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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, 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...

  1. 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....

  2. 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.

  3. 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...

  4. 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....

  5. 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,...

  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 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....

  1. 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...

  2. 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...

  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. 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

  5. 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

  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 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

  5. 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

  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

    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

    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.

  14. 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

  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. 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

  2. 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

  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. 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.

  14. 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.

  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 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

  19. 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

  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. 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

  16. 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

  17. 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

  18. 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.

  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

    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.

  7. 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

  8. 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.

  9. 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

  10. 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.

  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. 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

  16. 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

  17. 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

  18. 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

  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. 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. ...

  18. 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

  19. 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

  20. 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.

  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. 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.

  3. 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

  4. 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

  5. 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.

  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. 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

  8. 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

  9. 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

  10. 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

  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. 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

  8. 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.

  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. 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.

  13. 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

  14. 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.

  15. 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

  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. 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

  9. 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

  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