x)C x B1.7 alloy system. Considering driving force curves of Fe3P and Fe3C, the carbon contents were selected to be 6.90 and 7.47 at. pct, when the thermodynamic calculation temperatures were 697 K (414 °C) and 715 K (442 °C), respectively. According to the microstructural analysis of suction-cast alloys, the Fe78Al2P10.83C7.47B1.7 alloy showed a fully amorphous microstructure, whereas the Fe78Al2P11.40C6.9B1.7 and Fe78Al2P10.3C8.0B1.7 alloys contained Fe3P and Fe3C phases. This Fe78Al2P10.83C7.47B1.7 alloy showed the better hardness and corrosion resistance than those of conventional thermal spray coating alloys, and its production cost could be lowered using cheaper alloying elements, thereby leading to the practical application to amorphous thermal spray coatings.

  14. Adsorption of sodium polyacrylate in high solids loading calcium carbonate slurries.

    PubMed

    Taylor, Joshua J; Sigmund, Wolfgang M

    2010-01-15

    The adsorption of sodium polyacrylate (NaPAA) in slurries with up to 75 wt.% calcium carbonate was investigated with the use of attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and adsorption of probe molecules. Analysis of the IR spectra demonstrated that the carboxylate groups of NaPAA adsorbed onto ground calcium carbonate (GCC) in three different modes. These modes were shown to be dependent on the solids loading and age of the slurry. Further investigation lead to the determination of the chelating ability of NaPAA at high solids loading. PMID:19875128

  15. Physicochemical Characterization and In Vivo Evaluation of Amorphous and Partially Crystalline Calcium Phosphate Coatings Fabricated on Ti-6Al-4V Implants by the Plasma Spray Method.

    PubMed

    Bonfante, Estevam A; Witek, Lukasz; Tovar, Nick; Suzuki, Marcelo; Marin, Charles; Granato, Rodrigo; Coelho, Paulo G

    2012-01-01

    Objective. To characterize the topographic and chemical properties of 2 bioceramic coated plateau root form implant surfaces and evaluate their histomorphometric differences at 6 and 12 weeks in vivo. Methods. Plasma sprayed hydroxyapatite (PSHA) and amorphous calcium phosphate (ACP) surfaces were characterized by scanning electron microscopy (SEM), interferometry (IFM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). Implants were placed in the radius epiphysis, and the right limb of dogs provided implants that remained for 6 weeks, and the left limb provided implants that remained 12 weeks in vivo. Thin sections were prepared for bone-to-implant contact (BIC) and bone-area-fraction occupancy (BAFO) measurements (evaluated by Friedman analysis P < 0.05). Results. Significantly, higher S(a) (P < 0.03) and S(q) (P < 0.02) were observed for ACP relative to PSHA. Chemical analysis revealed significantly higher HA, calcium phosphate, and calcium pyrophosphate for the PSHA surface. BIC and BAFO measurements showed no differences between surfaces. Lamellar bone formation in close contact with implant surfaces and within the healing chambers was observed for both groups. Conclusion. Given topographical and chemical differences between PSHA and ACP surfaces, bone morphology and histomorphometric evaluated parameters showed that both surfaces were osseoconductive in plateau root form implants. PMID:22969806

  16. Thermally induced crystallization and phase evolution in powders derived from amorphous calcium phosphate precipitates with a Ca/P ratio of 1:1

    NASA Astrophysics Data System (ADS)

    Zyman, Zoltan; Epple, Matthias; Goncharenko, Anton; Rokhmistrov, Dmytro; Prymak, Oleg; Loza, Kateryna

    2016-09-01

    Calcium phosphate powders of calcium pyrophosphate α1-CPP (the metastable phase of the high-temperature polymorph α-CPP) and the polymorph β-CPP (stable in this range), of α1-CPP, β-CPP, α1-TCP (metastable polymorph of the high-temperature phase α-tricalcium phosphate) and β-tricalcium phosphate β-TCP were prepared by heating amorphous calcium phosphate (ACP) precipitates with the nominal Ca/P ratio of 1:1 by nitrate synthesis. α1-CPP/β-CPP resulted from a crystallization at 530-640 °C and subsequent heating to 980 °C of unwashed and lyophilized ACP. α1-CPP/β-CPP/α1-TCP/β-TCP was formed by crystallization at 620-720 °C, followed by heating of six-time washed and lyophilized ACP precipitates from an ultra-short synthesis. The activation energy for the crystallization of ACP to α1-CPP was determined with 165 kJ mol-1. The reason for the occurrence of the TCP phases (Ca/P ratio=1.5) from ACP (Ca/P ratio=1) is discussed. The powders are prospective biomaterials for bone substitution because they combine effective bioactive phases with the metastable polymorphs α1-CPP and α1-TCP.

  17. Phototransformation-Induced Aggregation of Functionalized Single-Walled Carbon Nanotubes: The Importance of Amorphous Carbon

    EPA Science Inventory

    Single-walled carbon nanotubes (SWCNTs) with proper functionalization are desirable for applications that require dispersion in aqueous and biological environments, and functionalized SWCNTs also serve as building blocks for conjugation with specific molecules in these applicatio...

  18. Development of spin-on carbon hardmasks with comparable etch resistance to Amorphous Carbon Layer (ACL)

    NASA Astrophysics Data System (ADS)

    Cheon, Hwan-Sung; Yoon, Kyong-Ho; Kim, Min-Soo; Oh, Seung Bae; Song, Jee-Yun; Tokareva, Nataliya; Kim, Jong-Seob; Chang, Tuwon

    2008-11-01

    In recent microlithography of semiconductor fabrication, spin-on hardmask (SOH) process continue to gain popularity as it replaces the traditional SiON/ACL hardmask scheme which suffers from high CoO, low productivity, particle contamination, and layer alignment issues. In the SOH process, organic polymer with high carbon content is spin-cast to form a carbon hardmask film. In the previous papers, we reported the development of organic SOH materials and their application in sub-70 nm lithography. In this paper, we describe the synthesis of organic polymers with very high carbon contents (>92 wt.%) and the evaluation of the spin-coated films for the hardmask application. The high carbon content of the polymer ensures improved etch resistance which amounts to >90% of ACL's resistance. However, as the carbon content of the polymers increases, the solubility in common organic solvents becomes lower. Here we report the strategies to improve the solubility of the high carbon content resins and optimization of the film properties for the SOH application.

  19. Thermal breakdown of calcium carbonate and constraints on its use as a biomarker

    NASA Astrophysics Data System (ADS)

    Thompson, Stephen P.; Parker, Julia E.; Tang, Chiu C.

    2014-02-01

    Observed differences in the thermal behaviour of calcium carbonates of biogenic and abiogenic origin (phase transformation and breakdown temperatures) are widely cited as potential biomarkers for whether life once existed on Mars. Although seemingly compelling, there has been no systematic investigation into the physical mechanism behind these apparent differences and therefore no direct proof that they are uniquely diagnostic of a biogenic versus abiogenic formation. In this paper we present a laboratory investigation into the thermal behaviour of two high purity calcium carbonates, one of which was produced in the presence of an amino acid as a biomimetic carbonate. In situ synchrotron X-ray powder diffraction measurements show the aragonite-to-calcite phase transition and calcite-to-oxide breakdown temperatures are significantly lower in the biomimetic carbonate. The observed thermal differences closely match reported differences between biogenic and geological abiogenic carbonates. The biomimetic carbonate exhibits a modified crystal morphology, with a highly strained internal crystal lattice, similar to biogenic carbonate structures. Since biogenic carbonates are formed in the presence of organic macromolecules such as amino acids, the induced microstrain appears to be the defining common factor as it adds an additional energy term to the carbonate lattice energy, which lowers the activation energy required for structural transformation or decomposition. Although produced via biomimetic means, the carbonate investigated here is nevertheless abiogenic in origin and we propose that given suitable localised conditions such as pooled water and a supply of organic molecules, naturally occurring biomimetic carbonates could have similarly formed on the martian surface and could therefore exhibit the same thermal characteristics as biogenic carbonate. Thus as a limiting case - without other supporting observations - the thermal behaviour of martian calcium carbonate

  20. Nanocomposite metal amorphous-carbon thin films deposited by hybrid PVD and PECVD technique.

    PubMed

    Teixeira, V; Soares, P; Martins, A J; Carneiro, J; Cerqueira, F

    2009-07-01

    Carbon based films can combine the properties of solid lubricating graphite structure and hard diamond crystal structure, i.e., high hardness, chemical inertness, high thermal conductivity and optical transparency without the crystalline structure of diamond. Issues of fundamental importance associated with nanocarbon coatings are reducing stress, improving adhesion and compatibility with substrates. In this work new nanocomposite coatings with improved toughness based in nanocrystalline phases of metals and ceramics embedded in amorphous carbon matrix are being developed within the frame of a research project: nc-MeNxCy/a-C(Me) with Me = Mo, Si, Al, Ti, etc. Carbide forming metal/carbon (Me/C) composite films with Me = Mo, W or Ti possess appropriate properties to overcome the limitation of pure DLC films. These novel coating architectures will be adopted with the objective to decrease residual stress, improve adherence and fracture toughness, obtain low friction coefficient and high wear-resistance. Nanocomposite DLC's films were deposited by hybrid technique using a PVD-Physically Vapor Deposition (magnetron sputtering) and Plasma Enhanced Chemical Vapor Deposition (PECVD), by the use of CH4 gas. The parameters varied were: deposition time, substrate temperature (180 degrees C) and dopant (Si + Mo) of the amorphous carbon matrix. All the depositions were made on silicon wafers and steel substrates precoated with a silicon inter-layer. The characterisation of the film's physico-mechanical properties will be presented in order to understand the influence of the deposition parameters and metal content used within the a-C matrix in the thin film properties. Film microstructure and film hybridization state was characterized by Raman Spectroscopy. In order to characterize morphology SEM and AFM will be used. Film composition was measured by Energy-Dispersive X-ray analysis (EDS) and by X-ray photoelectron spectroscopy (XPS). The contact angle for the produced DLC's on

  1. No-flash-point electrolytes applied to amorphous carbon/Li 1+ xMn 2O 4 cells for EV use

    NASA Astrophysics Data System (ADS)

    Arai, Juichi

    Use of no-flash-point electrolytes (NFEs) containing non-flammable solvent for an amorphous carbon/Li 1+ xMn 2O 4 cell has been studied. We prepared three NFEs: NFE1 was composed of 1 M (mol dm -3) of LiN[SO 2C 2F 5] 2 as supporting electrolyte, and 80 vol.% of methyl nonafluorobutyl ether (MFE) and 20 vol.% of ethyl methyl carbonate (EMC) as solvents; NFE2 was prepared by adding 0.5 M of EC (ethylene carbonate) to NFE1; and NFE3 was prepared by adding 0.1 M of LiPF 6 to NFE2. Charge-discharge performance of Li 1+ xMn 2O 4/Li cells and amorphous carbon/Li cells with NFEs were investigated. The amorphous carbon/Li 1+ xMn 2O 4 18650 cells were fabricated and investigated in terms of rate capability and cycle life. NFE2 showed good rate performance. NFE3 showed the best cycle life among the NFE electrolyte cells, though it had only fair rate performance. Electrochemical impedance spectroscopy (EIS), attenuated total reflection infrared (ATR-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) were measured to study the effect of EC and LiPF 6.

  2. Nanoanalytical Electron Microscopy Reveals a Sequential Mineralization Process Involving Carbonate-Containing Amorphous Precursors.

    PubMed

    Nitiputri, Kharissa; Ramasse, Quentin M; Autefage, Hélène; McGilvery, Catriona M; Boonrungsiman, Suwimon; Evans, Nicholas D; Stevens, Molly M; Porter, Alexandra E

    2016-07-26

    A direct observation and an in-depth characterization of the steps by which bone mineral nucleates and grows in the extracellular matrix during the earliest stages of maturation, using relevant biomineralization models as they grow into mature bone mineral, is an important research goal. To better understand the process of bone mineralization in the extracellular matrix, we used nanoanalytical electron microscopy techniques to examine an in vitro model of bone formation. This study demonstrates the presence of three dominant CaP structures in the mineralizing osteoblast cultures: <80 nm dense granules with a low calcium to phosphate ratio (Ca/P) and crystalline domains; calcium phosphate needles emanating from a focus: "needle-like globules" (100-300 nm in diameter) and mature mineral, both with statistically higher Ca/P compared to that of the dense granules. Many of the submicron granules and globules were interspersed around fibrillar structures containing nitrogen, which are most likely the signature of the organic phase. With high spatial resolution electron energy loss spectroscopy (EELS) mapping, spatially resolved maps were acquired showing the distribution of carbonate within each mineral structure. The carbonate was located in the middle of the granules, which suggested the nucleation of the younger mineral starts with a carbonate-containing precursor and that this precursor may act as seed for growth into larger, submicron-sized, needle-like globules of hydroxyapatite with a different stoichiometry. Application of analytical electron microscopy has important implications in deciphering both how normal bone forms and in understanding pathological mineralization. PMID:27383526

  3. The Influence of Calcium Carbonate Grain Coatings on Contaminant Reactivity in Vadose Zone Sediments

    SciTech Connect

    Zachara, John M.; Chambers, Scott; Brown Jr., Gordon E.; Eggleston, Carrick M.

    2001-06-01

    Calcium carbonate (CaCO3) is widely distributed through the Hanford vadose zone as a minor phase. As a result of current and past geochemical processes, CaCO3 exists as grain coatings, intergrain fill, and distinct caliche layers in select locations. Calcium carbonate may also precipitate when high-level wastes react with naturally Ca- and Mg-saturated Hanford sediments. Calcium carbonate is a very reactive mineral phase. Sorption reactions on its surface may slow the migration of certain contaminants (Co, Sr), but its surface coatings on other mineral phases may diminish contaminant retardation (for example, Cr) by blocking surface reaction sites of the substrate. This project explores the behavior of calcium carbonate grain coatings, including how they form and dissolve, their reactivity toward key Hanford contaminants, their impact (as surface coatings) on the reactivity of other mineral substrates, and on their in-ground composition and minor element enrichment. The importance of CaCO3 as a contaminant sorbent will be defined in all of its different manifestations in Hanford sediments: dispersed minor lithic fragments, pedogenic carbonate coatings on gravel and stringers in silt, and nodules in clay and paleosols. Mass action models will be developed that allow understanding and prediction of the geochemical effects of CaCO3 on contaminant retardation in Hanford sediments.

  4. Carbonation of calcium phosphate cements after long-term exposure to Na[sub 2]CO[sub 3]-laden water at 250[degree]C

    SciTech Connect

    Sugama, T.; Carciello, N.R. )

    1993-11-01

    The rates of Na[sub 2]CO[sub 3]-induced carbonation of calcium phosphate cements (CPC) at 250 C derived from various calcium aluminate cement (CAC) reactants, depended primarily on the amount of non-reactive CAC reactants remaining in the CPC material after it was autoclaved. Secar 41 CAC, consisting of monocalcium aluminate (CA) and gehlenite (C[sub 2]AS), had a high reactivity with the NH[sub 4]H[sub 2]PO[sub 4]-based fertilizer (Poly-N) forming a CPC matrix, thereby resulting in rapid setting. Such behavior reflected the formation of hydroxyapatite (HOAp) and boehmite which play an important role in minimizing the carbonation rate at a hydrothermal temperature of 250 C. In contrast, Secar 80, having monocalcium dialuminate (CA[sub 2]) as its major component, retarded the reaction between CAC and Poly-N, so that a large amount of non-reactive CAC remained in the 250 C-autoclaved CPC specimens. Thus, the high susceptibility of the remaining CAC reactant to carbonation resulted in a yield of [approx] 1.7 % CaCO[sub 3] after exposure for 120 days. The loss of strength for all CPC specimens depended on the degree of crystallinity of the HOAp and [gamma]-AlOOH phases growing in the amorphous phases, but was independent of its rate of carbonation.

  5. Enzyme-accelerated and structure-guided crystallization of calcium carbonate: role of the carbonic anhydrase in the homologous system.

    PubMed

    Müller, Werner E G; Schlossmacher, Ute; Schröder, Heinz C; Lieberwirth, Ingo; Glasser, Gunnar; Korzhev, Michael; Neufurth, Meik; Wang, Xiaohong

    2014-01-01

    The calcareous spicules from sponges, e.g. from Sycon raphanus, are composed of almost pure calcium carbonate. In order to elucidate the formation of those structural skeletal elements, the function of the enzyme carbonic anhydrase (CA), isolated from this species, during the in vitro calcium carbonate-based spicule formation, was investigated. It is shown that the recombinant sponge CA substantially accelerates calcium carbonate formation in the in vitro diffusion assay. A stoichiometric calculation revealed that the turnover rate of the sponge CA during the calcification process amounts to 25 CO2s(-1) × molecule CA(-1). During this enzymatically driven process, initially pat-like particles are formed that are subsequently transformed to rhomboid/rhombohedroid crystals with a dimension of ~50 μm. The CA-catalyzed particles are smaller than those which are formed in the absence of the enzyme. The Martens hardness of the particles formed is ~4 GPa, a value which had been determined for other biogenic calcites. This conclusion is corroborated by energy-dispersive X-ray spectroscopy, which revealed that the particles synthesized are composed predominantly of the elements calcium, oxygen and carbon. Surprising was the finding, obtained by light and scanning electron microscopy, that the newly formed calcitic crystals associate with the calcareous spicules from S. raphanus in a highly ordered manner; the calcitic crystals almost perfectly arrange in an array orientation along the two opposing planes of the spicules, leaving the other two plane arrays uncovered. It is concluded that the CA is a key enzyme controlling the calcium carbonate biomineralization process, which directs the newly formed particles to existing calcareous spicular structures. It is expected that with the given tools new bioinspired materials can be fabricated. PMID:23978410

  6. The determination of calcium in phosphate, carbonate, and silicate rocks by flame photometer

    USGS Publications Warehouse

    Kramer, Henry

    1956-01-01

    A method has been developed for the determination of calcium in phosphate, carbonate, and silicate rocks using the Beckman flame photometer, with photomultiplier attachement. The sample is dissolved in hydrofluoric, nitric, and perchloric acids, the hydrofluoric and nitric acids are expelled, a radiation buffer consisting of aluminum, magnesium, iron, sodium, potassium, phosphoric acid, and nitric acid is added, and the solution is atomized in an oxy-hydrogen flame with an instrument setting of 554 mµ. Measurements are made by comparison against calcium standards, prepared in the same manner, in the 0 to 50 ppm range. The suppression of calcium emission by aluminum and phosphate was overcome by the addition of a large excess of magnesium. This addition almost completely restores the standard curve obtained from a solution of calcium nitrate. Interference was noted when the iron concentration in the aspirated solution (including the iron from the buffer) exceeded 100 ppm iron. Other common rock-forming elements did not interfere. The results obtained by this procedure are within ± 2 percent of the calcium oxide values obtained by other methods in the range 1 to 95 percent calcium oxide. In the 0 to 1 percent calcium oxide range the method compares favorably with standard methods.

  7. CO.sub.2 Pretreatment prevents calcium carbonate formation

    DOEpatents

    Neavel, Richard C.; Brunson, Roy J.; Chaback, Joseph J.

    1980-01-01

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by pretreatment with carbon dioxide. The carbon dioxide pretreatment is believed to convert the scale-forming components to the corresponding carbonate prior to liquefaction. The pretreatment is accomplished at a total pressure within the range from about 14 to about 68 atmospheres and a carbon dioxide partial pressure within the range from about 14 to about 34 atmospheres. Temperature during pretreatment will generally be within the range from about 100.degree. to about 200.degree. C.

  8. Chemical analysis and molecular models for calcium-oxygen-carbon interactions in black carbon found in fertile Amazonian anthrosoils.

    PubMed

    Archanjo, Braulio S; Araujo, Joyce R; Silva, Alexander M; Capaz, Rodrigo B; Falcão, Newton P S; Jorio, Ado; Achete, Carlos A

    2014-07-01

    Carbon particles containing mineral matter promote soil fertility, helping it to overcome the rather unfavorable climate conditions of the humid tropics. Intriguing examples are the Amazonian Dark Earths, anthropogenic soils also known as "Terra Preta de Índio'' (TPI), in which chemical recalcitrance and stable carbon with millenary mean residence times have been observed. Recently, the presence of calcium and oxygen within TPI-carbon nanoparticles at the nano- and mesoscale ranges has been demonstrated. In this work, we combine density functional theory calculations, scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, Fourier transformed infrared spectroscopy, and high resolution X-ray photoelectron spectroscopy of TPI-carbons to elucidate the chemical arrangements of calcium-oxygen-carbon groups at the molecular level in TPI. The molecular models are based on graphene oxide nanostructures in which calcium cations are strongly adsorbed at the oxide sites. The application of material science techniques to the field of soil science facilitates a new level of understanding, providing insights into the structure and functionality of recalcitrant carbon in soil and its implications for food production and climate change. PMID:24892495

  9. Factors affecting ex-situ aqueous mineral carbonation using calcium and magnesium silicate minerals

    SciTech Connect

    Gerdemann, Stephen J.; Dahlin, David C.; O'Connor, William K.; Penner, Larry R.; Rush, G.E.

    2004-01-01

    Carbonation of magnesium- and calcium-silicate minerals to form their respective carbonates is one method to sequester carbon dioxide. Process development studies have identified reactor design as a key component affecting both the capital and operating costs of ex-situ mineral sequestration. Results from mineral carbonation studies conducted in a batch autoclave were utilized to design and construct a unique continuous pipe reactor with 100% recycle (flow-loop reactor). Results from the flow-loop reactor are consistent with batch autoclave tests, and are being used to derive engineering data necessary to design a bench-scale continuous pipeline reactor.

  10. Porous one-dimensional Mo2C-amorphous carbon composites: high-efficient and durable electrocatalysts for hydrogen generation.

    PubMed

    Zhang, Kai; Li, Chunyan; Zhao, Yang; Yu, Xianbo; Chen, Yujin

    2015-07-01

    Porous one-dimensional Mo2C-amorphous carbon composites, fabricated by in situ solid state reactions, are exhibited as effective and high-performance electrocatalysts towards the hydrogen evolution reaction (HER). The morphological and structural characteristics of the Mo2C based electrocatalysts were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The analyses showed that they had various advantages for the HER, including a high crystallinity, porous and tubular characteristics and good conductivity. The porous one-dimensional Mo2C-amorphous carbon composites with a larger content of Mo2C and moderate thickness of the carbon layers exhibited superior catalytic activities for HER to most of the Mo2C based electrocatalysts recently reported. PMID:26055048

  11. High density amorphous carbon films and the preparation of diamond membranes for X-ray lithography

    NASA Astrophysics Data System (ADS)

    Cuomo, Jerome J.; Doyle, J. P.; Pappas, David L.; Saenger, Katherine L.; Guarnieri, C. R.; Whitehair, S. J.

    Trends in recently reported data on high sp exp 3 fraction (up to 85 percent), nonhydrogenated amorphous diamond-like carbon films deposited by ion beam sputtering and laser vaporization are examined. The degree of diamond-like film character is found to depend upon the deposition technique as well as the substrate temperature and thermal diffusivity. The combination of incident particle kinetic energy and surface accommodation determine the physical properties of the film. A model is proposed for the condensation of energetic carbon atoms into diamond-like films in which a quench-type surface accommodation mechanism is operative. Diamond membranes are being developed for X-ray lithographic masks; these 1-3 micron thick membranes are deposited onto Si substrates using microwave-driven plasmas. To obtain smooth films with uniform tensile stress, spray and electrophoretic deposition of 0.1 micron diamond seeds were used to control the initial nucleation and growth of the diamond films. The films have a biaxial modulus of 800 GPa. X-ray lithography masks have been made and used to print patterns with X-rays from a synchrotron source.

  12. Electronic structure and conductivity of nanocomposite metal (Au,Ag,Cu,Mo)-containing amorphous carbon films

    SciTech Connect

    Endrino, Jose L.; Horwat, David; Gago, Raul; Andersson, Joakim; Liu, Y.S.; Guo, Jinghua; Anders, Andre

    2008-05-14

    In this work, we study the influence of the incorporation of different metals (Me = Au, Ag, Cu, Mo) on the electronic structure of amorphous carbon (a-C:Me) films. The films were produced at room temperature using a novel pulsed dual-cathode arc deposition technique. Compositional analysis was performed with secondary neutral mass spectroscopy whereas X-ray diffraction was used to identify the formation of metal nanoclusters in the carbon matrix. The metal content incorporated in the nanocomposite films induces a drastic increase in the conductivity, in parallel with a decrease in the band gap corrected from Urbach energy. The electronic structure as a function of the Me content has been monitored by x-ray absorption near edge structure (XANES) at the C K-edge. XANES showed that the C host matrix has a dominant graphitic character and that it is not affected significantly by the incorporation of metal impurities, except for the case of Mo, where the modifications in the lineshape spectra indicated the formation of a carbide phase. Subtle modifications of the spectral lineshape are discussed in terms of nanocomposite formation.

  13. Gold nanoclusters on amorphous carbon synthesized by ion-beam deposition

    SciTech Connect

    Thune, Elsa; Carpene, Ettore; Sauthoff, Katharina; Seibt, Michael; Reinke, Petra

    2005-08-01

    Gold clusters have been deposited by a monoenergetic, mass-selected ion beam with low energies (20-350 eV) on amorphous carbon substrates in order to minimize the influence of the surface crystallinity and the ion-induced structural changes. Gold has been used as a model system, due to the poor reactivity with carbon, to study the ion-energy dependence, the temporal evolution, and the influence of the temperature on the cluster distribution. The cluster size is very sensitive to the energy and the mean size strongly decreases from 4 to less than 1 nm as the ion energy increases. We can also note that the size distribution becomes broader. For impact energies below 100 eV, surface processes dominate the cluster nucleation and growth. If higher energies are used, an increasing number of ions is implanted below the surface and different processes control the cluster formation. When the energy increases above 350 eV, the cluster size drastically drops below 5 nm. The samples are analyzed with different methods such as atomic force microscopy, transmission electron microscopy, and x-ray photoelectron spectroscopy to determine their size distribution, composition, and structure.

  14. Composition and properties of the so-called 'diamond-like' amorphous carbon films

    NASA Technical Reports Server (NTRS)

    Angus, J. C.; Stultz, J. E.; Shiller, P. J.; Macdonald, J. R.; Mirtich, M. J.

    1984-01-01

    The composition of amorphous 'diamond-like' films made by direct low energy ion beam deposition, R.F. discharge and sputtering was determined by nuclear reaction analysis, IR spectroscopy and microcombustion chemical analysis. The nuclear reaction analysis showed very similar hydrogen depth profiles for all three types of samples. The atomic ratio of hydrogen to carbon was approximately 0.2 at the film surface and rose to approximately 1.0 at a depth of 500 A. The integrated intensity of the C-H stretching band at about 2900 per cm indicates that the amount of chemically bonded hydrogen is less than the total hydrogen content. Combustion analysis confirmed the overall atomic ratio of hydrogen to carbon determined by nuclear reaction analysis. The chemical state of the non-bonded hydrogen was not determined; however, the effective diffusion coefficient computed from the hydrogen depth profile was extremely low. This indicates either that the films are exceedingly impermeable or that the non-bonded hydrogen requires an additional activated step to leave the films, e.g., desorption or chemical reaction.

  15. Semiconducting Properties of Nanostructured Amorphous Carbon Thin Films Incorporated with Iodine by Thermal Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Kamaruzaman, Dayana; Ahmad, Nurfadzilah; Annuar, Ishak; Rusop, Mohamad

    2013-11-01

    Nanostructured iodine-post doped amorphous carbon (a-C:I) thin films were prepared from camphor oil using a thermal chemical vapor deposition (TCVD) technique at different doping temperatures. The structural properties of the films were studied by field-emission scanning electron microscopy (FESEM), energy-dispersive spectroscopy (EDS), Raman, and Fourier transform infrared (FTIR) studies. FESEM and EDS studies showed successful iodine doping. FTIR and Raman studies showed that the a-C:I thin films consisted of a mixture of sp2- and sp3-bonded carbon atoms. The optical and electrical properties of a-C:I thin films were determined by UV-vis-NIR spectroscopy and current-voltage (I-V) measurement respectively. The optical band gap of a-C thin films decreased upon iodine doping. The highest electrical conductivity was found at 400 °C doping. Heterojunctions are confirmed by rectifying the I-V characteristics of an a-C:I/n-Si junction.

  16. Evidence for Calcium Carbonate at the Phoenix Landing Site

    NASA Technical Reports Server (NTRS)

    Boynton, W. V.; Ming, D. W.; Sutter, B.; Arvidson, R. E.; Hoffman, J.; Niles, P. B.; Smith, P.

    2009-01-01

    The Phoenix mission has recently finished its study of the north polar environment of Mars with the aim to help understand both the current climate and to put constraints on past climate. An important part of understanding the past climate is the study of secondary minerals, those formed by reaction with volatile compounds such as H2O and CO2. This work describes observations made by the Thermal and Evolved-Gas Analyzer (TEGA) on the Phoenix Lander related to carbonate minerals. Carbonates are generally considered to be products of aqueous processes. A wet and warmer climate during the early history of Mars coupled with a much denser CO2 atmosphere are ideal conditions for the aqueous alteration of basaltic materials and the subsequent formation of carbonates. Carbonates (Mg- and Ca-rich) are predicted to be thermodynamically stable minerals in the present martian environment, however, there have been only a few indications of carbonates on the surface by a host of orbiting and landed missions to Mars. Carbonates (Mg-rich) have been suggested to be a component (2-5 wt %) of the martian global dust based upon orbital thermal emission spectroscopy. The identifications, based on the presence of a 1480 cm-1 absorption feature, are consistent with Mgcarbonates. A similar feature is observed in brighter, undisturbed soils by Mini-TES on the Gusev plains. Recently, Mg-rich carbonates have been identified in the Nili Fossae region by the CRISM instrument onboard the Mars Reconnaissance Orbiter. Carbonates have also been confirmed as aqueous alteration phases in martian meteorites so it is puzzling why there have not been more discoveries of carbonates by landers, rovers, and orbiters. Carbonates may hold important clues about the history of liquid water and aqueous processes on the surface of Mars.

  17. Fine-Tuning of Polymeric Resins and Their Interfaces with Amorphous Calcium Phosphate. A Strategy for Designing Effective Remineralizing Dental Composites

    PubMed Central

    Antonucci, Joseph M.; Skrtic, Drago

    2011-01-01

    For over a decade our group has been designing, preparing and evaluating bioactive, remineralizing composites based on amorphous calcium phosphate (ACP) fillers embedded in polymerized methacrylate resin matrices. In these studies a major focus has been on exploring structure-property relationships of the matrix phase of these composites on their anti-cariogenic potential. The main challenges were to gain a better understanding of polymer matrix/filler interfacial properties through controlling the surface properties of the fillers or through fine-tuning of the resin matrix. In this work, we describe the effect of chemical structure and composition of the resin matrices on some of the critical physicochemical properties of the copolymers and their ACP composites. Such structure-property studies are essential in formulating clinically effective products, and this knowledge base is likely to have strong impact on the future design of therapeutic materials, appropriate for mineral restoration in defective tooth structures. PMID:21283507

  18. 40 CFR 415.300 - Applicability; description of the calcium carbonate production subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 29 2014-07-01 2012-07-01 true Applicability; description of the calcium carbonate production subcategory. 415.300 Section 415.300 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS INORGANIC CHEMICALS MANUFACTURING...

  19. 40 CFR 415.300 - Applicability; description of the calcium carbonate production subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 29 2011-07-01 2009-07-01 true Applicability; description of the calcium carbonate production subcategory. 415.300 Section 415.300 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS INORGANIC CHEMICALS MANUFACTURING...

  20. 40 CFR 415.300 - Applicability; description of the calcium carbonate production subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 30 2013-07-01 2012-07-01 true Applicability; description of the calcium carbonate production subcategory. 415.300 Section 415.300 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS INORGANIC CHEMICALS MANUFACTURING...

  1. PROGRESS REPORT. THE INFLUENCE OF CALCIUM CARBONATE GRAIN COATINGS ON CONTAMINANT REACTIVITY IN VADOSE ZONE SEDIMENTS

    EPA Science Inventory

    This project explores the behavior of calcium carbonate grain coatings, including how they form and dissolve, their reactivity toward key Hanford contaminants, their impact (as surface coatings) on the reactivity of other mineral substrates, and on their in-ground composition and...

  2. ANNUAL REPORT. THE INFLUENCE OF CALCIUM CARBONATE GRAIN COATINGS ON CONTAMINANT REACTIVITY IN VADOSE ZONE SEDIMENTS

    EPA Science Inventory

    The primary objective of this project is to investigate the role of calcium carbonate grain coatings on adsorption and heterogeneous reduction reactions of key chemical and radioactive contaminants in sediments on the Hanford Site. Research will ascertain whether these coatings p...

  3. Coexistence of three calcium carbonate polymorphs in the shell of the Antarctic clam Laternula elliptica

    NASA Astrophysics Data System (ADS)

    Nehrke, Gernot; Poigner, Harald; Wilhelms-Dick, Dorothee; Brey, Thomas; Abele, Doris

    2012-05-01

    We analyzed shell cuts of five individuals of the Antarctic bivalve Laternula elliptica from three locations along the Antarctic Peninsula by means of Confocal Raman Microscopy (CRM) as well as Electron Microprobe (EMP). The shell of L. elliptica has been previously described as being composed of aragonite exclusively. Now, CRM mapping reveals that three polymorphs of calcium carbonate - aragonite, calcite, and vaterite - are present in the chondrophore region of the examined individuals. Annual shell growth layers continue through aragonite and vaterite, suggesting simultaneous mineralization of both polymorphs. Spatially congruent EMP scans showed that the calcium carbonate polymorph affects the distribution of magnesium and strontium within the chondrophore. This is, to our knowledge, the first report of the coexistence of these three calcium carbonate polymorphs within the mineralized structures of a marine calcifying organism. Particularly the presence of vaterite is unexpected, but shows striking similarities to some fish otoliths. The strong effect of the calcium carbonate polymorph on trace element incorporation restrict the suitability of magnesium and strontium based proxies for the chondrophore area of L. elliptica.

  4. EXPERIMENTAL DETERMINATION OF THE CALCIUM CARBONATE SATURATION STATES OF WATER SYSTEMS (TECHNICAL NOTE)

    EPA Science Inventory

    Emphasis is given to the fact that saturation indexes only indicate the tendency of a water to dissolve or precipitate calcium carbonate (CaCo3). The rate at which a given water attains equilibrium cannot be derived from the saturation index value.

  5. Transformation of Graphitic and Amorphous Carbon Dust to Complex Organic Molecules in a Massive Carbon Cycle in Protostellar Nebulae

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A., III; Johnson, Natasha M.

    2012-01-01

    More than 95% of silicate minerals and other oxides found in meteorites were melted, or vaporized and recondensed in the Solar Nebula prior to their incorporation into meteorite parent bodies. Gravitational accretion energy and heating via radioactive decay further transformed oxide minerals accreted into planetesimals. In such an oxygen-rich environment the carbonaceous dust that fell into the nebula as an intimate mixture with oxide grains should have been almost completely converted to CO. While some pre-collapse, molecular-cloud carbonaceous dust does survive, much in the same manner as do pre-solar oxide grains, such materials constitute only a few percent of meteoritic carbon and are clearly distinguished by elevated D/H, N-15/N-16, C-13/C-12 ratios or noble gas patterns. Carbonaceous Dust in Meteorites: We argue that nearly all of the carbon in meteorites was synthesized in the Solar Nebula from CO and that this CO was generated by the reaction of carbonaceous dust with solid oxides, water or OH. It is probable that some fraction of carbonaceous dust that is newly synthesized in the Solar Nebula is also converted back into CO by additional thermal processing. CO processing might occur on grains in the outer nebula through irradiation of CO-containing ice coatings or in the inner nebula via Fischer-Tropsch type (FTT) reactions on grain surfaces. Large-scale transport of both gaseous reaction products and dust from the inner nebula out to regions where comets formed would spread newly formed carbonaceous materials throughout the solar nebula. Formation of Organic Carbon: Carbon dust in the ISM might easily be described as inorganic graphite or amorphous carbon, with relatively low structural abundances of H, N, O and S . Products of FTT reactions or organics produced via irradiation of icy grains contain abundant aromatic and aliphatic hydrocarbons. aldehydes, keytones, acids, amines and amides.. The net result of the massive nebular carbon cycle is to convert

  6. Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous UIV-phosphate

    NASA Astrophysics Data System (ADS)

    Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; Boyanov, Maxim I.

    2016-02-01

    The mobility of uranium in subsurface environments depends strongly on its redox state, with UIV phases being significantly less soluble than UVI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of UVI reduction in natural systems, a nanoparticulate UO2 phase and an amorphous UIV-Ca-PO4 analog to ningyoite (CaUIV(PO4)2·1-2H2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for UIVO2 and UIV-phosphate in solutions equilibrated with atmospheric O2 and CO2 at pH 7.0 (kobs,UO2 = 0.17 ± 0.075 h-1 vs. kobs,UIVPO4 = 0.30 ± 0.25 h-1). Addition of up to 400 μM Ca and PO4 decreased the oxidation rate constant by an order of magnitude for both UO2 and UIV-phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO4, the product of UO2 oxidation is Na-uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO4 and low carbonate concentration), resulting in low concentrations of dissolved UVI (<2.5 × 10-7 M). Oxidation of UIV-phosphate produced a Na-autunite phase (Na2(UO2)PO4·xH2O), resulting in similarly low dissolved U concentrations (<7.3 × 10-8 M). When Ca and PO4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO2 and UIV-phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca-UVI-PO4 layer on the UO2 surface and suggest a passivation layer mechanism for the decreased rate of UO2 oxidation in the presence of Ca and PO4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO2 solids, suggesting that oxidized U is distributed between

  7. Laser ablation MC-ICP-MS U/Pb geochronology of ocean basement calcium carbonate veins

    NASA Astrophysics Data System (ADS)

    Harris, M.; Coggon, R. M.; Teagle, D. A. H.; Roberts, N. M. W.; Parrish, R. R.

    2014-12-01

    Given the vast areas of mid ocean ridge flanks, even small chemical changes dues to fluid-rock interaction on the flanks may significantly influence global geochemical cycles. A conductive heat flow anomaly associated with hydrothermal circulation in ocean crust exists until on average 65Ma, but it is not known whether the thermal signature is accompanied by continued fluid-rock chemical exchange. Constraining the duration of fluid-rock chemical exchange is critical for calculating robust chemical fluxes associated with ridge flank hydrothermal circulation. Calcium carbonate veins form during relatively late-stage hydrothermal alteration and can be used to estimate the duration of ridge flank hydrothermal circulation. LA-MC-ICP-MS U/Pb geochronology provides a novel and independent approach to date calcium carbonate veins, and is advantageous over using the seawater Sr isotope curve that is in part non-unique and requires assumptions about the contribution of MORB Sr from fluid-rock exchange. LA-MC-ICP-MS U/Pb analyses have been undertaken on a suite of calcium carbonate veins from a range of basement ages (1.6 - 170 Ma), spreading rates and sediment thickness. Preliminary results indicate that the temperature of formation of calcium carbonate veins place a strong control on achieving a successful U/Pb isochron. This is likely related to the temperature dependent geochemical evolution of basement fluids due to fluid-rock reaction, and the partitioning of U and Pb into calcite/aragonite. Successful U/Pb isochrons have been achieved for a range of crustal ages and spreading rates, and indicate that calcium carbonate precipitation occurs within 25Myrs of crustal formation. This is substantially shorter than 65Ma, the average extent of the conductive heat flow anomaly, and will allow for more robust estimates of the contribution of hydrothermal chemical fluxes to global geochemical cycles.

  8. Carbon dioxide transport in molten calcium carbonate occurs through an oxo-Grotthuss mechanism via a pyrocarbonate anion

    NASA Astrophysics Data System (ADS)

    Corradini, Dario; Coudert, François-Xavier; Vuilleumier, Rodolphe

    2016-05-01

    The reactivity, speciation and solvation structure of CO2 in carbonate melts are relevant for both the fate of carbon in deep geological formations and for its electroreduction to CO (to be used as fuel) when solvated in a molten carbonate electrolyte. In particular, the high solubility of CO2 in carbonate melts has been tentatively attributed to the formation of the pyrocarbonate anion, C2O52–. Here we study, by first-principles molecular dynamics simulations, the behaviour of CO2 in molten calcium carbonate. We find that pyrocarbonate forms spontaneously and the identity of the CO2 molecule is quickly lost through O2– exchange. The transport of CO2 in this molten carbonate thus occurs in a fashion similar to the Grotthuss mechanism in water, and is three times faster than molecular diffusion. This shows that Grotthuss-like transport is more general than previously thought.

  9. Carbon dioxide transport in molten calcium carbonate occurs through an oxo-Grotthuss mechanism via a pyrocarbonate anion.

    PubMed

    Corradini, Dario; Coudert, François-Xavier; Vuilleumier, Rodolphe

    2016-05-01

    The reactivity, speciation and solvation structure of CO2 in carbonate melts are relevant for both the fate of carbon in deep geological formations and for its electroreduction to CO (to be used as fuel) when solvated in a molten carbonate electrolyte. In particular, the high solubility of CO2 in carbonate melts has been tentatively attributed to the formation of the pyrocarbonate anion, C2O5(2-). Here we study, by first-principles molecular dynamics simulations, the behaviour of CO2 in molten calcium carbonate. We find that pyrocarbonate forms spontaneously and the identity of the CO2 molecule is quickly lost through O(2-) exchange. The transport of CO2 in this molten carbonate thus occurs in a fashion similar to the Grotthuss mechanism in water, and is three times faster than molecular diffusion. This shows that Grotthuss-like transport is more general than previously thought. PMID:27102679

  10. Amorphous red phosphorous embedded in carbon nanotubes scaffold as promising anode materials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Yuan, Demao; Cheng, Jianli; Qu, Guoxing; Li, Xiaodong; Ni, Wei; Wang, Bin; Liu, Heng

    2016-01-01

    Amorphous red phosphorus/carbon nanotubes (ARPC) composites are prepared by planetary ball-milling technique with the pre-milling red phosphorus processes, consisting of uniformly distributing amorphous red phosphorus embedding in a three-dimensional conductive scaffold of interconnected carbon nanotubes (CNTs). Combining the three-dimensional conductive network with the amorphous red phosphorus can not only alleviate the volumetric change in the charging/discharging processes, but also provide conductive network for electron transport and dramatically improve the specific capacity, cycling stability and rate capability of the composite electrode. The ARPC composites deliver a high initial charge capacity of 2133.4 mAh g-1 at a current density of 0.05 C and maintain a reversible capacity of 998.5 mAh g-1 with a high Coulombic efficiency of approximately 99% after 50 cycles. Meanwhile, the composite can maintain high specific capacities of 1993.8 mAh g-1, 1896.9 mAh g-1, 1546.8 mAh g-1 and 816.6 mAh g-1 at 0.01 C, 0.05 C, 0.1 C and 0.5 C, respectively. Compared with that of the ball-milled amorphous red phosphorus with or without CNTs, the pre-milled ARPC composites show much better electrochemical performances.

  11. [First-principles study of vibrational Raman spectra of amorphous carbon].

    PubMed

    Niu, Li; Zhu, Jia-qi; Gao, Wei; Du, Shan-yi

    2009-09-01

    The vibrational density of states and nonresonant reduced Raman spectra of amorphous carbon at densities of 2.6, 2.9 and 3.2 g x cm(-3) were calculated by the use of a first-principles plane-wave pesudopotential method. Three structural models were generated by liquid-quench method using Car-Parinello molecular dynamics, their vibrational frequencies and eigenmodes were determined using the linear response approach, and Raman coupling tensors were calculated using the finite electric field method. The calculated results show that the sp3 fraction increases from 50% to 84.4%, the sp2 configuration changes from mainly rings to short chains, the position of the G peak moves to higher frequencies, the intensity ratio of D and G peaks decreases, the position of the T peak moves to lower frequencies and the intensity ratio of T and G peaks increases as density increases from 2.6 to 3.2 g x cm(-3). The authors' calculated Raman spectra show an overall good agreement with experimental spectra. The analysis in terms of atomic vibrations confirms that the G and D peaks both come from sp2 C contribution, G peak is due to the stretching vibration of any pair of sp2 atoms and the T peak is due to the C-C sp3 vibration. The authors' analysis also confirms that the dispersion of G and T peaks is due to bond-length changes. The bond length of chains (olefins) is shorter than that of rings, so their vibrational frequency is higher and the G-peak position moves to higher frequencies with increasing the sp3 fraction. The number of sp3-sp2 type bonds decreases as the sp3 fraction increases. These bonds are shorter than pure sp3-sp3 bonds, hence the T-peak position moves to lower frequencies. The research results provide a theoretic basis for analyzing experimental Raman spectra of amorphous carbon. PMID:19950647

  12. Influence of the incident angle of energetic carbon ions on the properties of tetrahedral amorphous carbon (ta-C) films

    NASA Astrophysics Data System (ADS)

    Liu, Dongping; Benstetter, Günther; Lodermeier, Edgar; Vancea, Johann

    2003-09-01

    Tetrahedral amorphous carbon (ta-C) films have been grown on Ar+-beam-cleaned silicon substrates by changing the incident angle of energetic carbon ions produced in the plasma of pulsed cathodic vacuum arc discharge. Their surface roughness, deposition rate, composition, and mechanical and frictional properties as a function of the incident angle of energetic carbon ions were reported. The substrate holder can be rotated, and so an angle of deposition was defined as the angle of ion flux with respect to the substrate surface. While the deposition angle is varied from 20° to 59°, the root-mean-square (rms) roughness decreases from 0.5 to 0.1 nm, then it turns to increase at a slow rate when the deposition angle is over 77°. The variation correlates well with the one of hardness with the deposition angle and the films with lower rms roughness exhibit the higher hardness. The soft graphite-like surface layers existing at the surfaces of these films were revealed by atomic force microscopy-based nanowear tests and their thickness increases from 0.35 to 2.9 nm with the deposition angle decreasing from 90° to 30°. The soft surface layer thickness can have a great effect on the sp3 contents measured by x-ray photoelectron spectra. Nanoscale friction coefficient measurements were performed from lateral force microscopy by using a V-shaped Si3N4 cantilever. The low friction coefficients (0.076-0.093) of ta-C films can be attributed to their graphite-like surface structure. The implications of these results on the mechanisms proposed for the film formation were discussed.

  13. Study of hMSC proliferation and differentiation on Mg and Mg-Sr containing biphasic β-tricalcium phosphate and amorphous calcium phosphate ceramics.

    PubMed

    Singh, Satish S; Roy, Abhijit; Lee, Boeun; Kumta, Prashant N

    2016-07-01

    Biphasic mixtures of either Mg(2+) or combined Mg(2+) and Sr(2+) cation substituted β-tricalcium phosphate (β-TCP) and amorphous calcium phosphate (ACP) were prepared using a low temperature chemical phosphatizing and hydrolysis reaction approach. Scaffolds prepared using the cation substituted calcium phosphates were capable of supporting similar levels of human mesenchymal stem cell proliferation in comparison to commercially available β-TCP. The concentrations of Mg(2+), Sr(2+), and PO4(3-) released from these scaffolds were also within the ranges desired from previous reports to support both hMSC proliferation and osteogenic differentiation. Interestingly, hMSCs cultured directly on scaffolds prepared with only Mg(2+) substituted β-TCP were capable of supporting statistically significantly increased alkaline phosphatase activity, osteopontin, and osteoprotegerin expression in comparison to all compositions containing both Mg(2+) and Sr(2+), and commercially available β-TCP. hMSCs cultured in the presence of scaffold extracts also exhibited similar trends in the expression of osteogenic markers as was observed during direct culture. Therefore, it was concluded that the enhanced differentiation observed was due to the release of bioactive ions rather than the surface microstructure. The role of these ions on transforming growth factor-β and bone morphogenic protein signaling was also evaluated using a PCR array. It was concluded that the release of these ions may support enhanced differentiation through SMAD dependent TGF-β and BMP signaling. PMID:27127047

  14. Climatically driven loss of calcium in steppe soil as a sink for atmospheric carbon

    USGS Publications Warehouse

    Lapenis, A.G.; Lawrence, G.B.; Bailey, S.W.; Aparin, B.F.; Shiklomanov, A.I.; Speranskaya, N.A.; Torn, M.S.; Calef, M.

    2008-01-01

    During the last several thousand years the semi-arid, cold climate of the Russian steppe formed highly fertile soils rich in organic carbon and calcium (classified as Chernozems in the Russian system). Analysis of archived soil samples collected in Kemannaya Steppe Preserve in 1920, 1947, 1970, and fresh samples collected in 1998 indicated that the native steppe Chernozems, however, lost 17-28 kg m-2 of calcium in the form of carbonates in 1970-1998. Here we demonstrate that the loss of calcium was caused by fundamental shift in the steppe hydrologic balance. Previously unleached soils where precipitation was less than potential evapotranspiration are now being leached due to increased precipitation and, possibly, due to decreased actual evapotranspiration. Because this region receives low levels of acidic deposition, the dissolution of carbonates involves the consumption of atmospheric CO2. Our estimates indicate that this climatically driven terrestrial sink of atmospheric CO2 is ???2.1-7.4 g C m-2 a-1. In addition to the net sink of atmospheric carbon, leaching of pedogenic carbonates significantly amplified seasonal amplitude of CO2 exchange between atmosphere and steppe soil. Copyright 2008 by the American Geophysical Union.

  15. Nanoscale analysis of the morphology and surface stability of calcium carbonate polymorphs

    NASA Astrophysics Data System (ADS)

    Sekkal, W.; Zaoui, A.

    2013-04-01

    Under earth surface conditions, in ocean and natural water, calcium carbonate is ubiquitous, forming anhydrous and hydrous minerals. These hydrous phases are of considerable interest for their role as precursors to stable carbonate minerals. Atomistic simulation techniques have been employed here to perform a comprehensive and quantitative study of the structural and energetic stability of dry and hydrous surfaces of calcium carbonate polymorphs using two recently developed forcefields. Results show that the dry forms are prone to ductility; while hydrous phases are found to be brittle. The (001) surface of monohydrocalcite appears to be the most stable (0.99 J/m2) whereas for the ikaite phase, the (001) surface is the most stable. The corresponding value is 0.2 J/m2, i.e. even lower than the surface energy of the Beautiful computed morphology pictures are obtained with Xiao's model and are very similar to the observed SEM images.

  16. Nanoscale analysis of the morphology and surface stability of calcium carbonate polymorphs.

    PubMed

    Sekkal, W; Zaoui, A

    2013-01-01

    Under earth surface conditions, in ocean and natural water, calcium carbonate is ubiquitous, forming anhydrous and hydrous minerals. These hydrous phases are of considerable interest for their role as precursors to stable carbonate minerals. Atomistic simulation techniques have been employed here to perform a comprehensive and quantitative study of the structural and energetic stability of dry and hydrous surfaces of calcium carbonate polymorphs using two recently developed forcefields. Results show that the dry forms are prone to ductility; while hydrous phases are found to be brittle. The (001) surface of monohydrocalcite appears to be the most stable (0.99 J/m(2)) whereas for the ikaite phase, the (001) surface is the most stable. The corresponding value is 0.2 J/m(2), i.e. even lower than the surface energy of the Beautiful computed morphology pictures are obtained with Xiao's model and are very similar to the observed SEM images. PMID:23545842

  17. Complexation/encapsulation of green tea polyphenols in mixed calcium carbonate and phosphate micro-particles.

    PubMed

    Elabbadi, Amal; Jeckelmann, Nicolas; Haefliger, Olivier P; Ouali, Lahoussine

    2011-01-01

    We used a double-jet mixer to encapsulate water-soluble polyphenols, green tea extract (GTE), with calcium-based inorganic materials. The device mixed calcium chloride solutions with a solution of carbonate and phosphate in the presence of a GTE solution, and formed micro-particles which capture the GTE molecules. The micro-particles were analysed by liquid chromatography coupled to tandem mass spectroscopy to determine the encapsulation yield and loading of the different GTE components. We established correlations between (1) the efficiency of the GTE encapsulation and the composition of the mixed anion solutions and (2) the protonation degree of the ions and the molar ratio of calcium cations and carbonate/phosphate anions. An optimal and reproducible GTE loading of about 40% with an encapsulation yield of 65% was observed for a carbonate/phosphate molar composition of 4 : 1. In addition, our experimental results showed that the process is selective and favours the encapsulation of gallated species which form stronger complexes with calcium cations. PMID:20945969

  18. Roles of larval sea urchin spicule SM50 domains in organic matrix self-assembly and calcium carbonate mineralization.

    PubMed

    Rao, Ashit; Seto, Jong; Berg, John K; Kreft, Stefan G; Scheffner, Martin; Cölfen, Helmut

    2013-08-01

    The larval spicule matrix protein SM50 is the most abundant occluded matrix protein present in the mineralized larval sea urchin spicule. Recent evidence implicates SM50 in the stabilization of amorphous calcium carbonate (ACC). Here, we investigate the molecular interactions of SM50 and CaCO3 by investigating the function of three major domains of SM50 as small ubiquitin-like modifier (SUMO) fusion proteins - a C-type lectin domain (CTL), a glycine rich region (GRR) and a proline rich region (PRR). Under various mineralization conditions, we find that SUMO-CTL is monomeric and influences CaCO3 mineralization, SUMO-GRR aggregates into large protein superstructures and SUMO-PRR modifies the early CaCO3 mineralization stages as well as growth. The combination of these mineralization and self-assembly properties of the major domains synergistically enable the full-length SM50 to fulfill functions of constructing the organic spicule matrix as well as performing necessary mineralization activities such as Ca(2+) ion recruitment and organization to allow for proper growth and development of the mineralized larval sea urchin spicule. PMID:23796503

  19. Comparative study on in vivo response of porous calcium carbonate composite ceramic and biphasic calcium phosphate ceramic.

    PubMed

    He, Fupo; Ren, Weiwei; Tian, Xiumei; Liu, Wei; Wu, Shanghua; Chen, Xiaoming

    2016-07-01

    In a previous study, robust calcium carbonate composite ceramics (CC/PG) were prepared by using phosphate-based glass (PG) as an additive, which showed good cell response. In the present study the in vivo response of porous CC/PG was compared to that of porous biphasic calcium phosphate ceramics (BCP), using a rabbit femoral critical-size grafting model. The materials degradation and bone formation processes were evaluated by general observation, X-ray radiography, micro-computed tomography, and histological examination. The results demonstrated excellent biocompatibility and osteoconductivity, and progressive degradation of CC/PG and BCP. Although the in vitro degradation rate of CC/PG was distinctly faster than that of BCP, at 4week post-implantation, the bone generation and material degradation of CC/PG were less than those of BCP. Nevertheless, at postoperative week 8, the increment of bone formation and material degradation of CC/PG was pronouncedly larger than that of BCP. These results show that CC/PG is a potential resorbable bone graft aside from the traditional synthetic ones. PMID:27127035

  20. The Properties and Characteristics of Concretes Containing Calcium Carbonate (CaCO3) and Synthetic Lightweight Aggregate

    NASA Astrophysics Data System (ADS)

    Ramos, Matthew J.

    The purpose of this study was to investigate the efficacy of precipitated calcium carbonate as a means for enhancing the mechanical and environmental favorability of concretes containing synthetic lightweight aggregates (SLA), which are comprised of recycled mixed plastic and fly ash. Compressive strength tests show that 2% calcium carbonate additions are able to mitigate strength decreases induced by SLA as well as decrease concrete density when compared to NWA concretes. SLA concretes containing 5% calcium carbonate do not show the same trend. Instead, strength decreases and density increases are observed. Furthermore, increases in aluminum trisulphate (AFt) phase mineralization are observed through scanning electron microscopy. Results suggest that calcium carbonate additions increase early hydration and stabilize AFt minerals thaumasite and ettringite throughout hydration. It is proposed that increased AFt phase mineralization causes reductions in concrete density. However, a limit to this relationship was observed as additions of greater than 2% calcium carbonate exceed the potential for increased hydration, causing a threshold effect that resulted in calcium carbonate acting as filler, which increases density. Improved mechanical properties and the ability to stabilize waste plastics, fly ash, and CO2 emissions make the use of 2% calcium carbonate in conjunction with SLA a favorable alternative to ordinary concretes.

  1. Influence of Substrate Mineralogy on Bacterial Mineralization of Calcium Carbonate: Implications for Stone Conservation

    PubMed Central

    Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa

    2012-01-01

    The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed. PMID:22447589

  2. Influence of substrate mineralogy on bacterial mineralization of calcium carbonate: implications for stone conservation.

    PubMed

    Rodriguez-Navarro, Carlos; Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa

    2012-06-01

    The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed. PMID:22447589

  3. A calcium oxide sorbent process for bulk separation of carbon dioxide

    SciTech Connect

    Harrison, D.P.

    1990-09-01

    This research effort is designed to investigate the technical feasibility of a high-temperature, high-pressure process for the bulk separation of CO{sub 2} from coal-derived gases. The two-year contract was awarded in September 1989. This report describes the research effort and results obtained during the first year of the effort. The overall project consists of 6 tasks, four of which were active during year 01. Tasks 1 and 2 were completed during the year while activity in Tasks 3 and 6 will carry over into year 02. Tasks 4 and 5 will be initiated during year 02. Three primary objectives were met in Task 1. A literature search on the calcination-carbonation reactions of CO{sub 2} with calcium-based sorbents was completed. A high temperature, high pressure (HTHP) electrobalance reactor suitable for studying the calcination and carbonation reactions was constructed. This reactor system is now fully operable and we are routinely collecting kinetics data at temperatures in the range of 550-900{degree}C and pressures of 1 to 15 atm. Samples of nine candidate calcium-based sorbents were acquired and tested. These samples were subjected to reaction screening tests as part of Task 2. As a result of these screening tests, chemically pure calcium carbonate, chemically pure calcium acetate, and the commercial dolomite were selected for more detailed kinetic testing. In Task 3, the HTHP electrobalance reactor is being used to study the calcination-carbonation behavior of the three base sorbents as a function of calcination temperature, carbonation temperature, carbonation pressure, and CO{sub 2} concentration.

  4. Theoretical model of the interaction of glycine with hydrogenated amorphous carbon (HAC).

    PubMed

    Timón, Vicente; Gálvez, Óscar; Maté, Belén; Tanarro, Isabel; Herrero, Víctor J; Escribano, Rafael

    2015-11-21

    A theoretical model of hydrogenated amorphous carbon (HAC) is developed and applied to study the interaction of glycine with HAC surfaces at astronomical temperatures. Two models with different H content are tried for the HAC surface. The theory is applied at the Density Functional Theory (DFT) level, including a semiempirical dispersion correlation potential, d-DFT or Grimme DFT-D2. The level of theory is tested on glycine adsorption on a Si(001) surface. Crystalline glycine is also studied in its two stable phases, α and β, and the metastable γ phase. For the adsorption on Si or HAC surfaces, molecular glycine is introduced in the neutral and zwitterionic forms, and the most stable configurations are searched. All theoretical predictions are checked against experimental observations. HAC films are prepared by plasma enhanced vapor deposition at room temperature. Glycine is deposited at 20 K into a high vacuum, cold temperature chamber, to simulate astronomical conditions. Adsorption takes place through the acidic group COO(-) and when several glycine molecules are present, they form H-bond chains among them. Comparison between experiments and predictions suggests that a possible way to improve the theoretical model would require the introduction of aliphatic chains or a polycyclic aromatic core. The lack of previous models to study the interaction of amino-acids with HAC surfaces provides a motivation for this work. PMID:26456640

  5. Graphitic clusters in hydrogenated amorphous carbon induced by keV-ion irradiation

    SciTech Connect

    Compagnini, G.; Foti, G.; Reitano, R. ); Mondio, G. )

    1990-12-10

    Energy gap and hydrogen concentration have been measured in hydrogenated amorphous carbon ({ital a}-C:H) after bombardment with 100 keV He{sup +} and 300 keV Ar{sup +} ion beams, up to ion fluences 3{times}10{sup 16} ions/cm{sup 2}. {ital a}-C:H films have been obtained by ion irradiation at low ion fluences of polystyrene layers and with a subsequent low-temperature annealing (400 {degree}C, 10 min). Experimental values for the energy gap (2.5--0.5 eV) and hydrogen concentration (7.4{times}10{sup 22}--1.8{times}10{sup 22} H atoms/cm{sup 3}) have been interpreted in terms of a graphitic cluster structure with a different size (3--20 A). We were able to determine experimentally the value of the bond integral {vert bar}{beta}{vert bar} and we found it in good agreement with the calculated one for graphite.

  6. Introducing novel amorphous carbon nanoparticles as energy acceptors into a chemiluminescence resonance energy transfer immunoassay system.

    PubMed

    Wang, Zhenxing; Gao, Hongfei; Fu, Zhifeng

    2013-11-21

    A novel chemiluminescence resonance energy transfer (CRET) system for competitive immunoassay of biomolecules was developed by using novel amorphous carbon nanoparticles (CNPs) prepared from candle soot as energy acceptors. The CNPs were firstly prepared to bind with the antigen (Ag) for obtaining the nanocomposite CNP-Ag, and this obtained CNP-Ag was then reacted with the horseradish peroxidase-labeled antibody (HRP-Ab) to assemble the CRET system. The luminol catalyzed by HRP serving as the energy donor for CNPs triggered the CRET phenomenon between luminol and CNPs, which led to the chemiluminescence signal decrease. Due to the competitive immunoreaction of the target antigen and the CNP-Ag, a part of the CNP-Ag was replaced from the HRP-Ab, and then resulted in a weaker interaction between luminol and CNPs. Thus the competitive immunoreaction led to a higher chemiluminescence emission. This CNP-based CRET system was successfully applied to detect the human IgG as a model analyte, and a linear range of 10-200 ng mL(-1) and a detection limit of 1.9 ng mL(-1) (S/N = 3) were obtained. The results for real sample analysis demonstrated its application potential in some important areas such as clinical diagnosis. PMID:23979821

  7. Tribological properties, corrosion resistance and biocompatibility of magnetron sputtered titanium-amorphous carbon coatings

    NASA Astrophysics Data System (ADS)

    Dhandapani, Vishnu Shankar; Subbiah, Ramesh; Thangavel, Elangovan; Arumugam, Madhankumar; Park, Kwideok; Gasem, Zuhair M.; Veeraragavan, Veeravazhuthi; Kim, Dae-Eun

    2016-05-01

    Amorphous carbon incorporated with titanium (a-C:Ti) was coated on 316L stainless steel (SS) by magnetron sputtering technique to attain superior tribological properties, corrosion resistance and biocompatibility. The morphology, topography and functional groups of the nanostructured a-C:Ti coatings in various concentrations were analyzed using atomic force microscopy (AFM), Raman, X-Ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Raman and XPS analyses confirmed the increase in sp2 bonds with increasing titanium content in the a-C matrix. TEM analysis confirmed the composite nature of the coating and the presence of nanostructured TiC for Ti content of 2.33 at.%. This coating showed superior tribological properties compared to the other a-C:Ti coatings. Furthermore, electrochemical corrosion studies were performed against stimulated body fluid medium in which all the a-C:Ti coatings showed improved corrosion resistance than the pure a-C coating. Preosteoblasts proliferation and viability on the specimens were tested and the results showed that a-C:Ti coatings with relatively high Ti (3.77 at.%) content had better biocompatibility. Based on the results of this work, highly durable coatings with good biocompatibility could be achieved by incorporation of optimum amount of Ti in a-C coatings deposited on SS by magnetron sputtering technique.

  8. Modification of the amorphous carbon films by the ns-laser irradiation

    NASA Astrophysics Data System (ADS)

    Grigonis, Alfonsas; Marcinauskas, Liutauras; Vinciunaite, Vinga; Raciukaitis, Gediminas

    2011-10-01

    The effect of a nanosecond laser irradiation of thin (60 and 145 nm) amorphous, diamond-like carbon films deposited on Si substrate by an ion beam deposition (IBD) from pure acetylene and acetylene/hydrogen (1:2) gas mixture was analyzed in this work. The films were irradiated with the infrared (IR) and ultraviolet (UV) radiation of the nanosecond Nd:YAG lasers working at the first (1.16 eV) and the third (3.48 eV) harmonics, using a multi-shot regime. The IR laser irradiation stimulated a minor increase in the fraction of sp2 bonds, causing a slight decrease in the hardness of the films and initiated SiC formation. Irradiation with the UV laser caused the formation of carbides and increased hydrogenization of the Si substrate and the fraction of sp2 sites. Spalliation and ablation were observed at a higher energy density and with a large number of laser pulses per spot.

  9. Microstructure and tribological properties of Ti-contained amorphous carbon film deposited by DC magnetron sputtering

    SciTech Connect

    Li, R. L.; Tu, J. P.; Hong, C. F.; Liu, D. G.; Zhou, D. H.; Sun, H. L.

    2009-12-15

    Pure amorphous carbon (a-C) film and that with a small amount of Ti were deposited on high speed steel (W18Cr4V) substrates by means of dc closed field unbalanced magnetron sputtering. The chemical composition and microstructure of the a-C films were performed using x-ray photoelectron spectroscopy, x-ray diffraction, Raman spectra, and transmission electron microscopy. The mechanical and tribological properties were evaluated using a nanoindentor, Rockwell and scratch tests, and a conventional ball-on-disk tribometer, respectively. The pure a-C film showed the high hardness (53 GPa), elastic modulus (289 GPa), but the poor adhesive strength. When adding a small amount of Ti to the a-C film, both the adhesive strength and the tribological properties were improved. The Ti contained a-C film had the low wear rate (1.9x10{sup -17} m{sup 3} N{sup -1} m{sup -1}) and friction coefficient in humid air.

  10. Amorphous carbon nanoparticle used as novel resonance energy transfer acceptor for chemiluminescent immunoassay of transferrin.

    PubMed

    Gao, Hongfei; Wang, Wenwen; Wang, Zhenxing; Han, Jing; Fu, Zhifeng

    2014-03-28

    Amorphous carbon nanoparticles (ACNPs) showing highly efficient quenching of chemiluminescence (CL) were prepared from candle soot with a very simple protocol. The prepared ACNP was employed as the novel energy acceptor for a chemiluminescence resonance energy transfer (CRET)-based immunoassay. In this work, ACNP was linked with transferrin (TRF), and horseradish peroxidase (HRP) was conjugated to TRF antibody (HRP-anti-TRF). The immunoreaction rendered the distance between the ACNP acceptor and the HRP-catalyzed CL emitter to be short enough for CRET occurring. In the presence of TRF, this antigen competed with ACNP-TRF for HRP-anti-TRF, thus led to the decreased occurrence of CRET. A linear range of 20-400 ng mL(-1) and a limit of detection of 20 ng mL(-1) were obtained in this immunoassay. The proposed method was successfully applied for detection of TRF levels in human sera, and the results were in good agreement with ELISA method. Moreover, the ACNPs show higher energy transfer efficiency than other conventional nano-scaled energy acceptors such as graphene oxide in CRET assay. It is anticipated that this approach can be developed for determination of other analytes with low cost, simple manipulation and high specificity. PMID:24636417

  11. Hydrogenated amorphous carbon coatings on implants drastically reduce biofilm formation and water permeation

    NASA Astrophysics Data System (ADS)

    Bernsmann, Falk; Laube, Norbert; Baldsiefen, Gerhard; Castellucci, Mattia

    2014-11-01

    Inflammations and crystalline bacterial biofilms (encrustations) remain a major complication in long-term artificial urinary tract drainage. To solve this problem we present urological implants with coatings made of amorphous hydrogenated carbon (a-C:H) that show excellent protection from encrustation in-vitro as well as in-vivo. Part of the success of a-C:H coatings is attributed to their ability to act as a diffusion barrier between an implant and the body, which prevents leaching of solvents from polymeric implants. To further enhance their barrier properties a-C:H coatings are combined with parylene coatings to develop diffusion-barrier multilayer coatings with a total thickness between 0.2 μm and 0.8 μm. The combination of the two types of coatings leads to a reduction of water diffusion by a factor of up to ten with respect to uncoated 25 μm thick polyimide sub-strates. The diffusion of water vapour from a controlled atmospheric pressure chamber through coated foils to a vacuum chamber is measured in a custom-built device.

  12. Human Umbilical Vein Endothelial Cell Interaction with Fluorine-Incorporated Amorphous Carbon Films

    NASA Astrophysics Data System (ADS)

    Yoshimoto, Yukihiro; Hasebe, Terumitsu; Nagashima, So; Kamijo, Aki; Nakatani, Tatsuyuki; Yamagami, Takuji; Kitamura, Noriko; Kitagawa, Tomoya; Hotta, Atsushi; Takahashi, Koki; Suzuki, Tetsuya

    2012-09-01

    A major clinical concern in coronary intervention for cardiovascular disease is late stent thrombosis after the implantation of drug eluting stents (DES). DES widely used in clinical settings currently utilize polymer coatings, which can induce persistent arterial wall inflammation and delayed vascular healing, resulting in impaired endothelialization. We examined the viability of human umbilical vein endothelial cells (HUVECs) for fluorine-incorporated amorphous carbon (a-C:H:F) coatings, which are known to be anti-thrombogenic. a-C:H:F and a-C:H were synthesized on the tissue culture dishes using radio frequency plasma enhanced chemical vapor deposition by varying the ratio of hexafluoroethane and acetylene. HUVECs were seeded on coated dishes for 6 days. The results indicate that the a-C:H:F surface does not disturb HUVEC proliferation in 6 days of culture and is promising for stent materials that allows the preservation of endothelialization, even if the fluorine concentration of a-C:H surface affects the early adhesion of endothelial cells.

  13. Energy band alignment and electronic states of amorphous carbon surfaces in vacuo and in aqueous environment

    NASA Astrophysics Data System (ADS)

    Caro, Miguel A.; Määttä, Jukka; Lopez-Acevedo, Olga; Laurila, Tomi

    2015-01-01

    In this paper, we obtain the energy band positions of amorphous carbon (a-C) surfaces in vacuum and in aqueous environment. The calculations are performed using a combination of (i) classical molecular dynamics (MD), (ii) Kohn-Sham density functional theory with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional, and (iii) the screened-exchange hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE). PBE allows an accurate generation of a-C and the evaluation of the local electrostatic potential in the a-C/water system, HSE yields an improved description of energetic positions which is critical in this case, and classical MD enables a computationally affordable description of water. Our explicit calculation shows that, both in vacuo and in aqueous environment, the a-C electronic states available in the region comprised between the H2/H2O and O2/H2O levels of water correspond to both occupied and unoccupied states within the a-C pseudogap region. These are localized states associated to sp2 sites in a-C. The band realignment induces a shift of approximately 300 meV of the a-C energy band positions with respect to the redox levels of water.

  14. Inelastic and reactive scattering of hyperthermal atomic oxygen from amorphous carbon

    NASA Technical Reports Server (NTRS)

    Minton, Timothy K.; Nelson, Christine M.; Brinza, David E.; Liang, Ranty H.

    1991-01-01

    The reaction of hyperthermal oxygen atoms with an amorphous carbon-13 surface was studied using a modified universal crossed molecular beams apparatus. Time-of-flight distributions of inelastically scattered O-atoms and reactively scattered CO-13 and CO2-13 were measured with a rotatable mass spectrometer detector. Two inelastic scattering channels were observed, corresponding to a direct inelastic process in which the scattered O-atoms retain 20 to 30 percent of their initial kinetic energy and to a trapping desorption process whereby O-atoms emerge from the surface at thermal velocities. Reactive scattering data imply the formation of two kinds of CO products, slow products whose translational energies are determined by the surface temperature and hyperthermal (Approx. 3 eV) products with translational energies comprising roughly 30 percent of the total available energy (E sub avl), where E sub avl is the sum of the collision energy and the reaction exothermicity. Angular data show that the hyperthermal CO is scattered preferentially in the specular direction. CO2 product was also observed, but at much lower intensities than CO and with only thermal velocities.

  15. Patterning with amorphous carbon spacer for expanding the resolution limit of current lithography tool

    NASA Astrophysics Data System (ADS)

    Jung, Woo-Yung; Kim, Sang-Min; Kim, Choi-Dong; Sim, Guee-Hwang; Jeon, Sung-Min; Park, Sang-Wook; Lee, Byung-Seok; Park, Sung-Ki; Kim, Ji-Soo; Heon, Lee-Sang

    2007-03-01

    Double patterning technique using spacer which can avoid CD (Critical Dimension) uniformity problem mainly caused by overlay issue is one of the methods that could be applied to apply to manufacturing of memory devices. Though double exposure and etch technology (DEET) has comparative advantage in the number of process steps, it is required to dramatically improve overlay performance of current exposure tools for the realization of manufacturing. In this study, negative type-double pattering technique using spacer has been developed as the best way for the application of NAND flash memory device from the view point of CD uniformity and the number of mask layers used to complete double patterning. Negative type-double patterning technique using spacer consists of subsequent steps such as formation of poly line, spacer on sidewall of poly line, SOG gap fill into space between poly lines, SOG etch back, removal of spacer, and finally hard mask etch. We have used amorphous carbon as a spacer material to easily remove spacer from poly lines and adopted SOG material to easily fill in space between poly lines. When negative type-double patterning technique using spacer is applied to NAND flash memory device, we can expect that k1 factor of about 0.14~0.20 could be accomplished successfully.

  16. Energy band alignment and electronic states of amorphous carbon surfaces in vacuo and in aqueous environment

    SciTech Connect

    Caro, Miguel A.; Määttä, Jukka; Lopez-Acevedo, Olga; Laurila, Tomi

    2015-01-21

    In this paper, we obtain the energy band positions of amorphous carbon (a–C) surfaces in vacuum and in aqueous environment. The calculations are performed using a combination of (i) classical molecular dynamics (MD), (ii) Kohn-Sham density functional theory with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional, and (iii) the screened-exchange hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE). PBE allows an accurate generation of a-C and the evaluation of the local electrostatic potential in the a-C/water system, HSE yields an improved description of energetic positions which is critical in this case, and classical MD enables a computationally affordable description of water. Our explicit calculation shows that, both in vacuo and in aqueous environment, the a-C electronic states available in the region comprised between the H{sub 2}/H{sub 2}O and O{sub 2}/H{sub 2}O levels of water correspond to both occupied and unoccupied states within the a-C pseudogap region. These are localized states associated to sp{sup 2} sites in a-C. The band realignment induces a shift of approximately 300 meV of the a-C energy band positions with respect to the redox levels of water.

  17. Amorphous Carbon Deposited by a Novel Aerosol-Assisted Chemical Vapor Deposition for Photovoltaic Solar Cells

    NASA Astrophysics Data System (ADS)

    Ahmad, Nurfadzilah; Kamaruzzaman, Dayana; Rusop, Mohamad

    2012-06-01

    Amorphous carbon (a-C) solar cells were successfully prepared using a novel and self-designed aerosol-assisted chemical vapor deposition (AACVD) method using camphor oil as a precursor. The fabricated solar cell with the configuration of Au/p-C/n-Si/Au achieved an efficiency of 0.008% with a fill factor of 0.15 for the device deposited at 0.5 h. The current-voltage (I-V) graph emphasized on the linear graph (ohmic) for the a-C thin films, whereas for the p-n device structure, a rectifying curve was obtained. The rectifying curves signify the heterojunction between the p-type a-C film and the n-Si substrate and designate the generation of electron-hole pair of the samples under illumination. Photoresponse characteristics of the deposited a-C was highlighted when being illuminated (AM 1.5 illumination: 100 mW/cm2, 25 °C). Transmittance spectrum exhibit a large transmittance value (>85%) and absorption coefficient value of 103-104 cm-1 at the visible range of 390 to 790 nm. The atomization of a liquid precursor solution into fine sub-micrometre-sized aerosol droplets in AACVD induced the smooth surface of a-C films. To the best of our knowledge, fabrication of a-C solar cell using this AACVD method has not yet been reported.

  18. Breakthrough curves of oil adsorption on novel amorphous carbon thin film.

    PubMed

    El-Sayed, M; Ramzi, M; Hosny, R; Fathy, M; Abdel Moghny, Th

    2016-01-01

    A novel amorphous carbon thin film (ACTF) was prepared by hydrolyzing wood sawdust and delignificating the residue to obtain cellulose mass that was subjected to react with cobalt silicate nanoparticle as a catalyst under the influence of sudden concentrated sulfuric acid addition at 23 °C. The novel ACTF was obtained in the form of thin films like graphene sheets having winding surface. The prepared ACTF was characterized by Fourier-transform infrared spectrometer, transmission electron microscope (TEM), and Brunauer-Emmett-Teller (BET). The adsorption capacity of ACTF to remove oil from synthetic produced water was evaluated using the incorporation of Thomas and Yoon-Nelson models. The performance study is described through the breakthrough curves concept under relevant operating conditions such as column bed heights (3.8, 5 and 11 mm) and flow rate (0.5, 1 and 1.5 mL.min(-1)). It was found that the oil uptake mechanism is favoring higher bed height. Also, the highest bed capacity of 700 mg oil/g ACTF was achieved at 5 mm bed height, and 0.5 mL.min(-1) flow rate. The results of breakthrough curve for oil adsorption was best described using the Yoon-Nelson model. Finally, the results illustrate that ACTF could be utilized effectively for oil removal from synthetic produced water in a fixed-bed column system. PMID:27191556

  19. Behavior of Enterobacter pulveris in amorphous and crystalline powder matrices treated with supercritical carbon dioxide.

    PubMed

    Callanan, M; Paes, M; Iversen, C; Kleijn, R; Bravo Almeida, C; Peñaloza, W; Johnson, N; Vuataz, G; Michel, M

    2012-11-01

    The resistance of an Enterobacter pulveris strain to combined heat and supercritical carbon dioxide (scCO(2)) treatments in different powder matrices was examined. The strain proved resistant to scCO(2) treatment up to 50 MPa pressure at temperatures >73 °C for at least 20 min in a commercial infant formula. Water availability was shown to be important for the observed thermotolerance, because introduction of water in the scCO(2) gas flow during treatment resulted in a 1 log(10) cfu/g reduction of the initial inoculum. Interestingly, similar tolerance to heat and scCO(2) treatment was observed in a less complex matrix, a maltodextrin powder. In contrast, the bacterial strain proved sensitive to lower temperatures (55-65 °C) over shorter times (≤10 min) in a dextrose powder composed of crystalline particles. Therefore, the microorganism demonstrates heat sensitivity in the crystalline powder matrix closer to that of nonpowder liquid matrices. These data demonstrate the increased heat tolerance of the bacterium specifically in amorphous powders and indicate that this characteristic is not dependent on fat and other components commonly found in infant formula. The information is important in designing strategies to deal with contamination of powders with Enterobacteriacae, including pathogenic Cronobacter spp. PMID:22959935

  20. Precipitation of calcium carbonate in aqueous solutions in presence of ethylene glycol and dodecane.

    NASA Astrophysics Data System (ADS)

    Natsi, Panagiota D.; Rokidi, Stamatia; Koutsoukos, Petros G.

    2015-04-01

    The formation of calcium carbonate (CaCO3) in aqueous supersaturated solutions has been intensively studied over the past decades, because of its significance for a number of processes of industrial and environmental interest. In the oil and gas production industry the deposition of calcium carbonate affects adversely the productivity of the wells. Calcium carbonate scale deposits formation causes serious problems in water desalination, CO2 sequestration in subsoil wells, in geothermal systems and in heat exchangers because of the low thermal coefficient of the salt. Amelioration of the operational conditions is possible only when the mechanisms underlying nucleation and crystal growth of calcium carbonate in the aqueous fluids is clarified. Given the fact that in oil production processes water miscible and immiscible hydrocarbons are present the changes of the dielectric constant of the fluid phase has serious impact in the kinetics of calcium carbonate precipitation, which remains largely unknown. The problem becomes even more complicated if polymorphism exhibited by calcium carbonate is also taken into consideration. In the present work, the stability of aqueous solutions supersaturated with respect to all calcium carbonate polymorphs and the subsequent kinetics of calcium carbonate precipitation were measured. The measurements included aqueous solutions and solutions in the presence of water miscible (ethylene glycol, MEG) and water immiscible organics (n-dodecane). All measurements were done at conditions of sustained supersaturation using the glass/ Ag/AgCl combination electrode as a probe of the precipitation and pH as the master variable for the addition of titrant solutions with appropriate concentration needed to maintenance the solution supersaturation. Initially, the metastable zone width was determined from measurements of the effect of the solution supersaturation on the induction time preceding the onset of precipitation at free-drift conditions. The