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Sample records for amorphous calcium carbonate

  1. Biologically formed amorphous calcium carbonate.

    PubMed

    Weiner, Steve; Levi-Kalisman, Yael; Raz, Sefi; Addadi, Lia

    2003-01-01

    Many organisms from a wide variety of taxa produce amorphous calcium carbonate (ACC), despite the fact that it is inherently unstable and relatively soluble in its pure state. These properties also make it difficult to detect and characterize ACC. Raman spectroscopy is a particularly useful method for investigating ACC because the sample can be examined wet, and extended X-ray absorption fine structure (EXAFS) analysis can provide detailed information on the short-range order. Other methods for characterizing ACC include infrared spectroscopy, thermogravimetric analysis and differential thermal analysis (TGA and DTA), transmission electron microscopy (TEM), and electron and X-ray diffraction. Because of the difficulties involved, we suspect that ACC is far more widely distributed than is presently known, and a comparison of EXAFS spectra shows that different biogenic ACC phases have different short-range order structures. We also suspect that ACC fulfils many different functions, including as a transient precursor phase during the formation of crystalline calcium carbonate.

  2. Is Mg-stabilized amorphous calcium carbonate a homogeneous mixture of amorphous magnesium carbonate and amorphous calcium carbonate?

    PubMed

    Yang, Sheng-Yu; Chang, Hsun-Hui; Lin, Cang-Jie; Huang, Shing-Jong; Chan, Jerry C C

    2016-10-04

    We find two types of carbonate ions in Mg stabilized amorphous calcium carbonate (Mg-ACC), whose short-range orders are identical to those of ACC and amorphous magnesium carbonate (AMC). Mg-ACC comprises a homogeneous mixture of the nano-clusters of ACC and AMC. Their relative amount varies systematically at different pH.

  3. 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.

  4. Phase transitions in biogenic amorphous calcium carbonate

    PubMed Central

    Gong, Yutao U. T.; Killian, Christopher E.; Olson, Ian C.; Appathurai, Narayana P.; Amasino, Audra L.; Martin, Michael C.; Holt, Liam J.; Wilt, Fred H.; Gilbert, P. U. P. A.

    2012-01-01

    Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC·H2O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC·H2O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC·H2O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC·H2O in vitro. PMID:22492931

  5. 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.

  6. Disordered amorphous calcium carbonate from direct precipitation

    DOE PAGES

    Farhadi Khouzani, Masoud; Chevrier, Daniel M.; Güttlein, Patricia; ...

    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

  7. 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.

  8. 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.

  9. 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.

  10. Dehydration-induced amorphous phases of calcium carbonate.

    PubMed

    Saharay, Moumita; Yazaydin, A Ozgur; Kirkpatrick, R James

    2013-03-28

    Amorphous calcium carbonate (ACC) is a critical transient phase in the inorganic precipitation of CaCO3 and in biomineralization. The calcium carbonate crystallization pathway is thought to involve dehydration of more hydrated ACC to less hydrated ACC followed by the formation of anhydrous ACC. We present here computational studies of the transition of a hydrated ACC with a H2O/CaCO3 ratio of 1.0 to anhydrous ACC. During dehydration, ACC undergoes reorganization to a more ordered structure with a significant increase in density. The computed density of anhydrous ACC is similar to that of calcite, the stable crystalline phase. Compared to the crystalline CaCO3 phases, calcite, vaterite, and aragonite, the computed local structure of anhydrous ACC is most-similar to those of calcite and vaterite, but the overall structure is not well described by either. The strong hydrogen bond interaction between the carbonate ions and water molecules plays a crucial role in stabilizing the less hydrated ACC compositions compared to the more hydrated ones, leading to a progressively increasing hydration energy with decreasing water content.

  11. 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...

  12. Freeze-drying yields stable and pure amorphous calcium carbonate (ACC).

    PubMed

    Ihli, Johannes; Kulak, Alexander N; Meldrum, Fiona C

    2013-04-18

    A simple synthetic method is presented for the precipitation of high purity, dry amorphous calcium carbonate (ACC) based on freeze-drying saturated, counter ion free CaCO3 solutions, where the ACC produced shows an extended atmospheric stability. Translation of the methodology to amorphous calcium phosphate demonstrates the generality of the approach.

  13. Aragonite nanorods in calcium carbonate/polymer hybrids formed through self-organization processes from amorphous calcium carbonate solution.

    PubMed

    Kajiyama, Satoshi; Nishimura, Tatsuya; Sakamoto, Takeshi; Kato, Takashi

    2014-04-24

    Nanostructured inorganic/polymer hybrid thin films comprising aragonite nanorods derived from aqueous suspensions of amorphous calcium carbonate (ACC) are prepared. For the formation of calcium carbonate (CaCO₃)/polymer hybrids, spincoated and annealed films of poly(vinyl alcohol) (PVA) that function as polymer matrices are soaked in aqueous colloidal solutions dispersing ACC stabilized by poly(acrylic acid) (PAA). In the initial stage, calcite thin films form on the surface. Subsequently, aragonite crystals start to form inside the PVA matrix that contains PVA crystallites which induce aragonite nucleation. Nanostructured hybrids composed of calcite thin films consisting of nanoparticles and assembled aragonite nanorods are formed in the matrices of PVA.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Increased calcium absorption from synthetic stable amorphous calcium carbonate: double-blind randomized crossover clinical trial in postmenopausal women.

    PubMed

    Vaisman, Nachum; Shaltiel, Galit; Daniely, Michal; Meiron, Oren E; Shechter, Assaf; Abrams, Steven A; Niv, Eva; Shapira, Yami; Sagi, Amir

    2014-10-01

    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 (CCC) using the dual stable isotope technique. The study was conducted in the Unit of Clinical Nutrition, Tel Aviv Sourasky Medical Center, Israel. The study population included 15 early postmenopausal women aged 54.9 ± 2.8 (mean ± SD) years with no history of major medical illness or metabolic bone disorder, excess calcium intake, or vitamin D deficiency. Standardized breakfast was followed by randomly provided CCC or ACC capsules containing 192 mg elemental calcium labeled with 44Ca at intervals of at least 3 weeks. After swallowing the capsules, intravenous CaCl2 labeled with 42Ca on was administered on each occasion. Fractional calcium absorption (FCA) of ACC and CCC was calculated from the 24-hour urine collection following calcium administration. The results indicated that FCA of ACC was doubled (± 0.96 SD) on average compared to that of CCC (p < 0.02). The higher absorption of the synthetic stable ACC may serve as a more efficacious way of calcium supplementation.

  19. 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

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

    PubMed

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

    2011-12-23

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

  1. Amorphous and crystalline calcium carbonate distribution in the tergite cuticle of moulting Porcellio scaber (Isopoda, Crustacea).

    PubMed

    Neues, Frank; Hild, Sabine; Epple, Matthias; Marti, Othmar; Ziegler, Andreas

    2011-07-01

    The main mineral components of the isopod cuticle consists of crystalline magnesium calcite and amorphous calcium carbonate. During moulting isopods moult first the posterior and then the anterior half of the body. In terrestrial species calcium carbonate is subject to resorption, storage and recycling in order to retain significant fractions of the mineral during the moulting cycle. We used synchrotron X-ray powder diffraction, elemental analysis and Raman spectroscopy to quantify the ACC/calcite ratio, the mineral phase distribution and the composition within the anterior and posterior tergite cuticle during eight different stages of the moulting cycle of Porcellio scaber. The results show that most of the amorphous calcium carbonate (ACC) is resorbed from the cuticle, whereas calcite remains in the old cuticle and is shed during moulting. During premoult resorption of ACC from the posterior cuticle is accompanied by an increase within the anterior tergites, and mineralization of the new posterior cuticle by resorption of mineral from the anterior cuticle. This suggests that one reason for using ACC in cuticle mineralization is to facilitate resorption and recycling of cuticular calcium carbonate. Furthermore we show that ACC precedes the formation of calcite in distal layers of the tergite cuticle.

  2. 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.

  3. 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.

  4. 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

  5. Amorphous calcium carbonate precipitation by cellular biomineralization in mantle cell cultures of Pinctada fucata.

    PubMed

    Xiang, Liang; Kong, Wei; Su, Jing-Tan; Su, Jingtan; Liang, Jian; Zhang, Gui-You; Zhang, Guiyou; Xie, Li-Ping; Xie, Liping; Zhang, Rong-Qing; 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.

  6. Synthesis and structure of synthetically pure and deuterated amorphous (basic) calcium carbonates

    DOE PAGES

    Wang, Hsiu-Wen; Oak Ridge National Lab.; Daemen, Luke L.; ...

    2017-02-17

    It is generally believed that H2O and OH- are the key species stabilizing and controlling amorphous calcium carbonate “polyamorph” forms, and may in turn control the ultimate crystallization products during synthesis and in natural systems. Yet, the locations and hydrogen-bonding network of these species in ACC have never been measured directly using neutron diffraction. In this paper, we report a synthesis route that overcomes the existing challenges with respect to yield quantities and deuteration, both of which are critically necessary for high quality neutron studies.

  7. 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.

  8. 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.

  9. Properties of amorphous calcium carbonate and the template action of vaterite spheres.

    PubMed

    Shen, Qiang; Wei, Hao; Zhou, Yong; Huang, Yaping; Yang, Hengrui; Wang, Dujin; Xu, Duanfu

    2006-02-23

    The fast mixing of aqueous solutions of calcium chloride and sodium carbonate could immediately result in amorphous calcium carbonate (ACC). Under vigorous stirring, the formed ACC in the precipitation system will dissolve first and, then, transform within minutes to produce crystalline forms of vaterite and calcite. After that, the solution-mediated mechanism dominates the transformation of the thermodynamically unstable vaterite into the thermodynamically stable calcite. Although ACC is the least stable form of the six anhydrous phases of calcium carbonate (CaCO(3)), it could be, however, produced and stabilized by a variety of organisms. To better understand the formation-transformation mechanism of ACC and vaterite into calcite, ex-situ methods (i.e., scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction spectroscopy) were used to characterize the formation-transformation process of ACC and vaterite in aqueous systems without organic additives, showing that ACC sampled at different conditions has different properties (i.e., lifetime, morphology, and spectrum characterization). It is also very interesting to capture the obviously polycrystalline particles of CaCO(3) during the transformation process from vaterite to calcite, which suggests the formation mechanism for the calcite superstructure with multidimensional morphology.

  10. Two modes of transformation of amorphous calcium carbonate films in air.

    PubMed

    Xu, Xurong; Han, Joong Tark; Kim, Do Hwan; Cho, Kilwon

    2006-02-16

    Large-area amorphous calcium carbonate (ACC) films in air are shown to be transformed into crystalline calcium carbonate (CaCO(3)) films via two modes-dissolution-recrystallization and solid-solid phase transition-depending on the relative humidity of the air and the temperature. Moisture in the air promotes the transformation of ACC into crystalline forms via a dissolution-recrystallization process. Increasing the humidity increases the rate of ACC crystallization and gives rise to films with numerous large pores. As the temperature is increased, the effect of moisture in the air is reduced and solid-solid transition by thermal activation becomes the dominant transformation mechanism. At 100 and 120 degrees C, ACC films are transformed into predominantly (110) oriented crystalline films. Collectively, the results show that calcium carbonate films with different morphologies, crystal phases, and structures can be obtained by controlling the humidity and temperature. This ability to control the transformation of ACC should assist in clarifying the role of ACC in the biomineralization of CaCO(3) and should open new avenues for preparing CaCO(3) films with oriented and fine structure.

  11. Distinct Short-Range Order Is Inherent to Small Amorphous Calcium Carbonate Clusters (<2 nm)

    SciTech Connect

    Sun, Shengtong; Chevrier, Daniel M.; Zhang, Peng; Gebauer, Denis; Cölfen, Helmut

    2016-09-09

    Amorphous intermediate phases are vital precursors in the crystallization of many biogenic minerals. While inherent short-range orders have been found in amorphous calcium carbonates (ACCs) relating to different crystalline forms, it has never been clarified experimentally whether such orders already exist in very small clusters less than 2 nm in size. Here, we studied the stability and structure of 10,12-pentacosadiynoic acid (PCDA) protected ACC clusters with a core size of ca. 1.4 nm consisting of only seven CaCO3 units. Ligand concentration and structure are shown to be key factors in stabilizing the ACC clusters. More importantly, even in such small CaCO3 entities, a proto-calcite short-range order can be identified but with a relatively high degree of disorder that arises from the very small size of the CaCO3 core. Our findings support the notion of a structural link between prenucleation clusters, amorphous intermediates, and final crystalline polymorphs, which appears central to the understanding of polymorph selection.

  12. Coupled dissolution-precipitation as a mechanism for amorphous-to-crystalline calcium carbonate phase transition

    NASA Astrophysics Data System (ADS)

    Rodriguez-Navarro, Carlos Manuel; Kudłacz, Krzysztof; Ruiz-Agudo, Encarnacion

    2014-05-01

    Growing evidence shows that several calcium carbonate biominerals form via an amorphous precursor phase. Such a biomineralization strategy could also be applicable for the biomimetic synthesis of novel functional materials. A crucial step in this process is the transformation of amorphous calcium carbonate (ACC) into calcite. However, controversy exists as to what is the actual mechanism of this transformation: Is it a solid-solid (solid state) or a dissolution/precipitation mechanism? Determining the transition mechanism is critical for example in interpreting the formation of oriented crystalline structures in biominerals (e.g., echinoderm spicles). We studied calcium carbonate precipitation and phase transitions according to the overall reaction Ca(OH)2 + CO2 = CaCO3+ H2O. Mineral phase transformations during this reaction were studied using transmission electron microscopy (TEM). Our TEM analysis showed that two different types of ACC are sequentially formed during this reaction. Type I ACC shows no well-defined short-range order, while Type II ACC shows a short-range order corresponding to calcite. Following e-beam irradiation, Type I ACC particles transform into randomly oriented CaO nanocrystals, while irradiation of Type II ACC leads to the formation of pseudomorphs made up of perfectly oriented aggregates of calcite nanocrystals. Moreover, calcite crystals formed in solution or in air (85 % relative humidity) after Type II ACC are also pseudomorphs made up of porous aggregates of preferentially oriented calcite nanocrystals. Our results give experimental evidence showing that the ACC to calcite transformation under relevant biomineralization conditions (low T and P), also applicable in the biomimetic synthesis of calcite, is a pseudomorphic dissolution-precipitation process. This mechanism involves the tightly interface-coupled dissolution of the precursor amorphous phase (with the crystalline phase protostructure) and concomitant deposition of the

  13. Preparation and characterization of novel biphasic calcium phosphate powders (alpha-TCP/HA) derived from carbonated amorphous calcium phosphates.

    PubMed

    Li, Yanbao; Kong, Fanzhi; Weng, Wenjian

    2009-05-01

    Novel biphasic calcium phosphate (BCP) powders composed of alpha-tricalcium phosphate (alpha-TCP) and hydroxyapatite (HA) were prepared by thermal decomposition of carbonated amorphous calcium phosphates (CACP). At first, the CACP precipitates were synthesized by adding ammonium carbonate in the presence of poly(ethylene glycol) at pH 10 with an initial Ca/P molar ratio of 1.60 at 5 degrees C. The Ca/P molar ratios of the CACP precursors are between 1.50 and 1.67 investigated by ICP. Then BCP (alpha-TCP/HA) powders were obtained after heating the CACP precursors at relatively low temperature (800 degrees C) for 3 h. alpha-TCP/HA powders were characterized by X-ray diffractometry, Fourier transform infrared spectra, transmission electron microscopy/scanning electron microscopy, and sedimentation experiment. The results show that alpha-TCP and HA phases form in one powder, alpha-TCP/HA powders are sphere with the diameter of 300 nm to less than 100 nm varied with their chemical compositions and the ratio of alpha-TCP and HA in the powders can be adjusted by the adding amount of carbonates. The possible formation process of biphasic alpha-TCP/HA powders was proposed.

  14. 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.

  15. Formation of amorphous calcium carbonate in caves and its implications for speleothem research

    NASA Astrophysics Data System (ADS)

    Demény, Attila; Németh, Péter; Czuppon, György; Leél-Őssy, Szabolcs; Szabó, Máté; Judik, Katalin; Németh, Tibor; Stieber, József

    2016-12-01

    Speleothem deposits are among the most valuable continental formations in paleoclimate research, as they can be dated using absolute dating methods, and they also provide valuable climate proxies. However, alteration processes such as post-depositional mineralogical transformations can significantly influence the paleoclimatic application of their geochemical data. An innovative sampling and measurement protocol combined with scanning and transmission electron microscopy, X-ray diffraction and Fourier transform infrared spectroscopy is presented, demonstrating that carbonate precipitating from drip water in caves at ~10 °C contains amorphous calcium carbonate (ACC) that later transforms to nanocrystalline calcite. Stable oxygen isotope fractionations among calcite, ACC and water were also determined, proving that ACC is 18O-depleted (by >2.4 ± 0.8‰) relative to calcite. This, in turn, has serious consequences for speleothem-based fluid inclusion research as closed system transformation of ACC to calcite may induce a negative oxygen isotope shift in fluid inclusion water, resulting in deterioration of the original compositions. ACC formation increases the speleothems’ sensitivity to alteration as its interaction with external solutions may result in the partial loss of original proxy signals. Mineralogical analysis of freshly precipitating carbonate at the studied speleothem site is suggested in order to determine the potential influence of ACC formation.

  16. A mixed flow reactor method to synthesize amorphous calcium carbonate under controlled chemical conditions.

    PubMed

    Blue, Christina R; Rimstidt, J Donald; Dove, Patricia M

    2013-01-01

    This study describes a new procedure to synthesize amorphous calcium carbonate (ACC) from well-characterized solutions that maintain a constant supersaturation. The method uses a mixed flow reactor to prepare ACC in significant quantities with consistent compositions. The experimental design utilizes a high-precision solution pump that enables the reactant solution to continuously flow through the reactor under constant mixing and allows the precipitation of ACC to reach steady state. As a proof of concept, we produced ACC with controlled Mg contents by regulating the Mg/Ca ratio of the input solution and the carbonate concentration and pH. Our findings show that the Mg/Ca ratio of the reactant solution is the primary control for the Mg content in ACC, as shown in previous studies, but ACC composition is further regulated by the carbonate concentration and pH of the reactant solution. The method offers promise for quantitative studies of ACC composition and properties and for investigating the role of this phase as a reactive precursor to biogenic minerals.

  17. Formation of amorphous calcium carbonate in caves and its implications for speleothem research

    PubMed Central

    Demény, Attila; Németh, Péter; Czuppon, György; Leél-Őssy, Szabolcs; Szabó, Máté; Judik, Katalin; Németh, Tibor; Stieber, József

    2016-01-01

    Speleothem deposits are among the most valuable continental formations in paleoclimate research, as they can be dated using absolute dating methods, and they also provide valuable climate proxies. However, alteration processes such as post-depositional mineralogical transformations can significantly influence the paleoclimatic application of their geochemical data. An innovative sampling and measurement protocol combined with scanning and transmission electron microscopy, X-ray diffraction and Fourier transform infrared spectroscopy is presented, demonstrating that carbonate precipitating from drip water in caves at ~10 °C contains amorphous calcium carbonate (ACC) that later transforms to nanocrystalline calcite. Stable oxygen isotope fractionations among calcite, ACC and water were also determined, proving that ACC is 18O-depleted (by >2.4 ± 0.8‰) relative to calcite. This, in turn, has serious consequences for speleothem-based fluid inclusion research as closed system transformation of ACC to calcite may induce a negative oxygen isotope shift in fluid inclusion water, resulting in deterioration of the original compositions. ACC formation increases the speleothems’ sensitivity to alteration as its interaction with external solutions may result in the partial loss of original proxy signals. Mineralogical analysis of freshly precipitating carbonate at the studied speleothem site is suggested in order to determine the potential influence of ACC formation. PMID:28004767

  18. 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

  19. A carbonate controlled-addition method for amorphous calcium carbonate spheres stabilized by poly(acrylic acid)s.

    PubMed

    Huang, Shu-Chen; Naka, Kensuke; Chujo, Yoshiki

    2007-11-20

    Stable amorphous calcium carbonate (ACC) composite particle with a size-controlled monodispersed sphere was obtained by a new simple carbonate controlled-addition method by using poly(acrylic acid) (PAA) (Mw = 5000), in which an aqueous ammonium carbonate solution was added into an aqueous solution of PAA and CaCl2 with a different time period. The obtained ACC composite products consist of about 50 wt % of ACC, 30 wt % of PAA, and H2O. Average particle sizes of the ACC spheres increased from (1.8 +/- 0.4) x 102 to (5.5 +/- 1.2) x 102 nm with an increase of the complexation time of the PAA-CaCl2 solution from 3 min to 24 h, respectively. The ACC formed from the complexation time for 3 min was stable for 10 days with gentle stirring as well as 3 months under a quiescent condition in the aqueous solution. Moreover, the ACC was also stable at 400 degrees C. Stability of the amorphous phase decreased with an increase of the complexation time of the PAA-CaCl2 solution. No ACC was obtained when the lower molar mass PAAs (Mw = 1200 and 2100) were used. In the higher molar mass case (Mw = 25 000), a mixture of the amorphous phase and vaterite and calcite crystalline product was produced. The present results demonstrate that the interaction and the reaction kinetics of the PAA-Ca2+-H2O complex play an important role in the mineralization of CaCO3.

  20. 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.

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

    PubMed

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

    2011-01-01

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

  2. Carboxylated molecules regulate magnesium content of amorphous calcium carbonates during calcification

    PubMed Central

    Wang, Dongbo; Wallace, Adam F.; De Yoreo, James J.; Dove, Patricia M.

    2009-01-01

    With the realization that many calcified skeletons form by processes involving a precursor phase of amorphous calcium carbonate (ACC), a new paradigm for mineralization is emerging. There is evidence the Mg content in biogenic ACC is regulated by carboxylated (acidic) proteins and other macromolecules, but the physical basis for such a process is unknown. We test the hypothesis that ACC compositions express a systematic relationship to the chemistry of carboxyl-rich biomolecules. A series of inorganic control experiments were conducted to establish the dependence of Mg/Ca ratios in ACC on solution composition. We then determined the influence of a suite of simple carboxylated organic acids on Mg content. Molecules with a strong affinity for binding Ca compared with Mg promote the formation of Mg-enriched ACC that is compositionally equivalent to high-magnesium calcites and dolomite. Measurements show Mg/Ca ratios are controlled by a predictable dependence upon the binding properties of the organic molecules. The trend appears rooted in the conformation and electrostatic potential topology of each molecule, but dynamic factors also may be involved. The dependence suggests a physical basis for reports that specific sequences of calcifying proteins are critical to modulating mineralization. Insights from this study may provide a plausible explanation for why some biogenic carbonates and carbonaceous cements often contain higher Mg signatures than those that are possible by classical crystal growth processes. The findings reiterate the controls of microenvironment on mineralization and suggest an origin of compositional offsets, or vital effects, long recognized by the paleoclimate community. PMID:19955417

  3. 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.

  4. Biogenic fish-gut calcium carbonate is a stable amorphous phase in the gilt-head seabream, Sparus aurata.

    PubMed

    Foran, Elizabeth; Weiner, Steve; Fine, Maoz

    2013-01-01

    The main source of calcium carbonate (CaCO₃) in the ocean comes from the shells of calcifying planktonic organisms, but substantial amounts of CaCO₃ are also produced in fish intestines. The precipitation of CaCO₃ assists fish in intestinal water absorption and aids in whole body Ca²⁺ homeostasis. Here we report that the product formed in the intestinal lumen of the gilt-head seabream, Sparus aurata, is an amorphous calcium carbonate (ACC) phase. With FTIR spectroscopy and SEM imaging, our study shows that the fish-derived carbonates from S. aurata are maintained as a stable amorphous phase throughout the intestinal tract. Moreover, intestinal deposits contained up to 54 mol% Mg²⁺, the highest concentration yet reported in biogenic ACC. Mg is most likely responsible for stabilizing this inherently unstable mineral. The fish carbonates also displayed initial rapid dissolution when exposed to seawater, exhibiting a significant increase in carbonate concentration.

  5. 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.

  6. Chemical and physical controls on the transformation of amorphous calcium carbonate into crystalline CaCO3 polymorphs

    NASA Astrophysics Data System (ADS)

    Blue, C. R.; Giuffre, A.; Mergelsberg, S.; Han, N.; De Yoreo, J. J.; Dove, P. M.

    2017-01-01

    Calcite and other crystalline polymorphs of CaCO3 can form by pathways involving amorphous calcium carbonate (ACC). Apparent inconsistencies in the literature indicate the relationships between ACC composition, local conditions, and the subsequent crystalline polymorphs are not yet established. This experimental study quantifies the control of solution composition on the transformation of ACC into crystalline polymorphs in the presence of magnesium. Using a mixed flow reactor to control solution chemistry, ACC was synthesized with variable Mg contents by tuning input pH, Mg/Ca, and total carbonate concentration. ACC products were allowed to transform within the output suspension under stirred or quiescent conditions while characterizing the evolving solutions and solids. As the ACC transforms into a crystalline phase, the solutions record a polymorph-specific evolution of pH and Mg/Ca. The data provide a quantitative framework for predicting the initial polymorph that forms from ACC based upon the solution aMg2+/aCa2+ and aCO32-/aCa2+ and stirring versus quiescent conditions. This model reconciles discrepancies among previous studies that report on the nature of the polymorphs produced from ACC and supports the previous claim that monohydrocalcite may be an important, but overlooked, transient phase on the way to forming some aragonite and calcite deposits. By this construct, organic additives and extreme pH are not required to tune the composition and nature of the polymorph that forms. Our measurements show that the Mg content of ACC is recorded in the resulting calcite with a ≈1:1 dependence. By correlating composition of these calcite products with the Mgtot/Catot of the initial solutions, we find a ≈3:1 dependence that is approximately linear and general to whether calcite is formed via an ACC pathway or by the classical step-propagation process. Comparisons to calcite grown in synthetic seawater show a ≈1:1 dependence. The relationships suggest that the

  7. 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".

  8. 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.

  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. Biomimetic mineralization of CaCO3 on a phospholipid monolayer: from an amorphous calcium carbonate precursor to calcite via vaterite.

    PubMed

    Xiao, Junwu; Wang, Zhining; Tang, Yecang; Yang, Shihe

    2010-04-06

    A phospholipid monolayer, approximately half the bilayer structure of a biological membrane, can be regarded as an ideal model for investigating biomineralization on biological membranes. In this work on the biomimetic mineralization of CaCO(3) under a phospholipid monolayer, we show the initial heterogeneous nucleation of amorphous calcium carbonate precursor (ACC) nanoparticles at the air-water interface, their subsequent transformation into the metastable vaterite phase instead of the most thermodynamically stable calcite phase, and the ultimate phase transformation to calcite. Furthermore, the spontaneity of the transformation from vaterite to calcite was found to be closely related to the surface tension; high surface pressure could inhibit the process, highlighting the determinant of surface energy. To understand better the mechanisms for ACC formation and the transformation from ACC to vaterite and to calcite, in situ Brewster angle microscopy (BAM), ex situ scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray diffraction analysis were employed. This work has clarified the crystallization process of calcium carbonate under phospholipid monolayers and therefore may further our understanding of the biomineralization processes induced by cellular membranes.

  11. Allotropic composition of amorphous carbon

    SciTech Connect

    Yastrebov, S. G. Ivanov-Omskii, V. I.

    2007-08-15

    Using the concept of an inhomogeneous broadening of spectral lines of the basic oscillators responsible for forming the spectrum, the experimental dependences of the dispersion of the imaginary part of permittivity are analyzed for amorphous carbon. It turned out that four types of oscillators contribute to this dependence. The first three types represent the electron transitions from the energy-spectrum ground state for {pi} and {sigma} electrons of amorphous carbon to an excited state. The fourth type is related to the absorption of electromagnetic radiation by free charge carriers. The absolute values of squared plasma frequencies of oscillators are estimated, and, using them, the relative fraction of sp{sup 2}-bonded atoms forming the amorphous-carbon skeleton is calculated. This estimate agrees closely with the theoretical predictions for amorphous carbon of the same density as the material under study. The dependence of the relative fraction of sp{sup 2}-bonded atoms contained in amorphous hydrogenised carbon on annealing temperature is determined. The developed method is also applied to the analysis of the normalized curve for the light extinction in the interstellar medium. The contribution to the extinction of two varieties of interstellar matter is detected.

  12. TRANSIENT AMORPHOUS CALCIUM PHOSPHATE IN FORMING ENAMEL

    PubMed Central

    Beniash, Elia; Metzler, Rebecca A.; Lam, Raymond S.K.; Gilbert, P.U.P.A.

    2009-01-01

    Enamel, the hardest tissue in the body, begins as a three-dimensional network of nanometer size mineral particles, suspended in a protein gel. This mineral network serves as a template for mature enamel formation. To further understand the mechanisms of enamel formation we characterized the forming enamel mineral at an early secretory stage using x-ray absorption near-edge structure (XANES) spectromicroscopy, transmission electron microscopy (TEM), FTIR microspectroscopy and polarized light microscopy. We show that the newly formed enamel mineral is amorphous calcium phosphate (ACP), which eventually transforms into apatitic crystals. Interestingly, the size, shape and spatial organization of these amorphous mineral particles and older crystals are essentially the same, indicating that the mineral morphology and organization in enamel is determined prior to its crystallization. Mineralization via transient amorphous phases has been previously reported in chiton teeth, mollusk shells, echinoderm spicules and spines, and recent reports strongly suggest the presence transient amorphous mineral in forming vertebrate bones. The present finding of transient ACP in murine tooth enamel suggests that this strategy might be universal. PMID:19217943

  13. 21 CFR 184.1191 - Calcium carbonate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... soda process”; (2) By precipitation of calcium carbonate from calcium hydroxide in the “Carbonation process”; or (3) By precipitation of calcium carbonate from calcium chloride in the “Calcium...

  14. 21 CFR 184.1191 - Calcium carbonate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... soda process”; (2) By precipitation of calcium carbonate from calcium hydroxide in the “Carbonation process”; or (3) By precipitation of calcium carbonate from calcium chloride in the “Calcium...

  15. 21 CFR 184.1191 - Calcium carbonate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... soda process”; (2) By precipitation of calcium carbonate from calcium hydroxide in the “Carbonation process”; or (3) By precipitation of calcium carbonate from calcium chloride in the “Calcium...

  16. 21 CFR 184.1191 - Calcium carbonate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... soda process”; (2) By precipitation of calcium carbonate from calcium hydroxide in the “Carbonation process”; or (3) By precipitation of calcium carbonate from calcium chloride in the “Calcium...

  17. High resolution electron microscopy study of amorphous calcium phosphate

    NASA Astrophysics Data System (ADS)

    Brès, E. F.; Moebus, G.; Kleebe, H.-J.; Pourroy, G.; Werkmann, J.; Ehret, G.

    1993-03-01

    "Amorphous" calcium phosphate (ACP) from human tooth enamel and different synthetic materials has been analysed by high resolution electron microscopy (HREM). All the materials studied showed, in addition to a "truly" amorphous phase, other calcium phosphate phases such as poorly crystalline hydroxyapatite (OHAP), well crystallized OHAP and poorly crystalline CaO type phase. Such structural heterogeneities have not been observed before in ACP, and are only possible to be detected by HREM as this is the only technique able to analyse nanometre size materials in the real space.

  18. 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.

  19. Calcium carbonate phase transformations during the carbonation reaction of calcium heavy alkylbenzene sulfonate overbased nanodetergents preparation.

    PubMed

    Chen, Zhaocong; Xiao, Shan; Chen, Feng; Chen, Dongzhong; Fang, Jianglin; Zhao, Min

    2011-07-01

    The preparation and application of overbased nanodetergents with excess alkaline calcium carbonate is a good example of nanotechnology in practice. The phase transformation of calcium carbonate is of extensive concern since CaCO(3) serves both as an important industrial filling material and as the most abundant biomineral in nature. Industrially valuable overbased nanodetergents have been prepared based on calcium salts of heavy alkylbenzene sulfonate by a one-step process under ambient pressure, the carbonation reaction has been monitored by the instantaneous temperature changes and total base number (TBN). A number of analytical techniques such as TGA, DLS, SLS, TEM, FTIR, and XRD have been utilized to explore the carbonation reaction process and phase transformation mechanism of calcium carbonate. An enhanced understanding on the phase transformation of calcium carbonate involved in calcium sulfonate nanodetergents has been achieved and it has been unambiguously demonstrated that amorphous calcium carbonate (ACC) transforms into the vaterite polymorph rather than calcite, which would be of crucial importance for the preparation and quality control of lubricant additives and greases. Our results also show that a certain amount of residual Ca(OH)(2) prevents the phase transformation from ACC to crystalline polymorphs. Moreover, a vaterite nanodetergent has been prepared for the first time with low viscosity, high base number, and uniform particle size, nevertheless a notable improvement on its thermal stability is required for potential applications.

  20. 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.

  1. Structural modeling of amorphous conducting carbon film

    NASA Astrophysics Data System (ADS)

    Bhattacharyya, Somnath; Pati, Swapan K.; Subramanyam, S. V.

    1998-04-01

    Amorphous conducting carbon films are prepared using plasma assisted polymerization process. SEM and TEM shows random aggregate of globular clusters of micron size inside the samples. Electrical measurements indicate a near metallic nature. A tendency of saturation of resistivity at low temperature is observed. From spectroscopic analysis we find some unusual features. Based on these observations a structural model of this carbon is proposed.

  2. 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.

  3. Atomic structure of intracellular amorphous calcium phosphate deposits.

    PubMed

    Betts, F; Blumenthal, N C; Posner, A S; Becker, G L; Lehninger, A L

    1975-06-01

    The radial distribution function calculated from x-ray diffraction of mineralized cytoplasmic structures isolated from the hepatopancreas of the blue crab (Callinectes sapidus) is very similar to that previously found for synthetic amorphous calcium phosphate. Both types of mineral apparently have only short-range atomic order, represented as a neutral ion cluster of about 10 A in longest dimension, whose probable composition is expressed by the formula Ca9(PO4)6. The minor differences observed are attributed to the presence in the biological mineral of significant amounts of Mg-2+ and ATP. Synthetic amorphous calcium phosphate in contact with a solution containing an amount of ATP equivalent to that of the biological mineral failed to undergo conversion to the thermodynamically more stable hydroxyapatite. The amorphous calcium phosphate of the cytoplasmic mineral granules is similarly stable, and does not undergo conversion to hydroxyapatite, presumably owing to the presence of ATP and Mg-2+, known in inhibitors of the conversion process. The physiological implications of mineral deposits consisting of stabilized calcium phosphate ion clusters are discussed.

  4. Thermally induced evolution of hydrogenated amorphous carbon

    NASA Astrophysics Data System (ADS)

    Mangolini, Filippo; Rose, Franck; Hilbert, James; Carpick, Robert W.

    2013-10-01

    The thermally induced structural evolution of hydrogenated amorphous carbon (a-C:H) films was investigated in situ by X-ray photoelectron spectroscopy for annealing temperatures up to 500 °C. A model for the conversion of sp3- to sp2-hybridized carbon in a-C:H vs. temperature and time was developed and applied to determine the ranges of activation energies for the thermally activated processes occurring. The energies are consistent with ordering and clustering of sp2 carbon, scission of sp3 carbon-hydrogen bonds and formation of sp2 carbon, and direct transformation of sp3- to sp2-hybridized carbon.

  5. Continuous synthesis of amorphous carbonated apatites.

    PubMed

    Tadic, D; Peters, F; Epple, M

    2002-06-01

    Amorphous carbonated hydroxyapatite was prepared by rapid mixing of aqueous solutions of a continuous computer-controlled reactor. The variation of the carbonate content in the solid product is possible by adjustment of the ratios of phosphate to carbonate in the initial solution. The principal reaction parameters (temperature, pH, stirrer speed, solution composition and supersaturation) are controlled and monitored. By controlling these processing parameters, a non-stoichiometric hydroxyapatite with fine-tuned crystallinity, morphology, and carbonate content can be reproducibly prepared. The higher solubility under the conditions of osteoclastic resorption was tested in vitro at constant pH (4.4).

  6. Amorphous silica-like carbon dioxide

    NASA Astrophysics Data System (ADS)

    Santoro, Mario; Gorelli, Federico A.; Bini, Roberto; Ruocco, Giancarlo; Scandolo, Sandro; Crichton, Wilson A.

    2006-06-01

    Among the group IV elements, only carbon forms stable double bonds with oxygen at ambient conditions. At variance with silica and germania, the non-molecular single-bonded crystalline form of carbon dioxide, phase V, only exists at high pressure. The amorphous forms of silica (a-SiO2) and germania (a-GeO2) are well known at ambient conditions; however, the amorphous, non-molecular form of CO2 has so far been described only as a result of first-principles simulations. Here we report the synthesis of an amorphous, silica-like form of carbon dioxide, a-CO2, which we call `a-carbonia'. The compression of the molecular phase III of CO2 between 40 and 48GPa at room temperature initiated the transformation to the non-molecular amorphous phase. Infrared spectra measured at temperatures up to 680K show the progressive formation of C-O single bonds and the simultaneous disappearance of all molecular signatures. Furthermore, state-of-the-art Raman and synchrotron X-ray diffraction measurements on temperature-quenched samples confirm the amorphous character of the material. Comparison with vibrational and diffraction data for a-SiO2 and a-GeO2, as well as with the structure factor calculated for the a-CO2 sample obtained by first-principles molecular dynamics, shows that a-CO2 is structurally homologous to the other group IV dioxide glasses. We therefore conclude that the class of archetypal network-forming disordered systems, including a-SiO2, a-GeO2 and water, must be extended to include a-CO2.

  7. Calcium phosphate scaffold from biogenic calcium carbonate by fast ambient condition reactions

    NASA Astrophysics Data System (ADS)

    Dutta, Abhishek; Fermani, Simona; Arjun Tekalur, Srinivasan; Vanderberg, Abigail; Falini, Giuseppe

    2011-12-01

    Calcium phosphate biogenic materials are biocompatible and promote bioactivity and osteoconductivity, which implies their natural affinity and tendency to bond directly to bones subsequently replacing the host bone after implantation owing to its biodegradability. Calcium hydrogen phosphate dihydrate, CaHPO 4·2H 2O, is known to be a nucleation precursor, in aqueous solutions, for apatitic calcium phosphates and, hence, a potential starting material for bone substitutes. Numerous approaches, via hydrothermal and ambient synthetic routes, have been used to produce calcium phosphate from biogenic calcium carbonate, taking advantage of the peculiar architecture and composition of the latter. In this article, the lamellar region of the cuttlefish bone ( Sepia officinalis) was used as a framework for the organized deposition of calcium phosphate crystals, at ambient conditions via a fast procedure involving an amorphous calcium carbonate intermediate, and ending with a conversion to calcium phosphate and a fixation procedure, thereby resulting in direct conversion of biogenic calcium carbonate into calcium phosphates at ambient conditions from the scale of months to hours.

  8. 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.

  9. Amorphous calcium phosphate and its application in dentistry.

    PubMed

    Zhao, Jie; Liu, Yu; Sun, Wei-Bin; Zhang, Hai

    2011-07-08

    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.

  10. 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)

  11. Extracting Crystal Chemistry from Amorphous Carbon Structures.

    PubMed

    Deringer, Volker L; Csányi, Gábor; Proserpio, Davide M

    2017-03-08

    Carbon allotropes have been explored intensively by ab initio crystal structure prediction, but such methods are limited by the large computational cost of the underlying density functional theory (DFT). Here we show that a novel class of machine-learning-based interatomic potentials can be used for random structure searching and readily predicts several hitherto unknown carbon allotropes. Remarkably, our model draws structural information from liquid and amorphous carbon exclusively, and so does not have any prior knowledge of crystalline phases: it therefore demonstrates true transferability, which is a crucial prerequisite for applications in chemistry. The method is orders of magnitude faster than DFT and can, in principle, be coupled with any algorithm for structure prediction. Machine-learning models therefore seem promising to enable large-scale structure searches in the future.

  12. 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...

  13. Chemical elimination of amorphous carbon on amorphous carbon nanotubes and its electrochemical performance

    NASA Astrophysics Data System (ADS)

    He, Xiaojun; Jiang, Li; Fan, Chuangang; Lei, Jiangwei; Zheng, Mingdong

    2007-04-01

    Chemical elimination of amorphous carbon on amorphous carbon nanotubes (ACNTs) was for the first time investigated by different treatment processes. Electrochemical performance of the modified ACNTs/carbon paste electrode (ACNTs/CPE) was measured by cyclic voltammetry. Field emission scanning and transmission electron microscope (STEM) observation reveals that the diameter of ACNTs is in the range of 60-100 nm. The amorphous nature of ACNTs was proved by the result of Raman analysis. FT-IR spectra showed that it might be one of the low-cost ways to eliminate amorphous carbon on the surface of ACNTs to treat ACNTs with HNO 3 in microwave oven. Further oxidation in air would lead to the decrease of electron transfer rate on the ACNTs/CPE because OH groups on the wall of ACNTs were partly eliminated by oxidation in air. The results of cyclic voltammetry showed that ACNTs/CPE treated with HNO 3 in microwave oven has optimal peak in relation to the highest redox peak current.

  14. 21 CFR 73.1070 - Calcium carbonate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 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 of... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Calcium carbonate. 73.1070 Section 73.1070...

  15. 21 CFR 73.1070 - Calcium carbonate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 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 of... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Calcium carbonate. 73.1070 Section 73.1070...

  16. 21 CFR 73.1070 - Calcium carbonate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 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 of... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Calcium carbonate. 73.1070 Section 73.1070...

  17. 21 CFR 73.1070 - Calcium carbonate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 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 of... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Calcium carbonate. 73.1070 Section 73.1070...

  18. 21 CFR 73.1070 - Calcium carbonate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 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 of... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Calcium carbonate. 73.1070 Section 73.1070...

  19. 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.

  20. Gold nanoparticles promote amorphous carbon to be ammonia gas sensor

    NASA Astrophysics Data System (ADS)

    Hsu, Hua-Shu; Ju, Shin-Pon; Sun, Shih-Jye; Chou, Hsiung; Chia, C. H.

    2016-05-01

    As gold-nanoparticles-embedded in amorphous carbon films the sp 3 carbon orbits near the interface will be partially transferred to sp 2. The Raman spectrum measurements as well as the molecular-dynamics simulations used the second reactive empirical bond order (REBO) potential simulating the interatomic force between carbon atoms both confirm the orbital transformations. The amorphous carbon films are initially inert to gases, while the films embedded with gold nanoparticles exhibit the increase of resistance in ammonia atmosphere. Namely, gold-nanoparticles-embedded amorphous carbon films become the candidate for ammonia gas sensor materials.

  1. 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.

  2. Nanocomposite containing amorphous calcium phosphate nanoparticles for caries inhibition

    PubMed Central

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

    2011-01-01

    Objectives The main challenges facing composite restorations are secondary caries and bulk fracture. The objectives of this study were to synthesize novel nanoparticles of amorphous calcium phosphate (NACP), develop NACP nanocomposite with calcium (Ca) and phosphate (PO4) ion release to combat caries, and investigate the effects of NACP filler level and glass co-filler reinforcement on composite properties. Methods NACP (diameter = 116 nm) were synthesized via a spray-drying technique for the first time. Since the local plaque pH in the oral cavity can decrease to 5 or 4, photo-activated composites were tested with immersion in solutions of pH 7, 5.5, and 4. Composite mechanical properties as well as Ca and PO4 ion release were measured vs. pH and filler level. Results Increasing the NACP filler level increased the ion release. At 28 d and pH 4, the Ca release was (4.66 ± 0.05) mmol/L at 20% NACP, much higher than (0.33 ± 0.08) at 10% NACP (p < 0.05). Decreasing the pH increased the ion release. At 20% NACP, the PO4 release at 28 d was (1.84 ± 0.12) mmol/L at pH 4, higher than (0.59 ± 0.08) at pH 5.5, and (0.12 ± 0.01) at pH 7 (p < 0.05). However, pH had little effect on composite mechanical properties. Flexural strength at 15% NACP was (96 ± 13) MPa at pH 4, similar to (89 ± 13) MPa at pH 5.5, and (89 ± 19) MPa at pH 7 (p > 0.1). The new NACP nanocomposites had strengths that were 2-fold those of previous calcium phosphate composites and resin-modified glass ionomer control. Significance NACP composites were developed for the first time. Their strengths matched or exceeded a commercial composite with little ion release, and were 2-fold those of previous Ca-PO4 composites. The nanocomposite was “smart” as it greatly increased the ion release at a cariogenic pH 4, when these ions would be most needed to inhibit caries. Hence, the new NACP composite may be promising for stress-bearing and caries-inhibiting restorations. PMID:21514655

  3. 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.

  4. Unveiling descriptors for predicting the bulk modulus of amorphous carbon

    NASA Astrophysics Data System (ADS)

    Takahashi, Keisuke; Tanaka, Yuzuru

    2017-02-01

    Descriptors for the bulk modulus of amorphous carbon are investigated through the implementation of data mining where data sets are prepared using first-principles calculations. Data mining reveals that the number of bonds in each C atom and the density of amorphous carbon are found to be descriptors representing the bulk modulus. Support vector regression (SVR) within machine learning is implemented and descriptors are trained where trained SVR is able to predict the bulk modulus of amorphous carbon. An inverse problem, starting from the bulk modulus towards structural information of amorphous carbon, is performed and structural information of amorphous carbon is successfully predicted from the desired bulk modulus. Thus, treating several physics factors in multidimensional space allows for the prediction of physical phenomena. In addition, the reported approach proposes that "big data" can be generated from a small data set using machine learning if descriptors are well defined. This would greatly change how amorphous carbon would be treated and help accelerate further development of amorphous carbon materials.

  5. 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

  6. Preparation, characterization and in vivo evaluation of amorphous atorvastatin calcium nanoparticles using supercritical antisolvent (SAS) process.

    PubMed

    Kim, Min-Soo; Jin, Shun-Ji; Kim, Jeong-Soo; Park, Hee Jun; Song, Ha-Seung; Neubert, Reinhard H H; Hwang, Sung-Joo

    2008-06-01

    In this work, amorphous atorvastatin calcium nanoparticles were successfully prepared using the supercritical antisolvent (SAS) process. The effect of process variables on particle size and distribution of atorvastatin calcium during particle formation was investigated. Solid state characterization, solubility, intrinsic dissolution, powder dissolution studies and pharmacokinetic study in rats were performed. Spherical particles with mean particle size ranging between 152 and 863 nm were obtained by varying process parameters such as precipitation vessel pressure and temperature, drug solution concentration and feed rate ratio of CO2/drug solution. XRD, TGA, FT-IR, FT-Raman, NMR and HPLC analysis indicated that atorvastatin calcium existed as anhydrous amorphous form and no degradation occurred after SAS process. When compared with crystalline form (unprocessed drug), amorphous atorvastatin calcium nanoparticles were of better performance in solubility and intrinsic dissolution rate, resulting in higher solubility and faster dissolution rate. In addition, intrinsic dissolution rate showed a good correlation with the solubility. The dissolution rates of amorphous atorvastatin calcium nanoparticles were highly increased in comparison with unprocessed drug by the enhancement of intrinsic dissolution rate and the reduction of particle size resulting in an increased specific surface area. The absorption of atorvastatin calcium after oral administration of amorphous atorvastatin calcium nanoparticles to rats was markedly increased.

  7. Novel low Wigner energy amorphous carbon-carbon composite

    NASA Astrophysics Data System (ADS)

    Dasgupta, Kinshuk; Prakash, Jyoti; Tripathi, B. M.

    2014-02-01

    A novel amorphous carbon-carbon composite has been developed using carbon black dispersed in carbonized phenolic resin matrix in order to avoid Wigner energy problem associated with graphite. The as prepared sample showed a density of 1320 kg m-3. This has been further densified by resin impregnation and chemical vapour infiltration. The effect of processing parameters on final density (1517 kg m-3) has been investigated. This composite possesses the compressive strength of 65 Mpa, coefficient of thermal expansion of 3 × 10-6 K-1 and the specific heat of 1.2 J g-1 K-1. This novel composite was subjected to 145 MeV Ne+6 heavy ion irradiation at different doses. The highest dose was kept at 3 × 10-4 dpa. The stored energy in the composite was found to be 212 J g-1 at the highest dose of irradiation, which is much below than that of graphite. The composite remained amorphous after irradiation as confirmed by X-ray diffraction.

  8. Induced calcium carbonate precipitation using Bacillus species.

    PubMed

    Seifan, Mostafa; Samani, Ali Khajeh; Berenjian, Aydin

    2016-12-01

    Microbially induced calcium carbonate precipitation is an emerging process for the production of self-healing concrete. This study was aimed to investigate the effects and optimum conditions on calcium carbonate biosynthesis. Bacillus licheniformis, Bacillus sphaericus, yeast extract, urea, calcium chloride and aeration were found to be the most significant factors affecting the biomineralization of calcium carbonate. It was noticed that the morphology of microbial calcium carbonate was mainly affected by the genera of bacteria (cell surface properties), the viscosity of the media and the type of electron acceptors (Ca(2+)). The maximum calcium carbonate concentration of 33.78 g/L was achieved at the optimum conditions This value is the highest concentration reported in the literature.

  9. 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

  10. Solid state characterization of commercial crystalline and amorphous atorvastatin calcium samples.

    PubMed

    Shete, Ganesh; Puri, Vibha; Kumar, Lokesh; Bansal, Arvind K

    2010-06-01

    Atorvastatin calcium (ATC), an anti-lipid BCS class II drug, is marketed in crystalline and amorphous solid forms. The objective of this study was to perform solid state characterization of commercial crystalline and amorphous ATC drug samples available in the Indian market. Six samples each of crystalline and amorphous ATC were characterized using X-ray powder diffractometry (XRPD), differential scanning calorimetry (DSC), thermogravimetric analysis, Karl Fisher titrimetry, microscopy (hot stage microscopy, scanning electron microscopy), contact angle, and intrinsic dissolution rate (IDR). All crystalline ATC samples were found to be stable form I, however one sample possessed polymorphic impurity, evidenced in XRPD and DSC analysis. Amongst the amorphous ATC samples, XRPD demonstrated five samples to be amorphous 'form 27', while, one matched amorphous 'form 23'. Thermal behavior of amorphous ATC samples was compared to amorphous ATC generated by melt quenching in DSC. ATC was found to be an excellent glass former with T(g)/T(m) of 0.95. Residual crystallinity was detected in two of the amorphous samples by complementary use of conventional and modulated DSC techniques. The wettability and IDR of all amorphous samples was found to be higher than the crystalline samples. In conclusion, commercial ATC samples exhibited diverse solid state behavior that can impact the performance and stability of the dosage forms.

  11. 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.

  12. Carbonated calcium phosphates are suitable pH-stabilising fillers for biodegradable polyesters.

    PubMed

    Schiller, Carsten; Epple, Matthias

    2003-05-01

    Carbonated amorphous calcium phosphates were prepared with different carbonate content. Their ability to neutralise acidity was probed by time-resolved titration experiments with lactic acid, the monomer that results from degradation of polylactide. The results show that although calcium phosphate as such can reduce acidity, their buffering range lies at a pH of about 4, i.e. outside the physiological range. This is not related to the rate of dissolution. Carbonated calcium phosphates as well as calcium carbonate (calcite) alone are able to keep the pH around 7.4. Consequently, carbonated calcium phosphates are suitable basic filler materials as they are able to compensate acidity, and to buffer within the physiological pH-range.

  13. 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.

  14. 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

  15. 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

  16. Elemental calcium intake associated with calcium acetate/calcium carbonate in the treatment of hyperphosphatemia

    PubMed Central

    Wilson, Rosamund J; Copley, J Brian

    2017-01-01

    Background Calcium-based and non-calcium-based phosphate binders have similar efficacy in the treatment of hyperphosphatemia; however, calcium-based binders may be associated with hypercalcemia, vascular calcification, and adynamic bone disease. Scope A post hoc analysis was carried out of data from a 16-week, Phase IV study of patients with end-stage renal disease (ESRD) who switched to lanthanum carbonate monotherapy from baseline calcium acetate/calcium carbonate monotherapy. Of the intent-to-treat population (N=2520), 752 patients with recorded dose data for calcium acetate (n=551)/calcium carbonate (n=201) at baseline and lanthanum carbonate at week 16 were studied. Elemental calcium intake, serum phosphate, corrected serum calcium, and serum intact parathyroid hormone levels were analyzed. Findings Of the 551 patients with calcium acetate dose data, 271 (49.2%) had an elemental calcium intake of at least 1.5 g/day at baseline, and 142 (25.8%) had an intake of at least 2.0 g/day. Mean (95% confidence interval [CI]) serum phosphate levels were 6.1 (5.89, 6.21) mg/dL at baseline and 6.2 (6.04, 6.38) mg/dL at 16 weeks; mean (95% CI) corrected serum calcium levels were 9.3 (9.16, 9.44) mg/dL and 9.2 (9.06, 9.34) mg/dL, respectively. Of the 201 patients with calcium carbonate dose data, 117 (58.2%) had an elemental calcium intake of at least 1.5 g/day, and 76 (37.8%) had an intake of at least 2.0 g/day. Mean (95% CI) serum phosphate levels were 5.8 (5.52, 6.06) mg/dL at baseline and 5.8 (5.53, 6.05) mg/dL at week 16; mean (95% CI) corrected serum calcium levels were 9.7 (9.15, 10.25) mg/dL and 9.2 (9.06, 9.34) mg/dL, respectively. Conclusion Calcium acetate/calcium carbonate phosphate binders, taken to control serum phosphate levels, may result in high levels of elemental calcium intake. This may lead to complications related to calcium balance. PMID:28182142

  17. Thermally reduced graphenes exhibiting a close relationship to amorphous carbon

    NASA Astrophysics Data System (ADS)

    An Wong, Colin Hong; Ambrosi, Adriano; Pumera, Martin

    2012-07-01

    Graphene is an important material for sensing and energy storage applications. Since the vast majority of sensing and energy storage chemical and electrochemical systems require bulk quantities of graphene, thermally reduced graphene oxide (TRGO) is commonly employed instead of pristine graphene. The sp2 planar structure of TRGO is heavily damaged, consisting of a very short sp2 crystallite size of nanometre length and with areas of sp3 hybridized carbon. Such a structure of TRGO is reminiscent of the key characteristic of the structure of amorphous carbon, which is defined as a material without long-range crystalline order consisting of both sp2 and sp3 hybridized carbons. Herein, we describe the characterization of TRGO, its parent graphite material and carbon black (a form of amorphous carbon) via transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry experiments. We used the data obtained as well as consideration of practical factors to perform a comparative assessment of the relative electrochemical performances of TRGO against amorphous carbon. We found out that TRGO and amorphous carbon exhibit almost identical characteristics in terms of density of defects in the sp2 lattice and a similar crystallite size as determined by Raman spectroscopy. These two materials also exhibit similar amounts of oxygen containing groups as determined by XPS and nearly indistinguishable cyclic voltammetric response providing almost identical heterogeneous electron transfer constants. This leads us to conclude that for some sensing and energy storage electrochemical applications, the use of amorphous carbon might be a much more economical solution than the one requiring digestion of highly crystalline graphite with strong oxidants to graphite oxide and then thermally exfoliating it to thermally reduced graphene oxide.

  18. Transformation of Amorphous Calcium Phosphate to Crystalline Dahllite in the Radular Teeth of Chitons

    NASA Astrophysics Data System (ADS)

    Lowenstam, H. A.; Weiner, S.

    1985-01-01

    A comparison of infrared spectra from individual teeth along the radula of a chiton (Polyplacophora, Mollusca) shows that the first-formed calcium phosphate mineral is amorphous. Over a period of weeks the mineral transforms to dahllite. The c axes of the dahllite crystals are aligned approximately perpendicular to the tooth surface.

  19. 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

  20. 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.

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

    PubMed

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

    2014-01-13

    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.

  2. Machine learning based interatomic potential for amorphous carbon

    NASA Astrophysics Data System (ADS)

    Deringer, Volker L.; Csányi, Gábor

    2017-03-01

    We introduce a Gaussian approximation potential (GAP) for atomistic simulations of liquid and amorphous elemental carbon. Based on a machine learning representation of the density-functional theory (DFT) potential-energy surface, such interatomic potentials enable materials simulations with close-to DFT accuracy but at much lower computational cost. We first determine the maximum accuracy that any finite-range potential can achieve in carbon structures; then, using a hierarchical set of two-, three-, and many-body structural descriptors, we construct a GAP model that can indeed reach the target accuracy. The potential yields accurate energetic and structural properties over a wide range of densities; it also correctly captures the structure of the liquid phases, at variance with a state-of-the-art empirical potential. Exemplary applications of the GAP model to surfaces of "diamondlike" tetrahedral amorphous carbon (ta -C) are presented, including an estimate of the amorphous material's surface energy and simulations of high-temperature surface reconstructions ("graphitization"). The presented interatomic potential appears to be promising for realistic and accurate simulations of nanoscale amorphous carbon structures.

  3. Deposition of superhard amorphous carbon films by pulsed arc sources

    SciTech Connect

    Scheibe, H.J.; Schultrich, B.; Ziegele, H.; Siemroth, P.

    1996-12-31

    Hydrogen-free amorphous carbon films with hardness comparable to crystalline superhard materials have been deposited by special Pulsed arc techniques. By the combination of very high hardness, low adhesion and high smoothness, these films show superior behaviour in wear and glide applications. The influence of plasma and deposition conditions on these film properties and the choice of optimum conditions are discussed.

  4. Hard, amorphous carbon deposited from a fullerene discharge

    SciTech Connect

    Maiken, E.B.; Taborek, P.

    1995-12-31

    Hard, amorphous carbon films were deposited from an ion source using fullerite as carbon feedstock. For fixed ion energies, the film resistivities decreased exponentially with substrate temperature, suggesting activated growth of a conductive phase. Resistivity at 300 K ranged from 10{sup -3} to 10{sup 4} {Omega}m. E{sub -4} optical gaps of conductive films ranged from 0.1 to 1.1 eV.

  5. Constraints on Biogenic Emplacement of Crystalline Calcium Carbonate and Dolomite

    NASA Astrophysics Data System (ADS)

    Colas, B.; Clark, S. M.; Jacob, D. E.

    2015-12-01

    Amorphous calcium carbonate (ACC) is a biogenic precursor of calcium carbonates forming shells and skeletons of marine organisms, which are key components of the whole marine environment. Understanding carbonate formation is an essential prerequisite to quantify the effect climate change and pollution have on marine population. Water is a critical component of the structure of ACC and the key component controlling the stability of the amorphous state. Addition of small amounts of magnesium (1-5% of the calcium content) is known to promote the stability of ACC presumably through stabilization of the hydrogen bonding network. Understanding the hydrogen bonding network in ACC is fundamental to understand the stability of ACC. Our approach is to use Monte-Carlo simulations constrained by X-ray and neutron scattering data to determine hydrogen bonding networks in ACC as a function of magnesium doping. We have already successfully developed a synthesis protocol to make ACC, and have collected X-ray data, which is suitable for determining Ca, Mg and O correlations, and have collected neutron data, which gives information on the hydrogen/deuterium (as the interaction of X-rays with hydrogen is too low for us to be able to constrain hydrogen atom positions with only X-rays). The X-ray and neutron data are used to constrain reverse Monte-Carlo modelling of the ACC structure using the Empirical Potential Structure Refinement program, in order to yield a complete structural model for ACC including water molecule positions. We will present details of our sample synthesis and characterization methods, X-ray and neutron scattering data, and reverse Monte-Carlo simulations results, together with a discussion of the role of hydrogen bonding in ACC stability.

  6. Amorphous diamond: a high-pressure superhard carbon allotrope.

    PubMed

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

    2011-10-21

    Compressing glassy carbon above 40 GPa, we have observed a new carbon allotrope with a fully sp(3)-bonded amorphous structure and diamondlike strength. Synchrotron x-ray Raman spectroscopy revealed a continuous pressure-induced sp(2)-to-sp(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.

  7. 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.

  8. 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}}.

  9. Microwave Switching in Amorphous-Carbon Quantum Wells

    NASA Astrophysics Data System (ADS)

    Bhattacharyya, Somnath; Gomez Rojas, Luis; Silva, S. Ravi. P.

    2007-03-01

    Demonstration of long phase coherence length showing resonant tunnelling and fast switching in amorphous carbon quantum well structures has recently been established [1]. Here we show a bias controlled reversible switching of the complex impedance by transmitting a microwave signal up to 110GHz through amorphous carbon resonant tunnel diodes. By employing a coplanar waveguide technique and through the analysis of the return loss (S11) microwave enhanced mobility greater than 30cm^2(Vs)-1 in the delocalized regime of (filamentary) conduction in these devices is demonstrated. Also a switching behaviour at about 85GHz can also be observed. We suggest a new model for the microscopic origin of the increased mobility and show routes to achieve longer coherence lengths. In addition microwave conductance of carbon quantum wells parallel to their plane and across a channel length larger than 100 nm determines the momentum scattering time of electrons in carbon. These results exhibit a potential for pure amorphous carbon-based fast memory devices. [1] S. Bhattacharyya, S.J. Henley, E. Mendoza, L. Gomez Rojas, J. Allam and S.R.P. Silva, Nature Mater. 5, 19 (2006).

  10. 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.

  11. A template route to the preparation of mesoporous amorphous calcium silicate with high in vitro bone-forming bioactivity.

    PubMed

    Li, Xia; Shi, Jianlin; Zhu, Yufang; Shen, Weihua; Li, Hua; Liang, Jian; Gao, Jianhua

    2007-11-01

    The mesoporous amorphous calcium silicate (MACS) was first synthesized using mesoporous silica SBA-15 as both the template and silicon source, and Ca(NO(3))(2) as the calcium source. The MACS shows a well-defined mesoporous structure with high specific surface area. In vitro bioactivity studies of the MACS were carried out by soaking it in simulated body fluid (SBF) solutions for 4 h up to 5 days. Owing to the high specific surface area and pore volume, the MACS had a significantly enhanced bone-forming bioactivity compared with the conventional amorphous CaSiO(3). The MACS did develop a carbonate-containing hydroxyapatite (HCA) layer on the surface after being immersed in SBF for 4 h with near-spherical agglomerated hydroxyapatite (HA) nanoparticles. At longer soaking times, the number of agglomerated HA particles increased and the surface structure of the samples became more compact. Such MACS could be useful in developing new biomaterials and may have potential use in implanting and drug delivery for tissue regeneration.

  12. 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...

  13. 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...

  14. 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...

  15. 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...

  16. 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...

  17. Raman spectra of amorphous carbon films deposited by SWP

    NASA Astrophysics Data System (ADS)

    Xu, Junqi; Liu, Weiguo; Hang, Lingxia; Su, Junhong; Fan, Huiqing

    2010-10-01

    Amorphous carbon film is one of the most important anti-reflection protective films coated on infrared optical components. In this paper, hydrogen-free amorphous carbon films were deposited by new type surface-wave-sustained plasma (SWP) source with a graphite target at various experiment parameters. The laser Raman spectroscopy at wavelength of 514 nm was used to investigate the structure and bonding of these carbon films. The results showed consanguineous correlations between the intensity ratio ID/IG and the experiment parameters such as microwave power, target voltage and gas pressure applied to the SWP source. Raman spectra proved the structure of these carbon films prepared by SWP technique is typical diamond-like carbon (DLC). The analysis on G peak position and intensity ratio ID/IG indicated that Raman shifts moves to low wavenumber and ID/IG decreases with the increasing of microwave power from 150 W to 330 W. These results means the formation of sp3 bond prefers higher microwave power. DLC films prepared at target voltage of -200 V have higher sp3 content than that of -350 V, moreover, an increase of gas pressure during experiments yields higher sp3 content at the microwave power below 270 W, whereas the change of sp3 content is slight with the various conditions when microwave power exceeds 270 W.

  18. 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.

  19. 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.

  20. Nonenzymatic Transformation of Amorphous CaCO3 into Calcium Phosphate Mineral after Exposure to Sodium Phosphate in Vitro: Implications for in Vivo Hydroxyapatite Bone Formation.

    PubMed

    Müller, Werner E G; Neufurth, Meik; Huang, Jian; Wang, Kui; Feng, Qingling; Schröder, Heinz C; Diehl-Seifert, Bärbel; Muñoz-Espí, Rafael; Wang, Xiaohong

    2015-06-15

    Studies indicate that mammalian bone formation is initiated at calcium carbonate bioseeds, a process that is driven enzymatically by carbonic anhydrase (CA). We show that amorphous calcium carbonate (ACC) and bicarbonate (HCO3 (-) ) cause induction of expression of the CA in human osteogenic SaOS-2 cells. The mineral deposits formed on the surface of the cells are rich in C, Ca and P. FTIR analysis revealed that ACC, vaterite, and aragonite, after exposure to phosphate, undergo transformation into calcium phosphate. This exchange was not seen for calcite. The changes to ACC, vaterite, and aragonite depended on the concentration of phosphate. The rate of incorporation of phosphate into ACC, vaterite, and aragonite, is significantly accelerated in the presence of a peptide rich in aspartic acid and glutamic acid. We propose that the initial CaCO3 bioseed formation is driven by CA, and that the subsequent conversion to calcium phosphate/calcium hydroxyapatite (exchange of carbonate by phosphate) is a non-enzymatic exchange process.

  1. The formation and transformation mechanism of calcium carbonate in water

    SciTech Connect

    Ogino, Takeshi; Suzuki, Toshio; Sawada, Kiyoshi )

    1987-10-01

    High supersaturated solutions of Ca{sup 2+} and CO{sub 3}{sup 2{minus}} ions rapidly precipitate amorphous calcium carbonate, ACC, the logarithmic thermodynamic solubility product of which is about {minus}6.0 at 25{degree}C. The ACC initially formed is transformed to a mixture of several crystalline calcium carbonate polymorphs within several minutes. The transformed polymorphs are vaterite and calcite at low temperature (14 to 30{degree}C), and aragonite and calcite at high temperature (60 to 80{degree}C). At intermediate temperatures (40 to 50{degree}C) the formation of all three polymorphs was observed. Metastable polymorphs are gradually transformed to the stable form, calcite. It takes about 200 min at 25{degree}C and 370 min at 30{degree}C for the complete transformation of vaterite to calcite, and 100-1300 min for that of aragonite to calcite at 60-80{degree}C. At 50{degree}C, vaterite is predominantly transformed at first to aragonite within 60 min, and then the aragonite is transformed to calcite in about 900 min. The results of the change in the ion activity product of the solution and the abundances of the polymorphs strongly suggest that the polymorphic transformation of vaterite and aragonite to calcite takes place through dissolution of the metastable phase and growth of the stable phase, calcite. The rate-determining step of the transformation is the growth of calcite. The relative abundance of vaterite becomes higher at 25{degree}C with increasing concentrations of calcium and carbonate ions in the supersaturated solution. When the ion activity product of the initial supersaturated solution is lower than the solubility product of ACC at 25{degree}c, only vaterite directly precipitates after some induction period. The vaterite crystals formed are free of calcite seeds and the vaterite saturated solutions are stable for several days.

  2. Physicochemical characterization of atorvastatin calcium/ezetimibe amorphous nano-solid dispersions prepared by electrospraying method.

    PubMed

    Jahangiri, Azin; Barzegar-Jalali, Mohammad; Javadzadeh, Yousef; Hamishehkar, Hamed; Adibkia, Khosro

    2016-07-13

    In the present study, electrospraying was applied as a novel method for the fabrication of amorphous nano-solid dispersions (N-SDs) of atorvastatin calcium (ATV), ezetimibe (EZT), and ATV/EZT combination as poorly water-soluble drugs. N-SDs were prepared using polyvinylpyrrolidone K30 as an amorphous carrier in 1:1 and 1:5 drug to polymer ratios and the total solid (including drug and polymer) concentrations of 10 and 20% (w/v). The prepared formulations were further investigated for their morphological, physicochemical, and dissolution properties. Scanning electron microscopy studies indicated that the morphology and diameter of the electrosprayed samples (ESs) were influenced by the solution concentration and drug:polymer ratio, so that an increase in the solution concentration resulted in fiber formation while an increase in the polymer ratio led to enhancement of the particle diameter. Differential scanning calorimetry and X-ray powder diffraction studies together with in vitro dissolution test revealed that the ESs were present in an amorphous form with improved dissolution properties. Infrared spectroscopic studies showed hydrogen-bonding interaction between the drug and polymer in ESs. Since the electrospraying method benefits from the both amorphization and nanosizing effect, this novel approach seems to be an efficient method for the fabrication of N-SDs of poorly water-soluble drugs.

  3. 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

  4. Chemical modification of sputtered amorphous-carbon surfaces

    NASA Astrophysics Data System (ADS)

    Leezenberg, Pieter B.; Johnston, William H.; Tyndall, George W.

    2001-03-01

    Methods to chemically passivate the surfaces of amorphous-carbon films (a-C) produced by dc magnetron sputtering were studied. The chemical composition of carbon surfaces produced via sputtering are dependent upon the environment to which the carbon is exposed immediately following deposition. When the sputtered film is vented to ambient conditions, free radicals produced at the surface during the deposition process are quenched by reaction with oxygen and/or water to form an oxidized, hydrophilic surface. If the sputtered carbon film is, however, exposed to a reactive gas prior to venting to ambient, the chemical nature of the resulting surface can be modified substantially. Specifically, a less highly oxidized and much more hydrophobic carbon surface is produced when the surface free radicals are quenched via either an addition reaction (demonstrated with a fluorinated olefin) or a hydrogen abstraction reaction (demonstrated with two alkyl amines). Chemical modification of amorphous-carbon films can also be accomplished by performing the sputtering in a reactive plasma formed from mixtures of argon with molecular hydrogen, amines, and perfluorocarbons. The elemental composition of these films, and the relative reactivity of the surfaces formed, were investigated via x-ray photoelectron spectroscopy and contact-angle goniometry, respectively. In the case of sputtering with a mixture of argon and hydrogen, increasing the hydrogen flow results in an increase in the amount of hydrogen incorporated into the carbon film and a decrease in the surface free energy. Sputtering in diethylamine produces an amorphous-carbon film into which nitrogen is incorporated. The free energies of the a-C:N surfaces produced in this process are similar to those of the a-C:H films. Sputtering in a fluorocarbon vapor results in the incorporation of fluorine into the film structure and the formation of very low free-energy surfaces. Increasing the concentration of the fluorocarbon in the

  5. 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.

  6. The effect of high calcium milk and casein phosphopeptide-amorphous calcium phosphate on enamel erosion caused by cholinated water.

    PubMed

    Vongsawan, Kadkao; Surarit, Rudee; Rirattanapong, Praphasri

    2010-11-01

    The aim of this study was to determine the effectiveness of high calcium milk and casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) on enamel erosion caused by chlorinated water. Thirty-six bovine enamel samples without wear or caries 3x4 mm in size were placed in acrylic blocks. All specimens were randomly allocated into 3 groups (n=12/group): CPP-ACP in the form of paste, Anlene concentrated milk and a control (no treatment). All specimens were soaked in chlorinated water (pH =5.0) at room temperature for 72 hours following by soaking in artificial saliva for 30 minutes. Then, microhardness was determined using a microhardness tester. Data were analyzed using a one-way ANOVA and paired t-test. The microhardness value change in the control group was significantly higher than the other groups. No significant differences were seen between the 2 study groups. High calcium milk and CPP-ACP enhanced remineralization of enamel erosion caused by chlorinated water.

  7. Ammonia sensitivity of amorphous carbon film/silicon heterojunctions

    SciTech Connect

    Gao Xili; Xue Qingzhong; Hao Lanzhong; Zheng Qingbin; Li Qun

    2007-09-17

    The amorphous carbon film/n-Si (a-C/Si) junctions have been fabricated by magnetron sputtering. The results show that these junctions have good rectifying properties and high ammonia (NH{sub 3}) gas sensitivity. For a given reverse bias voltage, the resistance of the junction can increase by 100 times rapidly when exposed to NH{sub 3} gas. This phenomenon may be attributed to the change of the space charge width of the junction, which is caused by the adsorption of NH{sub 3} gas molecules. This study shows that these a-C/Si junctions have potential application as NH{sub 3} gas detect sensors.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Proton and deuteron nuclear magnetic resonance studies of amorphous hydrogenated silicon, carbon, and carbon alloys

    NASA Astrophysics Data System (ADS)

    Kernan, Mary Jane Wurth

    Despite the profound influence of semiconductors and the changes they have produced, many fundamental questions remain unanswered. We have used proton and deuteron nuclear magnetic resonance (NMR) to explore the role of hydrogens in amorphous silicon and amorphous carbon and carbon alloy films. In the carbon films, dipolar filtering techniques reveal a two-component shifted lineshape in the proton NMR spectra and deuteron magnetic resonance (DMR) data demonstrate a feedstock gas dependence in the film deposition process. In these measurements, DMR is used to examine the effect of hydrogen on the photovoltaic properties of amorphous silicon thin films. We have measured the effects of photoillumination on amorphous silicon, particularly with respect to the process of metastable defect formation (the Staebler-Wronski effect). The creation and passivation of dangling silicon bonds is observed and quantified. We report large-scale light-induced atomic rearrangements which produce shifts and broadenings of the DMR lineshapes. The deuterium NMR lineshape component most affected by atomic rearrangements is a broad central feature which is shown to be molecular in origin. This spectral feature includes hydrogens trapped and immobile on surfaces created by strains and dislocations in the material. Narrowing of the lineshape at elevated temperatures indicates motion with a small activation energy. The substantial population represented by this feature is shown to account for at least 15% of the total hydrogens in high-quality amorphous silicon samples.

  14. 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.

  15. Clonorcis sinensis eggs are associated with calcium carbonate gallbladder stones.

    PubMed

    Qiao, Tie; Ma, Rui-hong; Luo, Zhen-liang; Yang, Liu-qing; Luo, Xiao-bing; Zheng, Pei-ming

    2014-10-01

    Calcium carbonate gallbladder stones were easily neglected because they were previously reported as a rare stone type in adults. The aim of this study was to investigate the relationship between calcium carbonate stones and Clonorchis sinensis infection. A total of 598 gallbladder stones were studied. The stone types were identified by FTIR spectroscopy. The C. sinensis eggs and DNA were detected by microscopic examination and real-time fluorescent PCR respectively. And then, some egg-positive stones were randomly selected for further SEM examination. Corresponding clinical characteristics of patients with different types of stones were also statistically analyzed. The detection rate of C. sinensis eggs in calcium carbonate stone, pigment stone, mixed stone and cholesterol stone types, as well as other stone types was 60%, 44%, 36%, 6% and 30%, respectively, which was highest in calcium carbonate stone yet lowest in cholesterol stone. A total of 182 stones were egg-positive, 67 (37%) of which were calcium carbonate stones. The C. sinensis eggs were found adherent to calcium carbonate crystals by both light microscopy and scanning electron microscopy. Patients with calcium carbonate stones were mainly male between the ages of 30 and 60, the CO2 combining power of patients with calcium carbonate stones were higher than those with cholesterol stones. Calcium carbonate gallbladder stones are not rare, the formation of which may be associated with C. sinensis infection.

  16. 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).

  17. 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.

  18. 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 40

  19. Preparation and fluorescence property of red-emitting Eu{sup 3+}-activated amorphous calcium silicate phosphor

    SciTech Connect

    Kojima, Yoshiyuki; Kamei, Shinnosuke; Nishimiya, Nobuyuki

    2010-02-15

    This paper describes the energy efficient synthesis of a red-emitting Eu{sup 3+}-activated amorphous calcium silicate phosphor produced by heating a Eu{sup 3+}-activated calcium silicate hydrate phosphor. Concentration quenching of the Eu{sup 3+}-activated calcium silicate hydrate phosphor was not observed and the emission intensity did not decrease up to a Eu/(Ca+Eu) atomic ratio of 0.46. Heating of the Eu{sup 3+}-activated calcium silicate hydrate (Eu/(Ca+Eu) atomic ratio = 0.32) phosphor produced an amorphous Eu{sup 3+}-activated calcium silicate phosphor, which had a maximum emission intensity at 870 {sup o}C and emitted in the red under near-ultraviolet irradiation (395 nm). The emission intensity of the Eu{sup 3+}-activated amorphous calcium silicate phosphor was about half that of a commercial BaMgAl{sub 10}O{sub 17}:Eu{sup 2+} phosphor, and shows great potential for application in white light-emitting diodes.

  20. 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.

  1. Structural and electronic properties of a tetrahedral amorphous carbon surface

    NASA Astrophysics Data System (ADS)

    Dong, Jianjun; Drabold, D. A.

    1997-03-01

    We present ab initio studies of a model of tetrahedral amorphous carbon (ta-C) surface. Our methodology is LDA (with Harris functional and local basis) molecular dynamics simulations. The surface is modeled by a 216 atom slab supercell. Several candidate slabs are constructed by starting with the DTW model (B.R. Djordjevic, M.F. Thorpe and F. Wooten, Phys. Rev. B 52) 5685 (1995) and applying various simulated heating/quenching cycles. We analyze the structural and electronic properties of the surface , with special attention forcused on the electronic signatures of surface structural defects. Preliminary results indicate that the surface layer significantly graphitizes, and many surface gap states are present in the electronic density of states.

  2. 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.

  3. Adsorption ability comparison of plasma proteins on amorphous carbon surface

    NASA Astrophysics Data System (ADS)

    Takeda, Aoi; Akasaka, Hiroki; Ohshio, Shigeo; Toda, Ikumi; Nakano, Masayuki; Saitoh, Hidetoshi

    2012-11-01

    To understand why amorphous carbon (a-C:H) film shows antithrombogenicity, an adsorption ability of plasma proteins on a-C:H surface was investigated. Protein adsorption is the initial process of clot formation. The protein adsorption ability on a-C:H film surface was compared by the detection using the surface plasmon resonance (SPR) phenomenon to estimate the protein adsorption. The protein adsorption abilities of a fibrinogen (Fib) and a human γ-globulin (HGG) were estimated by the SPR method using a multilayer structure of a-C:H/Au/Cr/glass. Although the adsorption of HGG for a-C:H was saturated at 32 μM in HGG concentration, the adsorption of Fib was not saturated under the detection limit of this method. These results indicated that the adsorption ability to the a-C:H film surface of Fib was higher than HGG.

  4. Amorphous carbon buffer layers for separating free gallium nitride films

    NASA Astrophysics Data System (ADS)

    Altakhov, A. S.; Gorbunov, R. I.; Kasharina, L. A.; Latyshev, F. E.; Tarala, V. A.; Shreter, Yu. G.

    2016-11-01

    The possibility of using amorphous diamond-like carbon (DLC) films for self-separation of gallium nitride (GaN) layers grown by hydride vapor-phase epitaxy has been analyzed. DLC films have been synthesized by plasma-enhanced chemical vapor deposition under low pressure on sapphire (Al2O3) substrates with a (0001) crystallographic orientation. The samples have been studied by the methods of Raman scattering and X-ray diffraction analysis. It is shown that thin DLC films affect only slightly the processes of nucleation and growth of gallium nitride films. Notably, the strength of the "GaN film-Al2O3" substrate interface decreases, which facilitates separation of the GaN layers.

  5. Properties of nitrogen-doped amorphous hydrogenated carbon films

    SciTech Connect

    Amir, O.; Kalish, R. )

    1991-11-01

    Nitrogen-containing hydrogenated amorphous carbon (a-C:H(N)) films are grown from a dc plasma of a N{sub 2}+C{sub 6}H{sub 6} gas mixture. By varying the N{sub 2} fraction in this mixture films with different amounts of N are produced. The actual amount of nitrogen in the {ital a}-C:H(N) films is determined by nuclear reaction analysis and by Auger electron spectroscopy profiling. The nitrogen concentration in the films grows exponentially with nitrogen content in the gas mixture reaching concentrations as high as 10 at.% for the films grown from a N{sub 2}-rich gas mixture (N{sub 2}/(N{sub 2}+C{sub 6}H{sub 6})=0.75). The electrical and structural properties of the N{sub 2}-doped films are studied by performing electrical conductivity, thermopower (TP), optical absorption, and electron-paramagnetic resonance measurements. Films with low ({lt}1 at.%) nitrogen content exhibit fairly high resistivities, have an optical gap of 1 eV, are rich with dangling bonds (5{times}10{sup 20} cm{sup {minus}3}) and their thermopower is positive and in the mV/K regime, indicating conductivity in the valence band tail. However, with increased N doping, the resistivity decreases and the optical band gap shrinks and reached zero for the highest doped film. The TPs for films containing more than 1 at.% are in the {mu}V/K range, indicating hopping conductivity around the Fermi level. The results of all measurements are consistent with the model of Robertson for the electrical structure of amorphous hydrogenated carbon and for the proposed doping mechanism in this material.

  6. Physicochemical properties and oral bioavailability of amorphous atorvastatin hemi-calcium using spray-drying and SAS process.

    PubMed

    Kim, Jeong-Soo; Kim, Min-Soo; Park, Hee Jun; Jin, Shun-Ji; Lee, Sibeum; Hwang, Sung-Joo

    2008-07-09

    The objective of the study was to prepare amorphous atorvastatin hemi-calcium using spray-drying and supercritical antisolvent (SAS) process and evaluate its physicochemical properties and oral bioavailability. Atorvastatin hemi-calcium trihydrate was transformed to anhydrous amorphous form by spray-drying and SAS process. With the SAS process, the mean particle size and the specific surface area of amorphous atorvastatin were drastically changed to 68.7+/-15.8nm, 120.35+/-1.40m2/g and 95.7+/-12.2nm, 79.78+/-0.93m2/g from an acetone solution and a tetrahydrofuran solution, respectively and appeared to be associated with better performance in apparent solubility, dissolution and pharmacokinetic studies, compared with unprocessed crystalline atorvastatin. Oral AUC0-8h values in SD rats for crystalline and amorphous atorvastatin were as follow: 1121.4+/-212.0ngh/mL for crystalline atorvastatin, 3249.5+/-406.4ngh/mL and 3016.1+/-200.3ngh/mL for amorphous atorvastatin from an acetone solution and a tetrahydrofuran solution with SAS process, 2227.8+/-274.5 and 2099.9+/-339.2ngh/mL for amorphous atorvastatin from acetone and tetrahydrofuran with spray-drying. The AUCs of all amorphous atorvastatin significantly increased (P<0.05) compared with crystalline atorvastatin, suggesting that the enhanced bioavailability was attributed to amorphous nature and particle size reduction. In addition, the SAS process exhibits better bioavailability than spray-drying because of particle size reduction with narrow particle size distribution. It was concluded that physicochemical properties and bioavailability of crystalline atorvastatin could be improved by physical modification such as particle size reduction and generation of amorphous state using spray-drying and SAS process. Further, SAS process was a powerful methodology for improving the physicochemical properties and bioavailability of atorvastatin.

  7. Oxidation of fluorinated amorphous carbon (a-CF(x)) films.

    PubMed

    Yun, Yang; Broitman, Esteban; Gellman, Andrew J

    2010-01-19

    Amorphous fluorinated carbon (a-CF(x)) films have a variety of potential technological applications. In most such applications these films are exposed to air and undergo partial surface oxidation. X-ray photoemission spectroscopy has been used to study the oxidation of fresh a-CF(x) films deposited by magnetron sputtering. The oxygen sticking coefficient measured by exposure to low pressures (<10(-3) Torr) of oxygen at room temperature is on the order of S approximately 10(-6), indicating that the surfaces of these films are relatively inert to oxidation when compared with most metals. The X-ray photoemission spectra indicate that the initial stages of oxygen exposure (<10(7) langmuirs) result in the preferential oxidation of the carbon atoms with zero or one fluorine atom, perhaps because these carbon atoms are more likely to be found in configurations with unsaturated double bonds and radicals than carbon atoms with two or three fluorine atoms. Exposure of the a-CF(x) film to atmospheric pressures of air (effective exposure of 10(12) langmuirs to O(2)) results in lower levels of oxygen uptake than the low pressure exposures (<10(7) langmuirs). It is suggested that this is the result of oxidative etching of the most reactive carbon atoms, leaving a relatively inert surface. Finally, low pressure exposures to air result in the adsorption of both nitrogen and oxygen onto the surface. Some of the nitrogen adsorbed on the surface at low pressures is in a reversibly adsorbed state in the sense that subsequent exposure to low pressures of O(2) results in the displacement of nitrogen by oxygen. Similarly, when an a-CF(x) film oxidized in pure O(2) is exposed to low pressures of air, some of the adsorbed oxygen is displaced by nitrogen. It is suggested that these forms of nitrogen and oxygen are bound to free radical sites in the film.

  8. 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.

  9. 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.

  10. 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}.

  11. Polymerization shrinkage and stress development in amorphous calcium phosphate/urethane dimethacrylate polymeric composites

    PubMed Central

    Antonucci, J.M.; Regnault, W. F.; Skrtic, D.

    2010-01-01

    This study explores how substituting a new high molecular mass oligomeric poly(ethylene glycol) extended urethane dimethacrylate (PEG-U) for 2-hydroxyethyl methacrylate (HEMA) in photo-activated urethane dimethacrylate (UDMA) resins affects degree of vinyl conversion (DC), polymerization shrinkage (PS), stress development (PSSD) and biaxial flexure strength (BFS) of their amorphous calcium phosphate (ACP) composites. The composites were prepared from four types of resins (UDMA, PEG-U, UDMA/HEMA and UDMA/PEG-U) and zirconia-hybridized ACP. Introducing PEG-U improved DC while not adversely affecting PS, PSSD and the BFS of composites. This improvement in DC is attributed to the long, more flexible structure between the vinyl groups of PEG-U and its higher molecular mass compared to poly(HEMA). The results imply that PEG-U has the potential to serve as an alternative to HEMA in dental and other biomedical applications. PMID:20169007

  12. 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

  13. Effect of glycoursodeoxycholate on precipitation of calcium carbonate.

    PubMed

    Marteau, C; Portugal, H; Pauli, A M; Gerolami, A

    1985-01-01

    The potential role of bile salts in preventing calcium carbonate precipitation was investigated by studying their interaction of Ca2+ and their inhibitory effects on calcium carbonate formation. Glycochenodeoxycholate micelles bound more calcium than did glycocholate. At bile salt concentrations exceeding 12.5 mM, glycoursodeoxycholate bound calcium as well as glycochenodexycholate did. Similar results for calcium binding were observed in mixed micelles of bile salts and lecithin. In bicarbonate (25 or 50 mM) and CaCl2 (10 mM) solutions, calcium carbonate formation was inhibited by the bile salts. Glycoursodeoxycholate and glycochenodeoxycholate (25 mM) prevented calcium carbonate formation which was delayed by glycocholate. This effect is not due to differences between both series of bile salts for calcium binding since glycoursodeoxycholate or glycochenodeoxycholate (25 mM) more efficiently prevented calcium carbonate precipitation than did 35 mM glycocholate in spite of the same Ca2+ binding. These results suggest that some bile salts may have a specific role in preventing calcium precipitation in bile. The mechanism is unknown. The physical properties of glycoursodeoxycholate and glycochenodeoxycholate do not support a role for CaCO3 precipitation in gallstone calcification during litholytic therapy.

  14. 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

  15. In Vitro Properties of Orthodontic Adhesives with Fluoride or Amorphous Calcium Phosphate

    PubMed Central

    Chow, Clara Ka Wai; Wu, Christine D.; Evans, Carla A.

    2011-01-01

    This in vitro study evaluated the efficacy of orthodontic adhesives with fluoride or amorphous calcium phosphate (ACP) in reducing bacterial adhesion and enamel demineralization. Forty human premolars each sectioned buccolingually into three parts were bracketed with control resin (Transbond XT) or adhesives containing ACP (Aegis Ortho) or fluoride (QuickCure). Artificial lesions induced by pH cycling were examined by X-ray photoelectron spectrophotometry (XPS) and polarized light microscopy (PLM). After 28 days, Aegis Ortho demonstrated the lowest calcium and phosphorous content by XPS analysis. After 42 days, reductions in lesion depth areas were 23.6% for Quick Cure and 20.3% for Aegis Ortho (P < 0.05). In the presence of 1% sucrose, adhesion of Streptococcus mutans to Aegis Ortho and Quick Cure was reduced by 41.8% and 37.7% (P < 0.05) as compared to Transbond XT. Composites containing ACP or fluoride reduced bacterial adherence and lesion formation as compared to a composite without ACP or fluoride. PMID:21912546

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

    PubMed

    Regnault, William F; Icenogle, Tonya B; Antonucci, Joseph M; Skrtic, Drago

    2008-02-01

    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.

  18. 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.

  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. Effect of amorphous calcium phosphate and silver nanocomposites on dental plaque microcosm biofilms

    PubMed Central

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

    2012-01-01

    A dental composite containing amorphous calcium phosphate nanoparticles (NACP) was developed that released calcium (Ca) and phosphate (PO4) ions and possessed acid-neutralization capability. There has been little study on incorporation of antibacterial agents into calcium phosphate composites. The objective of this study was to investigate the effect of silver nanoparticle (NAg) mass fraction in NACP nanocomposite on mechanical properties and dental plaque microcosm biofilm for the first time. NACP nanoparticles of 116 nm were synthesized via a spray-drying technique. NAg nanoparticles were synthesized using Ag 2-ethylhexanoate and 2-(tert-butylamino)ethyl methacrylate, yielding NAg of particle size of 2.7 nm that were well-dispersed in the resin. Five NACP nanocomposites were fabricated with NAg mass fractions of 0, 0.028, 0.042, 0.088, and 0.175%, respectively. Mechanical properties of NACP nanocomposites containing 0–0.042% of NAg matched those of a commercial composite without antibacterial activity. Live/dead assay of dental plaque microcosm biofilms showed complete coverage with live bacteria on commercial composite. However, there were increasingly more dead bacteria with higher NAg content in the NACP nanocomposite. Colony-forming unit (CFU) counts for total microorganisms, total Streptococci, and mutans Streptococci for NACP nanocomposite with 0.042% NAg were about 1/4 those of commercial composite. Lactic acid production on NACP nanocomposite with 0.042% NAg was 1/3 that on commercial composite. In conclusion, novel NACP–NAg nanocomposites were developed which possessed good mechanical properties and potent antibacterial properties, with substantially reduced biofilm viability and lactic acid production. Hence, the NACP–NAg nanocomposites are promising for dental restorations with remineralizing and antibacterial capabilities. PMID:22566464

  1. Elucidating the Effect of Biomolecule Structure on Calcium Carbonate Crystal Formation

    NASA Astrophysics Data System (ADS)

    Kulbok, K. E.; Duckworth, O.

    2011-12-01

    , as well as the effect of biomolecule structure on calcium carbonate crystals. Preliminary XRD and SEM analyses have shown vaterite, calcite, and amorphous CaCO3 to be the primary morphologies present. This analysis indicates a lack of stability for crystals grown quickly at elevated CO2 concentrations. The rate of precipitation of calcium carbonate solids and the subsequent decrease in free calcium concentration has been shown to be largely a function of pH.

  2. Fullerene nanostructure-induced excellent mechanical properties in hydrogenated amorphous carbon

    NASA Astrophysics Data System (ADS)

    Wang, Qi; Wang, Chengbing; Wang, Zhou; Zhang, Junyan; He, Deyan

    2007-10-01

    Hydrogenated amorphous carbon films were deposited by dc-pulse plasma chemical vapor deposition. The structure of as-prepared films, characterized by transmission electron microscopy, Raman spectra, and x-ray photoelectron spectra, is considered as nanocomposite thin films with C60 and fullerene crystalline nanoparticles embedded in amorphous sp2 and sp3 carbon matrices. The high hardness and high elastic recovery of as-prepared films are attributed to the unique structure that C60 and fullerene nanocrystalline grains (soft) dispersed in amorphous carbon phase (hard) to form a network structure, which restrains the dislocation migration, assists the stress relaxation, and hence, enhances the mechanical properties of the films.

  3. 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

  4. [Study on solid dispersion of precipitated calcium carbonate-based oleanolic acid].

    PubMed

    Yan, Hong-mei; Zhang, Zhen-hai; Jia, Xiao-bin; Jiang, Yan-rong; Sun, E

    2015-05-01

    Oleanolic acid-precipitated calcium carbonate solid dispersion was prepared by using solvent evaporation method. The microscopic structure and physicochemical properties of solid dispersion were analyzed using differential scanning calorimetry and scanning electron microscopy (SEM). And its in vitro release also was investigated. The properties of the precipitated calcium carbonate was studied which was as a carrier of oleanolic acid solid dispersion. Differential scanning calorimetry analysis suggested that oleanolic acid may be present in solid dispersion as amorphous substance. The in vitro release determination results of oleanolic acid-precipitated calcium carbonate (1: 5) solid dispersion showed accumulated dissolution rate of.oleanolic acid was up to 90% at 45 min. Accelerating experiment showed that content and in vitro dissolution of oleanolic acid solid dispersion did not change after storing over 6 months. The results indicated that in vitro dissolution of oleanolic acid was improved greatly by the solid dispersion with precipitated calcium carbonate as a carrier. The solid dispersion is a stabilizing system which has actual applied value.

  5. Influence of calcium sources on microbially induced calcium carbonate precipitation by Bacillus sp. CR2.

    PubMed

    Achal, Varenyam; Pan, Xiangliang

    2014-05-01

    Stimulation of microbially induced calcium carbonate precipitation (MICCP) is likely to be influenced by calcium sources. In order to study such influences, we performed MICCP using Bacillus sp. CR2 in nutrient broth containing urea, supplemented with different calcium sources (calcium chloride, calcium oxide, calcium acetate and calcium nitrate). The experiment lasted 7 days, during which bacterial growth, urease activity, calcite production and pH were measured. Our results showed that calcium chloride is the better calcium source for MICCP process, since it provides higher urease activity and more calcite production. The influences of calcium sources on MICCP were further studied using Fourier transform-infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses. These analyses confirmed that the precipitate formed was CaCO3 and composed of predominantly calcite crystals with a little amount of aragonite and vaterite crystals. The maximum yield of calcite precipitation was achievable with calcium chloride followed by calcium nitrate as a calcium source. The results of present study may be applicable to media preparation during efficient MICCP process.

  6. 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.

  7. Wake potential of swift ion in amorphous carbon target

    NASA Astrophysics Data System (ADS)

    Al-Bahnam, Nabil janan; Ahmad, Khalid A.; Aboo Al-Numan, Abdullah Ibrahim

    2017-02-01

    The wake potential and wake phenomena for swift proton in an amorphous carbon target were studied by utilising various dielectric function formalisms, including the Drude dielectric function, the Drude-Lorentz dielectric function and quantum dielectric function. The Drude model results exhibited a damped oscillatory behaviour in the longitudinal direction behind the projectile; the pattern of these oscillations decreases exponentially in the transverse direction. In addition, the wake potential extends slightly ahead of the projectile which also depends on the proton coordinate and velocity. The effect of electron binding on the wake potential, characterised by the ratio ωp2 / ω02 = 10 to 0.1, has been studied alongside the Drude-Lorentz dielectric function and quantum dielectric function formalisms; the results evidently show that the wake potential dip depth decreases with more oscillations when the electron density ratio ωp2 / ω02 decreases from 10 to 0.1. One of the primary objectives of the present work is to construct a reasonably realistic procedure for simulating the response of target to swift ions by combining an expression for the induced wake potential along with several important dielectric function models; the aim of this research is to reduce computational complexity without sacrificing accuracy. This is regarded as being an efficient strategy in that it creates suitable computer simulation procedures which are relevant to actual solids. After comparing this method with other models, the main differences and similarities have been noted while the end results have proved encouraging.

  8. Thermal decomposition of fullerene nanowhiskers protected by amorphous carbon mask

    PubMed Central

    Guo, Hongxuan; Wang, Chengxiang; Miyazawa, Kun’ichi; Wang, Hongxin; Masuda, Hideki; Fujita, Daisuke

    2016-01-01

    Fullerene nanostructures are well known for their unique morphology, physical and mechanical properties. The thermal stability of fullerene nanostructures, such as their sublimation at high temperature is also very important for studying their structures and applications. In this work, We observed fullerene nanowhiskers (FNWs) in situ with scanning helium ion microscopy (HIM) at elevated temperatures. The FNWs exhibited different stabilities with different thermal histories during the observation. The pristine FNWs were decomposed at the temperatures higher than 300 °C in a vacuum environment. Other FNWs were protected from decomposition with an amorphous carbon (aC) film deposited on the surface. Based on high spacial resolution, aC film with periodic structure was deposited by helium ion beam induced deposition (IBID) on the surface of FNWs. Annealed at the high temperature, the fullerene molecules were selectively sublimated from the FNWs. The periodic structure was formed on the surface of FNWs and observed by HIM. Monte Carlo simulation and Raman characterization proved that the morphology of the FNWs was changed by helium IBID at high temperature. This work provides a new method of fabricating artificial structure on the surface of FNWs with periodic aC film as a mask. PMID:27991498

  9. Thermal decomposition of fullerene nanowhiskers protected by amorphous carbon mask

    NASA Astrophysics Data System (ADS)

    Guo, Hongxuan; Wang, Chengxiang; Miyazawa, Kun’Ichi; Wang, Hongxin; Masuda, Hideki; Fujita, Daisuke

    2016-12-01

    Fullerene nanostructures are well known for their unique morphology, physical and mechanical properties. The thermal stability of fullerene nanostructures, such as their sublimation at high temperature is also very important for studying their structures and applications. In this work, We observed fullerene nanowhiskers (FNWs) in situ with scanning helium ion microscopy (HIM) at elevated temperatures. The FNWs exhibited different stabilities with different thermal histories during the observation. The pristine FNWs were decomposed at the temperatures higher than 300 °C in a vacuum environment. Other FNWs were protected from decomposition with an amorphous carbon (aC) film deposited on the surface. Based on high spacial resolution, aC film with periodic structure was deposited by helium ion beam induced deposition (IBID) on the surface of FNWs. Annealed at the high temperature, the fullerene molecules were selectively sublimated from the FNWs. The periodic structure was formed on the surface of FNWs and observed by HIM. Monte Carlo simulation and Raman characterization proved that the morphology of the FNWs was changed by helium IBID at high temperature. This work provides a new method of fabricating artificial structure on the surface of FNWs with periodic aC film as a mask.

  10. Laser induced crystallization of hydrogenated amorphous silicon-carbon alloys

    NASA Astrophysics Data System (ADS)

    Summonte, C.; Rizzoli, R.; Servidori, M.; Milita, S.; Nicoletti, S.; Bianconi, M.; Desalvo, A.; Iencinella, D.

    2004-10-01

    Laser induced crystallization of hydrogenated amorphous silicon carbon alloy (a-Si1-xCx:H) films has been investigated by means of synchrotron x-ray diffraction. The a-Si1-xCx:H films were deposited on (100) silicon wafers by very high frequency plasma enhanced chemical vapor deposition at 100MHz in hydrogen diluted silane-methane gas mixtures. The substrate was kept at 250°C or 350°C and the stoichiometry was changed from x =0.20 to 0.63. The structural characterization of the as-grown films has been carried out by Rutherford backscattering (hydrogen concentration) and infrared spectroscopy (film ordering). The films were irradiated by a KrF excimer laser (248nm ) with varying energy density and number of pulses. After irradiation, the formation of SiC crystallites has been revealed by synchrotron x-ray diffraction. Besides SiC nanocrystals, the formation of crystalline Si and graphite is observed for under- (x <0.50) and over-stoichiometric (x>0.50) samples, respectively. The essential role played by hydrogen concentration and hydrogen bonding configuration in determining the melting threshold and the consequent SiC grain formation is highlighted.

  11. Electromagnetic Wave Absorbing Properties of Amorphous Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    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.

  12. Electromagnetic wave absorbing properties of amorphous carbon nanotubes.

    PubMed

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

    2014-07-10

    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.

  13. 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

  14. Non-catalytic synthesis of diamond from amorphous carbon at high static pressure

    NASA Astrophysics Data System (ADS)

    Higashi, K.; Onodera, A.

    1986-05-01

    Amorphous carbon prepared from furfuryl alcohol resin was studied under static high pressure above 10 GPa without planned addition of catalyst. Diamond can be formed at temperatures lower than required for the catalytic process.

  15. 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

  16. 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

  17. Evidence for calcium carbonate at the Mars Phoenix landing site.

    PubMed

    Boynton, W V; Ming, D W; Kounaves, S P; Young, S M M; Arvidson, R E; Hecht, M H; Hoffman, J; Niles, P B; Hamara, D K; Quinn, R C; Smith, P H; Sutter, B; Catling, D C; Morris, R V

    2009-07-03

    Carbonates are generally products of aqueous processes and may hold important clues about the history of liquid water on the surface of Mars. Calcium carbonate (approximately 3 to 5 weight percent) has been identified in the soils around the Phoenix landing site by scanning calorimetry showing an endothermic transition beginning around 725 degrees C accompanied by evolution of carbon dioxide and by the ability of the soil to buffer pH against acid addition. Based on empirical kinetics, the amount of calcium carbonate is most consistent with formation in the past by the interaction of atmospheric carbon dioxide with liquid water films on particle surfaces.

  18. Urea hydrolysis and calcium carbonate reaction fronts

    NASA Astrophysics Data System (ADS)

    Fox, D. T.; Redden, G. D.; Henriksen, J.; Fujita, Y.; Guo, L.; Huang, H.

    2010-12-01

    The mobility of toxic or radioactive metal contaminants in subsurface environments can be reduced by the formation of mineral precipitates that form co-precipitates with the contaminants or that isolate them from the mobile fluid phase. An engineering challenge is to control the spatial distribution of precipitation reactions with respect to: 1) the location of a contaminant, and 2) where reactants are introduced into the subsurface. One strategy being explored for immobilizing contaminants, such as Sr-90, involves stimulating mineral precipitation by forming carbonate ions and hydroxide via the in situ, microbially mediated hydrolysis of urea. A series of column experiments have been conducted to explore how the construction or design of such an in situ reactant production strategy can affect the temporal and spatial distribution of calcium carbonate precipitation, and how the distribution is coupled to changes in permeability. The columns were constructed with silica gel as the porous media. An interval midway through the column contained an adsorbed urease enzyme in order to simulate a biologically active zone. A series of influent solutions were injected to characterize hydraulic properties of the column (e.g., bromide tracer), profiles of chemical conditions and reaction products as the enzyme catalyzes urea hydrolysis (e.g., pH, ammonia, urea), and changes that occur due to CaCO3 precipitation with the introduction of a calcium+urea solutions. In one experiment, hydraulic conductivity was reduced as precipitate accumulated in a layer within the column that had a higher fraction of fine grained silica gel. Subsequent reduction of permeability and flow (for a constant head condition) resulted in displacement of the hydrolysis and precipitation reaction profiles upstream. In another experiment, which lacked the physical heterogeneity (fine grained layer), the precipitation reaction did not result in loss of permeability or flow velocity and the reaction profile

  19. Behaviour of calcium carbonate in sea water

    USGS Publications Warehouse

    Cloud, P.E.

    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

  20. 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

  1. 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

  2. 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.

  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.

  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. 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

  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.

  7. The role of Carboxydothermus hydrogenoformans in the conversion of calcium phosphate from amorphous to crystalline state.

    PubMed

    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.

  8. Nanoparticle tracers in calcium carbonate porous media

    NASA Astrophysics Data System (ADS)

    Li, Yan Vivian; Cathles, Lawrence M.; Archer, Lynden A.

    2014-08-01

    Tracers are perhaps the most direct way of diagnosing subsurface fluid flow pathways for ground water decontamination and for natural gas and oil production. Nanoparticle tracers could be particularly effective because they do not diffuse away from the fractures or channels where flow occurs and thus take much less time to travel between two points. In combination with a chemical tracer they can measure the degree of flow concentration. A prerequisite for tracer applications is that the particles are not retained in the porous media as the result of aggregation or sticking to mineral surfaces. By screening eight nanoparticles (3-100 nm in diameter) for retention when passed through calcium carbonate packed laboratory columns in artificial oil field brine solutions of variable ionic strength we show that the nanoparticles with the least retention are 3 nm in diameter, nearly uncharged, and decorated with highly hydrophilic polymeric ligands. The details of these column experiments and the tri-modal distribution of zeta potential of the calcite sand particles in the brine used in our tests suggests that parts of the calcite surface have positive zeta potential and the retention of negatively charged nanoparticles occurs at these sites. Only neutral nanoparticles are immune to at least some retention.

  9. Hen eggwhite-mediated stack crystallization of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Hu, Yanli; Ma, Yongjun; Zhou, Yong; Nie, Fude; Duan, Xiaohui; Pei, Chonghua

    2010-03-01

    In this paper, the stack-like crystallization of calcium carbonate in the presence of hen eggwhite under direct drying and vacuum freeze drying was investigated, and marked morphological changes in the calcium carbonate particles were observed depending on the reaction condition used. Scanning electron microscopy (SEM), Powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Transmission electron microscopy (TEM), and Nano Mechanical Tester were employed to characterize the samples. Results indicate that gelling eggwhite-mediated the formation of the "stack-like" layered calcium carbonate aggregates composed of considerable nanosheets under direct drying while only rhombohedra calcite crystal (1 0 4) was formed without any additives. An analogous structure to the brick-and-mortar arrangement was attainted by vacuum freeze drying. The average elastic modulus and the hardness of "stack-like" calcium carbonate hybrid material were assessed 0.9952 and 0.0415 GPa with Nano-indenter test, respectively.

  10. 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

  11. 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.

  12. Calcium and calcium magnesium carbonate specimens submitted as urinary tract stones.

    PubMed

    Gault, M H; Chafe, L; Longerich, L; Mason, R A

    1993-02-01

    Of 8,129 specimens submitted as urinary stones from 6,095 patients, 67 from 15 patients were predominantly calcium carbonate or calcium magnesium carbonate (dolomite) by infrared analysis. Detailed study of 1 man and 4 women who submitted 3 or more such specimens showed that all were of aragonite calcium carbonate crystal form in 2 women and all calcite in the man. All 3 patients had a long history of nephrolithiasis preceding submission of calcium carbonate stones. There was frequent and often painful spontaneous passage of many small stones. Medullary sponge kidney was reported in 2 patients. Specimens submitted by the other 2 women included dolomite and quartz artifacts. Of the other 10 patients 4 had calcite and 1 had aragonite (possibly true stones). Five patients had artifacts with dolomite in 3 and mixed specimens in 2. True calcium carbonate kidney stones and calcium carbonate artifacts may be difficult to distinguish, and dolomite and quartz artifacts may require x-ray diffraction for clear-cut diagnosis.

  13. Optical characterization of 193nm amorphous carbon ARC films

    NASA Astrophysics Data System (ADS)

    Leng, Jingmin; Opsal, Jon; Pois, Heath

    2005-05-01

    In this study, the optical properties of amorphous carbon (aC) ARC films are investigated using an Opti-probe OP7341, and a metrology solution that robustly measures a broad range of process conditions is presented. We find that the aC material is consistent with uni-axial anisotropy, and that this effect may have important implications for photolithography. These results are obtained through the combination of multiple technologies in one tool: spectroscopic ellipsometry (SE); spectroscopic reflectometry or broadband (BB), with a wavelength range of 190-840 nm; single wavelength (673 nm) but multiple incident angle beam profile reflectometry (BPR) and beam profile ellipsometry (BPE), and single wavelength (633nm) absolute ellipsometry (AE). The combination of technologies at multiple angles and wavelengths provides additional optical information and sensitivity not possible with single-technology approaches. A complex wavelength dependent anisotropy model was developed for this analysis, and is compared with a real anisotropy model. The complex anisotropy model and the effective medium approximation (EMA) with two and three components were applied to a set of 12 wafer set with thickness swing aC films in the range of 500-750 Å as well as a second set of 23 pre- and post- etch wafers. The complex anisotropy model clearly has the advantage of best fit the BPR profiles along with the SE Fourier coefficients. The etch rate obtained by the complex anisotropy also showed a much narrower variation as compared with the EMA2 and EMA32 models with the real anisotropy.

  14. 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.

  15. Effect of amorphous phases during the hydraulic conversion of α-TCP into calcium-deficient hydroxyapatite.

    PubMed

    Hurle, Katrin; Neubauer, Juergen; Bohner, Marc; Doebelin, Nicola; Goetz-Neunhoeffer, Friedlinde

    2014-09-01

    Powders of α-tricalcium phosphate (α-TCP), which readily react with water to form calcium-deficient hydroxyapatite (CDHA), are frequently used in bone cements. As, for clinical applications, it is important to adjust the setting reaction of the cements to a reasonable reaction time, exact knowledge of the hydration mechanism is essential. It is known that prolonged milling results in partial amorphization of α-TCP powders and that dissolution of the amorphous phase significantly accelerates the hydration, but it is not clear yet when the amorphous phase reacts in comparison to the crystalline α-TCP. Therefore the aim of this study was to investigate the development of quantitative phase content of α-TCP samples during hydration. For this purpose, three α-TCP powders, containing 0, 16 and 71wt.% of amorphous phase (ATCP), were mixed with either deionized water or a 0.1M Na2HPO4 aqueous solution. The crystalline evolution of the paste was assessed quantitatively during the first 48h of hydration at 23°C by G-factor quantification. The present investigations demonstrate that ATCP reacted earlier than crystalline α-TCP. The results also suggest the formation of an X-ray amorphous phase during the hydraulic conversion formation of α-TCP into CDHA.

  16. Oral calcium carbonate affects calcium but not phosphorus balance in stage 3-4 chronic kidney disease.

    PubMed

    Hill, Kathleen M; Martin, Berdine R; Wastney, Meryl E; McCabe, George P; Moe, Sharon M; Weaver, Connie M; Peacock, Munro

    2013-05-01

    Patients with chronic kidney disease (CKD) are given calcium carbonate to bind dietary phosphorus, reduce phosphorus retention, and prevent negative calcium balance; however, data are limited on calcium and phosphorus balance during CKD to support this. Here, we studied eight patients with stage 3 or 4 CKD (mean estimated glomerular filtration rate 36 ml/min) who received a controlled diet with or without a calcium carbonate supplement (1500 mg/day calcium) during two 3-week balance periods in a randomized placebo-controlled cross-over design. All feces and urine were collected during weeks 2 and 3 of each balance period and fasting blood, and urine was collected at baseline and at the end of each week. Calcium kinetics were determined using oral and intravenous (45)calcium. Patients were found to be in neutral calcium and phosphorus balance while on the placebo. Calcium carbonate supplementation produced positive calcium balance, did not affect phosphorus balance, and produced only a modest reduction in urine phosphorus excretion compared with placebo. Calcium kinetics demonstrated positive net bone balance but less than overall calcium balance, suggesting soft-tissue deposition. Fasting blood and urine biochemistries of calcium and phosphate homeostasis were unaffected by calcium carbonate. Thus, the positive calcium balance produced by calcium carbonate treatment within 3 weeks cautions against its use as a phosphate binder in patients with stage 3 or 4 CKD, if these findings can be extrapolated to long-term therapy.

  17. Calcium acetate versus calcium carbonate as phosphorus binders in patients on chronic haemodialysis: a controlled study.

    PubMed

    Ring, T; Nielsen, C; Andersen, S P; Behrens, J K; Sodemann, B; Kornerup, H J

    1993-01-01

    The first reported double-blind cross-over comparison between the phosphorus binders calcium carbonate and calcium acetate was undertaken in 15 stable patients on chronic maintenance haemodialysis. Detailed registration of diet and analysis of the protein catabolic rate suggested an unchanged phosphorus intake during the study. It was found that predialytic serum phosphate concentration was significantly decreased by 0.11 mmol/l (0.34 mg/dl) (P = 0.021, 95% confidence limits 0.02-0.21 mmol/l; 0.06-0.65 mg/dl) during calcium acetate treatment. The calcium phosphate product was insignificantly decreased during treatment with calcium acetate whereas we could not exclude the possibility that calcium concentration had increased.

  18. 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.

  19. 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

    2011-07-05

    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.

  20. Characterization of cytolytic neutrophil activation in vitro by amorphous hydrated calcium phosphate as a model of biomaterial inflammation.

    PubMed

    Edwards, Felicity C; Taheri, Amir; Dann, Sophie C; Dye, Julian F

    2011-03-01

    Calcium ions are utilized in biomolecular biomaterial design for osteomimetic scaffolds and as divalent cross-linking agents, typically for gelation of alginates, stabilisation of protein structure (e.g., fibrinogen) and enzyme activation (e.g., thrombin). Biological interactions with defined calcium phosphates (e.g., hydroxyapatite) are exploited for osteogenesis, although crystalline calcium phosphates (e.g., calcium pyrophosphate) stimulate inflammation. We found that the calcium concentration used in the manufacture of prototype dermal scaffolds made from fibrin/alginate composite was related to the inflammatory infiltration during in vivo integration. In investigating a cause for this inflammatory response, we have identified and characterized a cytolytic inflammatory effect of amorphous calcium phosphate (CaP) formed in physiological solutions, relevant to biomaterial biocompatibility. Isolated human neutrophils (Nφ) were incubated in phosphate-buffered saline with CaCl(2) ranging 2.5-20 mM total calcium. Nφ activation was assessed by morphology and integrin-β2 (CD18a) expression. Mediator release (Nφ-elastase, IL-8, and TNFα) was measured from both Nφ and whole blood cultures plus CaCl(2). CaP exposure increased CD18a expression over 1 h (maximal at 10 mM calcium/ phosphate) with concurrent phagocytosis, cytolysis, and Nφ-elastase release. CaCl(2) induced expression of IL-8 and TNFα in whole blood cultures. These results suggest that CaP formed from the resorption of calcium-containing biomaterials could induce inflammation and accelerate biomaterial degradation, driving further CaP release. This demonstrates a novel mechanism for biomaterial-induced inflammation. The in vitro system described could aid preclinical evaluation of novel biomaterial inflammatory potential.

  1. 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

  2. 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

  3. 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

  4. 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

  5. Twelve-month bracket failure rate with amorphous calcium phosphate bonding system.

    PubMed

    Hammad, Shaza M; El Banna, Mai S; Elsaka, Shaymaa E

    2013-10-01

    The aim of the study was to compare the survival rate of orthodontic brackets over a 12-month period using amorphous calcium phosphate (ACP) bonding system with a conventional adhesive (CA). In 30 patients with a mean age of 15 years 7 months, one operator bonded 138 brackets with a split-mouth design, using a resin-based CA and ACP-containing adhesive. The survival rate of the brackets was estimated by Kaplan-Meier analysis. Bracket survival distributions with respect to bonding procedure, dental arch, type of tooth (incisor, canine, and premolar), and patients' gender were compared using the log-rank test. The bond failure interface was determined using the Adhesive Remnant Index (ARI). The bond failure rates of the CA and ACP-containing adhesive were 2.67 and 3.8 per cent, respectively. There was no significant difference between the failure rates of ACP and CA-bonded systems (P > 0.05). Survival rates did not show significant differences between the upper and lower dental arches (P > 0.05). Lower survival rates were found for canine and premolar teeth than incisors (P < 0.05). Bond failure rates were higher for males than females (P < 0.05). There was a significant difference for ARI scores between the adhesive materials (P = 0.028); more of the ACP-based adhesive was left on the tooth at debond. ACP-containing adhesive can be effectively used to bond orthodontic brackets and can serve as a practicable alternative to the conventional bonding adhesives.

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

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

    Amorphous carbon microspheres were synthesized using a dual-furnace chemical vapour deposition method at 800-1000° 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° C. At 800° C, no regular microspheres were formed but more uniform structure is observed at 900° C. Generally the microspheres size is uniform when the heating temperature was increased to 1000° 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-1 for the D and G bands, respectively. These bands become more prominent as the preparation temperature increased from 800 to 1000° 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.

  7. 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.

  8. 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.

  9. 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

  10. Highly conductive carbon black supported amorphous molybdenum disulfide for efficient hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Cao, Pengfei; Peng, Jing; Li, Jiuqiang; Zhai, Maolin

    2017-04-01

    Molybdenum disulfide (MoS2) is a promising electrocatalyst for hydrogen evolution reaction (HER), however, the catalytic activity of reported MoS2-based materials towards HER still can't satisfy the requirement of practical application. Herein, highly conductive carbon black (CB) supported amorphous MoS2 nanocomposite is synthesized by a facile one-pot hydrothermal process. XRD and TEM analysis proves the amorphous morphology of MoS2. XPS further confirms both hexagonal and orthorhombic S ligands exist in the amorphous MoS2. Compared with crystalline MoS2, amorphous MoS2/CB shows an onset overpotential of 78 mV and current density of 470 mA cm-2 at the overpotential of 200 mV, which is even 50% higher than that of the commercial 20% Pt/C catalyst. Furthermore, a fairly stable performance can be achieved even after 5000 CV cycles. The outstanding HER activity and stability of the amorphous MoS2/CB nanocomposite can be attributed to these advantages: (1) amorphous structure offers more active sites in MoS2; (2) highly conductive CB reduces the charge transfer resistance (RCT); (3) relative hydrophilic CB can largely reduce the resistance between catalyst/electrolyte interface and allows rapid mass transport; (4) electron penetration effect between amorphous MoS2 and CB increases the intrinsic activity of amorphous MoS2 by two orders of magnitude.

  11. Formation of hollow bone-like morphology of calcium carbonate on surfactant/polymer templates

    NASA Astrophysics Data System (ADS)

    Mantilaka, M. M. M. G. P. G.; Pitawala, H. M. T. G. A.; Rajapakse, R. M. G.; Karunaratne, D. G. G. P.; Upul Wijayantha, K. G.

    2014-04-01

    Novel hollow, bone-like structures of Precipitated Calcium Carbonate (PCC) are fabricated, for the first time, starting from naturally occurring dolomite. The hollow, bone-like structures are prepared by precipitating calcium carbonate on self-assembled poly(acrylic acid)/cetyltrimethylammonium chloride (PAA/CTAC) template. Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), Transmission Electron Microscopy (TEM) and Field Emission Scanning Electron Microscopic (FE-SEM) studies reveal that the bone-like structure is composed of Amorphous Calcium Carbonate (ACC) nanoparticles in the center and calcite nanoparticles at the edges. Bone-like PCC particles are in particle length of 2-3 μm and particle width of 1 μm. The internal hollow structures of bone-like particles are observed from TEM images. As identified by FE-SEM images, the bone-like structure has been formed through the crystal growth of initially formed ACC nanoparticles. The ACC particles are stabilized in the center while the calcite crystals have been grown from the ACC toward the edges of the structure to form a bone-like morphology. We also propose a possible mechanism for the formation of hollow bone-like PCC in this study. The fabricated hollow, bone-like PCC has potential applications in the preparation of release systems such as drugs, cosmetics and pigments.

  12. 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

  13. Intrinsically disordered mollusk shell prismatic protein that modulates calcium carbonate crystal growth.

    PubMed

    Ndao, Moise; Keene, Ellen; Amos, Fairland F; Rewari, Gita; Ponce, Christopher B; Estroff, Lara; Evans, John Spencer

    2010-10-11

    The formation of calcite prism architecture in the prismatic layer of the mollusk shell involves the participation of a number of different proteins. One protein family, Asprich, has been identified as a participant in amorphous calcium carbonate stabilization and calcite architecture in the prismatic layer of the mollusk, Atrina rigida . However, the functional role(s) of this protein family are not fully understood due to the fact that insufficient quantities of these proteins are available for experimentation. To overcome this problem, we employed stepwise solid-phase synthesis to recreate one of the 10 members of the Asprich family, the 61 AA single chain protein, Asprich "3". We find that the Asprich "3" protein inhibits the formation of rhombohedral calcite crystals and induces the formation of round calcium carbonate deposits in vitro that contain calcite and amorphous calcium carbonate (ACC). This mineralization behavior does not occur under control conditions, and the formation of ACC and calcite is similar to that reported for the recombinant form of the Asprich "g" protein. Circular dichroism studies reveal that Asprich "3" is an intrinsically disordered protein, predominantly random coil (66%), with 20-30% β-strand content, a small percentage of β-turn, and little if any α-helical content. This protein is not extrinsically stabilized by Ca(II) ions but can be stabilized by 2,2,2-trifluoroethanol to form a structure consisting of turn-like and random coil characteristics. This finding suggests that Asprich "3" may require other extrinsic interactions (i.e., with mineral or ionic clusters or other macromolecules) to achieve folding. In conclusion, Asprich "3" possesses in vitro functional and structural qualities that are similar to other reported for other Asprich protein sequences.

  14. Availability of calcium from skim milk, calcium sulfate and calcium carbonate for bone mineralization in pigs.

    PubMed

    Pointillart, A; Coxam, V; Sève, B; Colin, C; Lacroix, C H; Guéguen, L

    2000-01-01

    Dairy products provide abundant, accessible calcium for humans, while some calcium sulfate-rich mineral waters could provide appreciable amounts of calcium. But there is little evidence that this calcium is as available as milk calcium for making bone. The availability of calcium was studied by monitoring bone parameters in 2-month-old pigs fed restricted amounts of calcium (70% RDA) for 2.5 months. The 3 main (> or = 50% Ca intake) Ca sources were either CaCO3 or CaSO4 or skim milk powder (29% of the diet). The bones of the pigs fed the "milk" diet had higher (P < 0.01) ash contents, breaking strength and density (DEXA) than those of the two others groups, in which the bone values were similar. Thus, the calcium provided by a diet containing milk appears to ensure better bone mineralization than do calcium salts included in a non-milk diet. The calcium restriction may have enhanced some milk properties to stimulate calcium absorption in these young, rapidly growing pigs.

  15. Ultrasound influence upon calcium carbonate precipitation on bacterial cellulose membranes.

    PubMed

    Stoica-Guzun, Anicuta; Stroescu, Marta; Jinga, Sorin; Jipa, Iuliana; Dobre, Tanase; Dobre, Loredana

    2012-07-01

    The effect of ultrasonic irradiation (40 kHz) on the calcium carbonate deposition on bacterial cellulose membranes was investigated using calcium chloride (CaCl(2)) and sodium carbonate (Na(2)CO(3)) as starting reactants. The composite materials containing bacterial cellulose-calcium carbonate were characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and color measurements. The polymorphs of calcium carbonate that were deposited on bacterial cellulose membranes in the presence or in the absence of ultrasonic irradiation were calcite and vaterite. The morphology of the obtained crystals was influenced by the concentration of starting solutions and by the presence of ultrasonic irradiation. In the presence of ultrasonic irradiation the obtained crystals were bigger and in a larger variety of shapes than in the absence of ultrasounds: from cubes of calcite to spherical and flower-like vaterite particles. Bacterial cellulose could be a good matrix for obtaining different types of calcium carbonate crystals.

  16. Acute effects of calcium carbonate, calcium citrate and potassium citrate on markers of calcium and bone metabolism in young women.

    PubMed

    Karp, Heini J; Ketola, Maarit E; Lamberg-Allardt, Christel J E

    2009-11-01

    Both K and Ca supplementation may have beneficial effects on bone through separate mechanisms. K in the form of citrate or bicarbonate affects bone by neutralising the acid load caused by a high protein intake or a low intake of alkalising foods, i.e. fruits and vegetables. Ca is known to decrease serum parathyroid hormone (S-PTH) concentration and bone resorption. We compared the effects of calcium carbonate, calcium citrate and potassium citrate on markers of Ca and bone metabolism in young women. Twelve healthy women aged 22-30 years were randomised into four controlled 24 h study sessions, each subject serving as her own control. At the beginning of each session, subjects received a single dose of calcium carbonate, calcium citrate, potassium citrate or a placebo in randomised order. The diet during each session was identical, containing 300 mg Ca. Both the calcium carbonate and calcium citrate supplement contained 1000 mg Ca; the potassium citrate supplement contained 2250 mg K. Markers of Ca and bone metabolism were followed. Potassium citrate decreased the bone resorption marker (N-terminal telopeptide of type I collagen) and increased Ca retention relative to the control session. Both Ca supplements decreased S-PTH concentration. Ca supplements also decreased bone resorption relative to the control session, but this was significant only for calcium carbonate. No differences in bone formation marker (bone-specific alkaline phosphatase) were seen among the study sessions. The results suggest that potassium citrate has a positive effect on the resorption marker despite low Ca intake. Both Ca supplements were absorbed well and decreased S-PTH efficiently.

  17. Raman spectroscopic study of the phase transition of amorphous to crystalline beta-carbonic acid.

    PubMed

    Kohl, Ingrid; Winkel, Katrin; Bauer, Marion; Liedl, Klaus R; Loerting, Thomas; Mayer, Erwin

    2009-01-01

    What's the matter? The laboratory Raman spectra for carbonic acid (H(2)CO(3)), both for the beta-polymorph and its amorphous state, are required to detect carbonic acid on the surface of the pole caps of Mars in 2009, when the Mars Microbeam Raman Spectrometer lands on the planet. The picture shows a martian crater with ice of unknown composition, possibly containing carbonic acid (image adapted from DLR, with permission from ESA, DLR, and FU Berlin--G. Neukum).

  18. 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.

  19. 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.

  20. Growth Mechanism for Low Temperature PVD Graphene Synthesis on Copper Using Amorphous Carbon

    NASA Astrophysics Data System (ADS)

    Narula, Udit; Tan, Cher Ming; Lai, Chao Sung

    2017-03-01

    Growth mechanism for synthesizing PVD based Graphene using Amorphous Carbon, catalyzed by Copper is investigated in this work. Different experiments with respect to Amorphous Carbon film thickness, annealing time and temperature are performed for the investigation. Copper film stress and its effect on hydrogen diffusion through the film grain boundaries are found to be the key factors for the growth mechanism, and supported by our Finite Element Modeling. Low temperature growth of Graphene is achieved and the proposed growth mechanism is found to remain valid at low temperatures.

  1. Growth Mechanism for Low Temperature PVD Graphene Synthesis on Copper Using Amorphous Carbon

    PubMed Central

    Narula, Udit; Tan, Cher Ming; Lai, Chao Sung

    2017-01-01

    Growth mechanism for synthesizing PVD based Graphene using Amorphous Carbon, catalyzed by Copper is investigated in this work. Different experiments with respect to Amorphous Carbon film thickness, annealing time and temperature are performed for the investigation. Copper film stress and its effect on hydrogen diffusion through the film grain boundaries are found to be the key factors for the growth mechanism, and supported by our Finite Element Modeling. Low temperature growth of Graphene is achieved and the proposed growth mechanism is found to remain valid at low temperatures. PMID:28276475

  2. Formation and structure of amorphous carbon char from polymer materials

    NASA Astrophysics Data System (ADS)

    Lawson, John W.; Srivastava, Deepak

    2008-04-01

    Amorphous carbonaceous char produced from burning polymer solids has insulating properties that make it valuable in thermal protection and fire-retardant systems. A pyrolytic molecular dynamics simulation method is devised to study the transformation of the local microstructure from virgin polymer to a dense, disordered char. Release of polymer hydrogen is found to be critical to allow the system to collapse into a highly coordinated char structure. Mechanisms of the char formation process and the morphology of the resulting structures are elucidated.

  3. Sustained delivery of calcium and orthophosphate ions from amorphous calcium phosphate and poly(L-lactic acid)-based electrospinning nanofibrous scaffold

    PubMed Central

    Niu, Xufeng; Liu, Zhongning; Tian, Feng; Chen, Siqian; Lei, Lei; Jiang, Ting; Feng, Qingling; Fan, Yubo

    2017-01-01

    The purpose of this study is to investigate electrospinning poly(L-lactic acid) (PLLA) nanofibrous scaffold with different contents of amorphous calcium phosphate (ACP), which is suitable for using in bone regeneration through sustained release of calcium and orthophosphate ions. Three groups of nanofibrous scaffolds, ACP-free PLLA, ACP-5 wt%/PLLA and ACP-10 wt%/PLLA, are developed and characterized by scanning electron microscopy and gel permeation chromatography. Calcium and phosphate colorimetric assay kits are used to test ions released from scaffold during hydrolytic degradation. The results show ACP-5 wt%/PLLA and ACP-10 wt%/PLLA scaffolds have relatively high degradation rates than ACP-free PLLA group. The bioactivity evaluation further reveals that ACP-5 wt%/PLLA scaffold presents more biocompatible feature with pre-osteoblast cells and significant osteogenesis ability of calvarial bone defect. Due to the facile preparation method, sustained calcium and orthophosphate release behavior, and excellent osteogenesis capacity, the presented ACP/PLLA nanofibrous scaffold has potential applications in bone tissue engineering. PMID:28361908

  4. 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

  5. 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.

  6. 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.

  7. Carbon-Incorporated Amorphous Indium Zinc Oxide Thin-Film Transistors

    NASA Astrophysics Data System (ADS)

    Parthiban, S.; Park, K.; Kim, H.-J.; Yang, S.; Kwon, J.-Y.

    2014-11-01

    We propose the use of amorphous-carbon indium zinc oxide (a-CIZO) as a channel material for thin-film transistor (TFT) fabrication. This study chose a carbon dopant as a carrier suppressor and strong oxygen binder in amorphous-indium zinc oxide (a-IZO) channel material. a-CIZO thin films were deposited using radiofrequency (RF) sputtering and postannealed at 150°C. X-ray diffraction and transmission electron microscopy analysis revealed that the film remained amorphous even after postannealing. The a-CIZO TFT postannealed at 150°C exhibited saturation field-effect mobility of 16.5 cm2 V-1 s-1 and on-off current ratio of ˜4.3 × 107.

  8. 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.

  9. Formation and structure of amorphous carbon char from polymer materials

    NASA Astrophysics Data System (ADS)

    Lawson, John; Srivastava, Deepak

    2008-03-01

    Amorphous carbonaceous char produced from burning polymer solids has insulating properties that makes it valuable for aerospace thermal protection systems as well as for fire retardants. A pyrolytic molecular dynamics simulation method is devised to study the transformation of the local microstructure from virgin polymer to a dense, disordered char. Release of polymer hydrogen is found to be critical to allow the system to collapse into a highly coordinated structure. Mechanisms of the char formation process and the morphology of the resulting structure are elucidated.

  10. 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

  11. 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...

  12. Low-Temperature Synthesis of Hierarchical Amorphous Basic Nickel Carbonate Particles for Water Oxidation Catalysis.

    PubMed

    Yang, Yisu; Liang, Fengli; Li, Mengran; Rufford, Thomas E; Zhou, Wei; Zhu, Zhonghua

    2015-07-08

    Amorphous nickel carbonate particles are catalysts for the oxygen evolution reaction (OER), which plays a critical role in the electrochemical splitting of water. The amorphous nickel carbonate particles can be prepared at a temperature as low as 60 °C by an evaporation-induced precipitation (EIP) method. The products feature hierarchical pore structures. The mass-normalized activity of the catalysts, measured at an overpotential of 0.35 V, was 55.1 A g(-1) , with a Tafel slope of only 60 mV dec(-1) . This catalytic activity is superior to the performance of crystalline NiOx particles and β-Ni(OH)2 particles, and compares favorably to state-of-the-art RuO2 catalysts. The activity of the amorphous nickel carbonate is remarkably stable during a 10 000 s chronoamperometry test. Further optimization of synthesis parameters reveals that the amorphous structure can be tuned by adjusting the H2 O/Ni ratio in the precursor mixture. These results suggest the potential application of easily prepared hierarchical basic nickel carbonate particles as cheap and robust OER catalysts with high activity.

  13. Catalytic properties of composite amorphous carbon-platinum layers in fuel cells

    SciTech Connect

    Nechitailov, A. A. Zvonareva, T. K.; Remenyuk, A. D.; Tolmachev, V. A.; Goryachev, D. N.; El'tsina, O. S.; Belyakov, L. V.; Sreseli, O. M.

    2008-10-15

    Catalytic properties of composite amorphous carbon-platinum layers produced by magnetron cosputtering have been studied. The layers were characterized by electron microscopy, IR spectroscopy, ellipsometry, gravimetry, and spectrophotometric chemical analysis. The catalytic activity of the layers was studied in an air-hydrogen fuel cell by measuring its load and power characteristics.

  14. Design of Amorphous Manganese Oxide@Multiwalled Carbon Nanotube Fiber for Robust Solid-State Supercapacitor.

    PubMed

    Shi, Peipei; Li, Li; Hua, Li; Qian, Qianqian; Wang, Pengfei; Zhou, Jinyuan; Sun, Gengzhi; Huang, Wei

    2017-01-24

    Solid-state fiber-based supercapacitors have been considered promising energy storage devices for wearable electronics due to their lightweight and amenability to be woven into textiles. Efforts have been made to fabricate a high performance fiber electrode by depositing pseudocapacitive materials on the outer surface of carbonaceous fiber, for example, crystalline manganese oxide/multiwalled carbon nanotubes (MnO2/MWCNTs). However, a key challenge remaining is to achieve high specific capacitance and energy density without compromising the high rate capability and cycling stability. In addition, amorphous MnO2 is actually preferred due to its disordered structure and has been proven to exhibit superior electrochemical performance over the crystalline one. Herein, by incorporating amorphous MnO2 onto a well-aligned MWCNT sheet followed by twisting, we design an amorphous MnO2@MWCNT fiber, in which amorphous MnO2 nanoparticles are distributed in MWCNT fiber uniformly. The proposed structure gives the amorphous MnO2@MWCNT fiber good mechanical reliability, high electrical conductivity, and fast ion-diffusion. Solid-state supercapacitor based on amorphous MnO2@MWCNT fibers exhibits improved energy density, superior rate capability, exceptional cycling stability, and excellent flexibility. This study provides a strategy to design a high performance fiber electrode with microstructure control for wearable energy storage devices.

  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.

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

    SciTech Connect

    Rodriguez-Manzo, Julio A.; Banhart, Florian

    2011-05-02

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

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

    NASA Technical Reports Server (NTRS)

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

    2015-01-01

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

  18. Calcium carbonate crystallization in the α-chitin matrix of the shell of pink shrimp, Pandalus borealis, during frozen storage

    NASA Astrophysics Data System (ADS)

    Mikkelsen, A.; Engelsen, S. B.; Hansen, H. C. B.; Larsen, O.; Skibsted, L. H.

    1997-05-01

    Calcium carbonate precipitates in the shell of pink shrimp, Pandalus borealis, during frozen storage (investigated for temperatures above - 30°C), and as a result white spots appear in the shell. During continued frozen storage the white spots grow in size and eventually cover the entire, originally transparent, shell. Material isolated from shrimp shells was dried and subjected to infrared and Raman spectroscopy, X-ray diffraction, electron microscopy and EDX analyses. It was found that the white spots were composed of crystalline calcium carbonate in the two crystal forms of calcite and vaterite, and of amorphous α-chitin. It is proposed that α-chitin plays an important role in the crystallization process of white spots, as an integral part of the white spots. It is shown that the relative w/w-concentrations of α-chitin and calcium carbonate in white spots were constant (0.34 : 0.66), and it did not depend on chemical treatments comparable to those in use by the fishing industry for production of raw and frozen shrimps. However, the ratio of the polymorphic forms of calcium carbonate varied.

  19. 40 CFR 415.300 - Applicability; description of the calcium carbonate production subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... resulting from the production of calcium carbonate by the milk of lime process and by the recovery process... calcium carbonate production subcategory. 415.300 Section 415.300 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Calcium Carbonate Production Subcategory § 415.300 Applicability; description of...

  20. Calcium supplements

    MedlinePlus

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

  1. Direct Observation of Completely Processed Calcium Carbonate Dust Particles

    SciTech Connect

    Laskin, Alexander; Iedema, Martin J.; Ichkovich, Aviad; Graber, Ellen R.; Taraniuk, Ilya; Rudich, Yinon

    2005-05-27

    This study presents, for the first time, field evidence of complete, irreversible processing of solid calcium carbonate (calcite)-containing particles and quantitative formation of liquid calcium nitrate particles apparently as a result of heterogeneous reaction of calcium carbonate-containing mineral dust particles with gaseous nitric acid. Formation of nitrates from individual calcite and sea salt particles was followed as a function of time in aerosol samples collected at Shoresh, Israel. Morphology and compositional changes of individual particles were observed using conventional scanning electron microscopy with energy dispersive analysis of X-rays (SEM/EDX) and computer controlled SEM/EDX. Environmental scanning electron microscopy (ESEM) was utilized to determine and demonstrate the hygroscopic behavior of calcium nitrate particles found in some of the samples. Calcium nitrate particles are exceptionally hygroscopic and deliquesce even at very low relative humidity (RH) of 9 -11% which is lower than typical atmospheric environments. Transformation of non-hygroscopic dry mineral dust particles into hygroscopic wet aerosol may have substantial impacts on light scattering properties, the ability to modify clouds and heterogeneous chemistry.

  2. Dissolution and storage stability of nanostructured calcium carbonates and phosphates for nutrition

    NASA Astrophysics Data System (ADS)

    Posavec, Lidija; Knijnenburg, Jesper T. N.; Hilty, Florentine M.; Krumeich, Frank; Pratsinis, Sotiris E.; Zimmermann, Michael B.

    2016-10-01

    Rapid calcium (Ca) dissolution from nanostructured Ca phosphate and carbonate (CaCO3) powders may allow them to be absorbed in much higher fraction in humans. Nanosized Ca phosphate and CaCO3 made by flame-assisted spray pyrolysis were characterized by nitrogen adsorption, X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy. As-prepared nanopowders contained both CaCO3 and CaO, but storing them under ambient conditions over 130 days resulted in a complete transformation into CaCO3, with an increase in both crystal and particle sizes. The small particle size could be stabilized against such aging by cation (Mg, Zn, Sr) and anion (P) doping, with P and Mg being most effective. Calcium phosphate nanopowders made at Ca:P ≤ 1.5 were XRD amorphous and contained γ-Ca2P2O7 with increasing hydroxyapatite content at higher Ca:P. Aging of powders with Ca:P = 1.0 and 1.5 for over 500 days gradually increased particle size (but less than for CaCO3) without a change in phase composition or crystallinity. In 0.01 M H3PO4 calcium phosphate nanopowders dissolved ≈4 times more Ca than micronsized compounds and about twice more Ca than CaCO3 nanopowders, confirming that nanosizing and/or amorphous structuring sharply increases Ca powder dissolution. Because higher Ca solubility in vitro generally leads to greater absorption in vivo, these novel FASP-made Ca nanostructured compounds may prove useful for nutrition applications, including supplementation and/or food fortification.

  3. Core-shell amorphous silicon-carbon nanoparticles for high performance anodes in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Sourice, Julien; Bordes, Arnaud; Boulineau, Adrien; Alper, John P.; Franger, Sylvain; Quinsac, Axelle; Habert, Aurélie; Leconte, Yann; De Vito, Eric; Porcher, Willy; Reynaud, Cécile; Herlin-Boime, Nathalie; Haon, Cédric

    2016-10-01

    Core-shell silicon-carbon nanoparticles are attractive candidates as active material to increase the capacity of Li-ion batteries while mitigating the detrimental effects of volume expansion upon lithiation. However crystalline silicon suffers from amorphization upon the first charge/discharge cycle and improved stability is expected in starting with amorphous silicon. Here we report the synthesis, in a single-step process, of amorphous silicon nanoparticles coated with a carbon shell (a-Si@C), via a two-stage laser pyrolysis where decomposition of silane and ethylene are conducted in two successive reaction zones. Control of experimental conditions mitigates silicon core crystallization as well as formation of silicon carbide. Auger electron spectroscopy and scanning transmission electron microscopy show a carbon shell about 1 nm in thickness, which prevents detrimental oxidation of the a-Si cores. Cyclic voltammetry demonstrates that the core-shell composite reaches its maximal lithiation during the first sweep, thanks to its amorphous core. After 500 charge/discharge cycles, it retains a capacity of 1250 mAh.g-1 at a C/5 rate and 800 mAh.g-1 at 2C, with an outstanding coulombic efficiency of 99.95%. Moreover, post-mortem observations show an electrode volume expansion of less than 20% and preservation of the nanostructuration.

  4. 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

  5. Linking crystal structure with temperature-sensitive vibrational modes in calcium carbonate minerals.

    PubMed

    Xu, Ben; Poduska, Kristin M

    2014-09-07

    We demonstrate a correlation between how an IR-active vibrational mode responds to temperature changes and how it responds to crystallinity differences. Infrared (IR) spectroscopy was used to track changes in carbonate-related vibrational modes in three different CaCO3 polymorphs (calcite, aragonite, and vaterite) and CaMg(CO3)2 (dolomite) during heating. Of the three characteristic IR-active carbonate modes, the in-plane bending mode (ν4) shows the most pronounced changes with heating in polymorphs that have planar carbonate arrangements (calcite, aragonite, and dolomite). In contrast, this mode is virtually unchanged in vaterite, which has a canted arrangement of carbonate units. We correlate these trends with recent studies that identified the ν4 mode as most susceptible to changes related to crystallinity differences in calcite and amorphous calcium carbonate. Thus, our results suggest that studies of packing arrangements could provide a generalizable approach to identify the most diagnostic vibrational modes for tracking either temperature-dependent or crystallinity-related effects in IR-active solids.

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  9. Application of amorphous carbon based materials as antireflective coatings on crystalline silicon solar cells

    NASA Astrophysics Data System (ADS)

    da Silva, D. S.; Côrtes, A. D. S.; Oliveira, M. H.; Motta, E. F.; Viana, G. A.; Mei, P. R.; Marques, F. C.

    2011-08-01

    We report on the investigation of the potential application of different forms of amorphous carbon (a-C and a-C:H) as an antireflective coating for crystalline silicon solar cells. Polymeric-like carbon (PLC) and hydrogenated diamond-like carbon films were deposited by plasma enhanced chemical vapor deposition. Tetrahedral amorphous carbon (ta-C) was deposited by the filtered cathodic vacuum arc technique. Those three different amorphous carbon structures were individually applied as single antireflective coatings on conventional (polished and texturized) p-n junction crystalline silicon solar cells. Due to their optical properties, good results were also obtained for double-layer antireflective coatings based on PLC or ta-C films combined with different materials. The results are compared with a conventional tin dioxide (SnO2) single-layer antireflective coating and zinc sulfide/magnesium fluoride (ZnS/MgF2) double-layer antireflective coatings. An increase of 23.7% in the short-circuit current density, Jsc, was obtained using PLC as an antireflective coating and 31.7% was achieved using a double-layer of PLC with a layer of magnesium fluoride (MgF2). An additional increase of 10.8% was obtained in texturized silicon, representing a total increase (texturization + double-layer) of about 40% in the short-circuit current density. The potential use of these materials are critically addressed considering their refractive index, optical bandgap, absorption coefficient, hardness, chemical inertness, and mechanical stability.

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

    PubMed

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

    2015-07-28

    Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have characterized these precursors and the crystallization pathways and products with solid-state, spectroscopic and microscopic techniques to explain the differences in crystallization mechanisms between the La and Nd systems. ALC and ANC consist of highly hydrated, 10-20 nm spherical nanoparticles with a general formula of REE2(CO3)3·5H2O (REE = La, Nd). The stabilities differ by ∼2 orders of magnitude, with ANC being far more stable than ALC. This difference is due to the Nd(3+) ion having a far higher hydration energy compared to the La(3+) ion. This, together with temperature and reaction times, leads to clear differences not only in the kinetics and mechanisms of crystallization of the amorphous precursor La- and Nd-carbonate phases but also in the resulting crystallite sizes and morphologies of the end products. All crystalline La and Nd carbonates developed spherulitic morphologies when crystallization occurred from hydrous phases in solution at temperatures above 60 °C (La system) and 95 °C (Nd system). We suggest that spherulitic growth occurs due to a rapid breakdown of the amorphous precursors and a concurrent rapid increase in supersaturation levels in the aqueous solution. The kinetic data show that the crystallization pathway for both La and Nd carbonate systems is dependent on the reaction temperature and the ionic potential of the REE(3+) ion.

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

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

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

  12. Amorphous hollow carbon spheres synthesized using radio frequency plasma-enhanced chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Yang, G. M.; Xu, Q.; Tian, H. W.; Wang, X.; Zheng, W. T.

    2008-10-01

    We report a method to synthesize amorphous hollow carbon spheres, with diameters ranging from 100 to 800 nm, which are dispersed among bent graphitized carbon nanotubes using radio frequency plasma-enhanced chemical vapour deposition in mixed CH4/H2 gases. The products are characterized by techniques including scanning electron microscopy, energy-dispersive x-ray spectroscopy, Raman spectroscopy and transmission electron microscopy. It is found that MgO and Ni nanoparticles together with hydrogen play important roles in the formation of the spheres. A possible formation mechanism for the carbon composites has been proposed.

  13. Study of electrochemical performance of amorphous carbon-coated graphite for Li-ion battery

    NASA Astrophysics Data System (ADS)

    Rohman, Fadli; Azizah, Umi; Prihandoko, Bambang

    2017-03-01

    Electrochemical performance of graphite coated by amorphous carbon as anode material in the Li-ion battery has been studied with citric acid (labelled CA) as a carbon source with different composition. Citric acid as the amorphous carbon source was mixed with graphite in the ethanol solvent at 80°C using magnetic stirrer with the compositions CA: graphite 2:1, 1:1 and 1:3, respectively. The mixture of graphite and CA were dried at 350°C for 5 hours under Ar atmosphere to evaporate the solvent. This dried mixture was then sintered at 600°C under Ar atmosphere to form amorphous carbon layer on the surface of graphite. The crystal structure and morphology of the particles were characterized using XRD, SEM and TEM, respectively. Electrochemical properties of the samples have been evaluated by cyclic voltammetry and charge-discharge test using WBCS 3000. Cyclic voltammogram showed the working potential and redox reaction peak of the sample. Charge-discharge data was obtained to determine the specific capacity of the sample at 0.1C - 2C.

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

    SciTech Connect

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

    2014-07-28

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

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

    DOE PAGES

    Zhang, Fan; Allen, Andrew J.; Levine, Lyle E.; ...

    2014-07-28

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

  16. The structure and evolution of hydrogenated amorphous carbon grains and mantles in the interstellar medium

    NASA Astrophysics Data System (ADS)

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

    1990-12-01

    Hydrogenated amorphous carbons (HACs) have been proposed as the major constituent of interstellar dust. The HAC model can account successfully for observed properties of interstellar dust, and has great predictive power. A review is presented of relevant laboratory data on amorphous carbon, known to exist in three major phases: graphitic, diamondlike, and polymeric. These data indicate the probable nature of HAC in the interstellar medium. The properties of the HAC dust model, the deposition of HAC in the interstellar medium, and its evolution as interstellar conditions change are summarized. The properties of laboratory HAC in its various forms account successfully for observed interstellar extinction and for variations in extinction, for infrared emission features, and for extended red emission seen in reflection nebulae. A full evolutionary sequence that links the various HAC modifications found in different interstellar environments is proposed. It is concluded that the interstellar dust is an active component of the interstellar medium, responsive to its environment.

  17. Structural Models of Amorphous Carbon and its Surfaces by Tight-Binding Molecular Dynamics

    SciTech Connect

    Haerle, R.; Baldereschi, A.; Galli, G.

    1999-10-26

    We use liner-scaling tight-binding molecular dynamics to generate three structural models of bulk amorphous carbon with different atomic density. Amorphous carbon surfaces are then obtained by imposing tensile strain on these computer generated networks until fracture occurs. Our results show that for a given density, the formation energy of surfaces obtained with different tensile strains differ by only a few 10{sup -1} eV/atom and their structural properties are qualitatively similar. The presence of sp sites at the surface is observed at all densities, but with different values of the concentration. The surface thicknesses obtained in our simulations agree with experimental data. Furthermore we find that surface roughness increases with the amount of graphitic component in the bulk sample. The same trends of the macroscopic properties are obtained when using a two-center tight-binding Hamiltonian, an environmental dependent one, and first principles calculations.

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

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

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

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

    PubMed

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

    2016-05-06

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

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

    PubMed Central

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

    2015-01-01

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

  1. An atomistic study of growth mode and microstructure evolution of amorphous carbon films by different incident carbon atoms

    NASA Astrophysics Data System (ADS)

    Xue, Chen; Zhou, Jianqiu

    2014-09-01

    In this paper, molecular dynamics (MD) simulation has been performed to describe the growth and interfacial microstructure of amorphous carbon films. We focus on the film growth mode and surface morphology for diverse deposition process parameters mainly including incident energy and incident angle. To explore the relationship between the motion of deposition atoms and amorphous films growth, a series of snapshots for each deposition process has been taken for comparison. The snapshots show that the films growth modes are diverse at different incident parameters. In the next step, surface morphology, atom distribution along film growth direction and internal structure including vacancy defects evolution during deposition process are analyzed. The results reveal that incident energy on the horizontal plane dominates the surface roughness, and incident energy on the vertical plane dominates the compactness of the film. We conclude that a suitable incident parameter is not only beneficial to prepare amorphous films with compact and smooth or bump-like surface which will meet different needs, but also can avoid formation of defects during deposition. The simulation results are expected to provide useful guidance for improving amorphous carbon films quality.

  2. Polymorph-selective crystallization of calcium carbonate inspired by biomineralization

    NASA Astrophysics Data System (ADS)

    Kim, Il Won

    This dissertation primarily examines bioinspired mineralization, focusing on the polymorph-selective crystallization of calcium carbonate. (1) The effect of epitaxy on the polymorphic control of calcium carbonate was studied with aragonite-type inorganic substrates. The critical epitaxial mismatch for aragonite growth, when conditions disfavor aragonite, seems to be less than 7.1%. Larger epitaxial strain appeared to prohibit aragonite formation even though the substrates had the same crystal structure. The epitaxy required for aragonite nucleation seems to be more precise than that often suggested for biological systems. (2) Polymers of different aqueous-solution properties were tested to observe the effect on the crystallization of calcium carbonate. Near exclusive formation of aragonite was attained through the inhibition of more stable calcite with poly(vinyl alcohol). The contributing characteristics of poly(vinyl alcohol) seemed to be its ability to hydrogen bond and its tendency to adsorb non-specifically onto solid surfaces. Similar inhibition activity is suggested for various biomacromolecules involved in biogenic aragonite formation of mollusks, with the biomacromolecules acting in the same way as poly(vinyl alcohol). (3) Polymer surfaces imprinted by aragonite-type crystals (strontium carbonate) were studied as substrates for the crystallization of calcium carbonate. Only calcite formed under vaterite-, aragonite-, and calcite-favorable conditions. This result seemed to arise from the nature of functional groups, rather than from the molecular structure of the imprint. Interaction between the functional groups and calcium carbonate is suggested to have enhanced the crystallization rate, resulting in the rapid formation of the thermodynamically stable calcite irrespective of the bulk crystallization conditions. (4) A catechol-based monomer was synthesized in the course of developing a dental adhesive, which mimics the functionalities of mussel adhesive

  3. 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.

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

    DOE PAGES

    Baxamusa, Salmaan; Laurence, Ted; Worthington, Matthew; ...

    2015-11-10

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    NASA Astrophysics Data System (ADS)

    Xie, J.; Komvopoulos, K.

    2016-03-01

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

  8. Geometrically structured implants for cranial reconstruction made of biodegradable polyesters and calcium phosphate/calcium carbonate.

    PubMed

    Schiller, Carsten; Rasche, Christian; Wehmöller, Michael; Beckmann, Felix; Eufinger, Harald; Epple, Matthias; Weihe, Stephan

    2004-01-01

    The aim of this study was the development of a processing pathway for manufacturing of biodegradable skull implants with individual geometry. The implants on the basis of polylactide and calcium phosphate/calcium carbonate were prepared by a combination of hot pressing and gas foaming. On the inside, the implant consists of a macroporous and faster degradable material (poly(D,L-lactide)+CaCO3) to allow the ingrowth of bone cells. The pore size is in the range of 200-400 microm. On the outside, the implant consists of a compact and slower biodegradable material (poly(L-lactide) and calcium phosphate) to ensure mechanical stability and protection. To overcome problems like inflammatory reactions caused by acidic degradation products of polylactide, the polyester was combined with basic filling materials (calcium salts). The filler neutralises the lactic acid produced during polymer degradation and increases the bioactivity of the material. The stabilised pH was demonstrated by long-term in vitro pH studies. Over a time period of 250 d in demineralised water, the pH was in the physiological range. The in vitro biocompatibility was shown by cell cultures with human osteoblasts. A good proliferation of the cells was observed over the whole test period of 4 weeks.

  9. Plasma-deposited amorphous hydrogenated carbon films and their tribological properties

    NASA Technical Reports Server (NTRS)

    Miyoshi, Kazuhisa; Pouch, John J.; Alterovitz, Samuel A.

    1989-01-01

    Recent work on the properties of diamondlike carbon films and their dependence on preparation conditions are reviewed. The results of the study indicate that plasma deposition enables one to deposit a variety of amorphous hydrogenated carbon (a-C:H ) films exhibiting more diamondlike behavior to more graphitic behavior. The plasma-deposited a-C:H can be effectively used as hard, wear-resistant, and protective lubricating films on ceramic materials such as Si(sub 3)N(sub 4) under a variety of environmental conditions such as moist air, dry nitrogrn, and vacuum.

  10. Synthesis and optical enhancement of amorphous carbon nanotubes/silver nanohybrids via chemical route at low temperature.

    PubMed

    Han, Tan Kim; Fen, Leo Bey; Nee, Ng Meng; Johan, Mohd Rafie

    2014-01-01

    We report the synthesis of amorphous carbon nanotubes/silver (αCNTs/Ag) nanohybrids via simple chemical route without additional reactant and surfactant at low temperature. Field emission scanning microscope (FESEM) and transmission electron microscope (TEM) confirmed formation of CNTs. X-ray diffraction (XRD) pattern confirmed the amorphous phase of carbon and the formation of Ag nanoparticles crystalline phase. Raman spectra revealed the amorphous nature of α CNTs. UV-visible spectroscopy showed enhancement of optical properties of α CNTs/Ag nanohybrids.

  11. Modification of nanostructured calcium carbonate for efficient gene delivery.

    PubMed

    Zhao, Dong; Wang, Chao-Qun; Zhuo, Ren-Xi; Cheng, Si-Xue

    2014-06-01

    In this study, a facile method to modify nanostructured calcium carbonate (CaCO3) gene delivery systems by adding calcium phosphate (CaP) component was developed. CaCO3/CaP/DNA nanoparticles were prepared by the co-precipitation of Ca(2+) ions with plasmid DNA in the presence of carbonate and phosphate ions. For comparison, CaCO3/DNA nanoparticles and CaP/DNA co-precipitates were also prepared. The effects of carbonate ion/phosphate ion (CO3(2-)/PO4(3-)) ratio on the particle size and gene delivery efficiency were investigated. With an appropriate CO3(2-)/PO4(3-) ratio, the co-existence of carbonate and phosphate ions could control the size of co-precipitates effectively, and CaCO3/CaP/DNA nanoparticles with a decreased size and improved stability could be obtained. The in vitro gene transfections mediated by different nanoparticles in 293T cells and HeLa cells were carried out, using pGL3-Luc as a reporter plasmid. The gene transfection efficiency of CaCO3/CaP/DNA nanoparticles could be significantly improved as compared with CaCO3/DNA nanoparticles and CaP/DNA co-precipitates. The confocal microscopy study indicated that the cellular uptake and nuclear localization of CaCO3/CaP/DNA nanoparticles were significantly enhanced as compared with unmodified CaCO3/DNA nanoparticles.

  12. Hardness and modulus properties in ion-beam-modified amorphous carbon: Temperature and dose rate dependences

    SciTech Connect

    Lee, D.; Lee, H.; Park, B.

    1997-08-01

    Ion implantation into amorphous carbon has been initiated to investigate the possibility of superhard carbon-nitride formation. Studies of implantation-temperature effects by 100 keV N{sup +} or 80 keV C{sup +} ions at 50 {mu}A show a narrow temperature window at approximately {minus}100{degree}C for the optimum surface hardness and elastic modulus (measured by nanoindentation), both values much higher than those for the unimplanted amorphous carbon. No distinguishable properties are found between nitrogen and self (carbon) implantations. At a dose rate of 5 {mu}A, however, the optimum hardness and modulus are found at a lower implantation temperature, with a broader temperature window. The enhanced strengths are well correlated with the asymmetric diffuse peak at around 1500cm{sup {minus}1} in Raman spectroscopy, and the increased ratio of sp{sup 3}- over sp{sup 2}- bonded carbon sites observed by electron energy loss spectroscopy. {copyright} {ital 1997 Materials Research Society.}

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

    PubMed

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

    2015-04-01

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

  14. Carbonate-containing apatite (CAP) synthesis under moderate conditions starting from calcium carbonate and orthophosphoric acid.

    PubMed

    Pham Minh, Doan; Tran, Ngoc Dung; Nzihou, Ange; Sharrock, Patrick

    2013-07-01

    The synthesis of carbonate-containing apatite (CAP) from calcium carbonate and orthophosphoric acid under moderate conditions was investigated. In all cases, complete precipitation of orthophosphate species was observed. The reaction temperature influenced strongly the decomposition of calcium carbonate and therefore the composition of formed products. The reaction temperature of 80 °C was found to be effective for the complete decomposition of calcium carbonate particles after 48 h of reaction. Infra-red spectroscopy (IR), nuclear magnetic resonance (NMR), thermogravimetry/mass spectroscopy (TG-MS) coupling, and X-ray diffraction (XRD) characterizations allowed the identification of the composition of formed products. By increasing the reaction temperature from 20 °C to 80 °C, the content of A-type CAP increased and that of B-type CAP decreased, according to the favorable effect of temperature on the formation of A-type CAP. The total amount of carbonate content incorporated in CAP's structure, which was determined by TG-MS analysis, increased with the reaction temperature and reached up to 4.1% at 80 °C. At this temperature, the solid product was mainly composed of apatitic components and showed the typical flat-needle-like structure of CAP particles obtained in hydrothermal conditions. These results show an interesting one-step synthesis of CAP from calcium carbonate and orthophosphoric acid as low cost but high purity starting materials.

  15. 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.

  16. A study of the formation of amorphous calcium phosphate and hydroxyapatite on melt quenched Bioglass using surface sensitive shallow angle X-ray diffraction.

    PubMed

    Martin, R A; Twyman, H; Qiu, D; Knowles, J C; Newport, R J

    2009-04-01

    Melt quenched silicate glasses containing calcium, phosphorous and alkali metals have the ability to promote bone regeneration and to fuse to living bone. These glasses, including 45S5 Bioglass((R)) [(CaO)(26.9)(Na(2)O)(24.4)(SiO(2))(46.1)(P(2)O(5))(2.6)], are routinely used as clinical implants. Consequently there have been numerous studies on the structure of these glasses using conventional diffraction techniques. These studies have provided important information on the atomic structure of Bioglass((R)) but are of course intrinsically limited in the sense that they probe the bulk material and cannot be as sensitive to thin layers of near-surface dissolution/growth. The present study therefore uses surface sensitive shallow angle X-ray diffraction to study the formation of amorphous calcium phosphate and hydroxyapatite on Bioglass((R)) samples, pre-reacted in simulated body fluid (SBF). Unreacted Bioglass((R)) is dominated by a broad amorphous feature around 2.2 A(-1) which is characteristic of sodium calcium silicate glass. After reacting Bioglass((R)) in SBF a second broad amorphous feature evolves ~1.6 A(-1) which is attributed to amorphous calcium phosphate. This feature is evident for samples after only 4 h reacting in SBF and by 8 h the amorphous feature becomes comparable in magnitude to the background signal of the bulk Bioglass((R)). Bragg peaks characteristic of hydroxyapatite form after 1-3 days of reacting in SBF.

  17. 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 ...

  18. Proteomic analysis of a rare urinary stone composed of calcium carbonate and calcium oxalate dihydrate: a case report.

    PubMed

    Kaneko, Kiyoko; Matsuta, Yosuke; Moriyama, Manabu; Yasuda, Makoto; Chishima, Noriharu; Yamaoka, Noriko; Fukuuchi, Tomoko; Miyazawa, Katsuhito; Suzuki, Koji

    2014-03-01

    The objective of the present study was to investigate the matrix protein of a rare urinary stone that contained calcium carbonate. A urinary stone was extracted from a 34-year-old male patient with metabolic alkalosis. After X-ray diffractometry and infrared analysis of the stone, proteomic analysis was carried out. The resulting mass spectra were evaluated with protein search software, and matrix proteins were identified. X-ray diffraction and infrared analysis confirmed that the stone contained calcium carbonate and calcium oxalate dihydrate. Of the identified 53 proteins, 24 have not been previously reported from calcium oxalate- or calcium phosphate-containing stones. The protease inhibitors and several proteins related to cell adhesion or the cytoskeleton were identified for the first time. We analyzed in detail a rare urinary stone composed of calcium carbonate and calcium oxalate dihydrate. Considering the formation of a calcium carbonate stone, the new identified proteins should play an important role on the urolithiasis process in alkaline condition.

  19. 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.

  20. HRTEM low dose: the unfold of the morphed graphene, from amorphous carbon to morphed graphenes.

    PubMed

    Calderon, H A; Okonkwo, A; Estrada-Guel, I; Hadjiev, V G; Alvarez-Ramírez, F; Robles Hernández, F C

    We present experimental evidence under low-dose conditions transmission electron microscopy for the unfolding of the evolving changes in carbon soot during mechanical milling. The milled soot shows evolving changes as a function of the milling severity or time. Those changes are responsible for the transformation from amorphous carbon to graphenes, graphitic carbon, and highly ordered structures such as morphed graphenes, namely Rh6 and Rh6-II. The morphed graphenes are corrugated layers of carbon with cross-linked covalently nature and sp(2)- or sp(3)-type allotropes. Electron microscopy and numerical simulations are excellent complementary tools to identify those phases. Furthermore, the TEAM 05 microscope is an outstanding tool to resolve the microstructure and prevent any damage to the sample. Other characterization techniques such as XRD, Raman, and XPS fade to convey a true identification of those phases because the samples are usually blends or mixes of the mentioned phases.

  1. Supplemental Information: Phototransformation-Induced Aggregation of Functionalized Single-Walled Carbon Nanotubes: the Importance of Amorphous Carbon

    EPA Pesticide Factsheets

    Additional information about the carboxylated SWCNT calibration curve, AFM images, EDS results, solar simulator light and UVB lamp spectra, TEM image ofparent carboxylated SWCNTs, XPS spectra of the dark control P3 sample and the irradiated P3 sample, and a table summarizing the kinetic parameters (PDF)This dataset is associated with the following publication:Hou, W., C. He, Y. Wang, D. Wang, and R. Zepp. Phototransformation-Induced Aggregation of Functionalized Single-Walled Carbon Nanotubes: The Importance of Amorphous Carbon. ENVIRONMENTAL SCIENCE & TECHNOLOGY. American Chemical Society, Washington, DC, USA, 50(7): 3494–3502, (2016).

  2. In situ electron microscopy studies of calcium carbonate precipitation from aqueous solution with and without organic additives.

    PubMed

    Verch, Andreas; Morrison, Ian E G; Locht, Renee van de; Kröger, Roland

    2013-08-01

    For the understanding of mineral formation processes from solution it is important to obtain a deeper insight into the dynamics of crystal growth. In this study we applied for this purpose a novel atmospheric scanning electron microscope that allows the investigation of CaCO3 particle formation in solution under atmospheric conditions with a resolution of approximately 10nm. Furthermore it permits the in situ observation of the dynamics of crystal evolution. With this tool the precipitation of CaCO3 was studied in the absence and presence of additives, namely poly(acrylic acid) and poly(styrene sulfonate-co-maleic acid) which are known to influence the crystal growth rate and morphology. We determined particle growth rates and investigated the formation and dissolution dynamics of an observed transient phase, believed to be amorphous calcium carbonate. This technique also enabled us to study the depletion zones, areas of lower intensity due to reduced ion concentrations. Ion flux rates were obtained from the depletion zone width, which amounted to several μm assuming the formation and dissolution dynamics of amorphous calcium carbonate being the rate determining process. This assumption was confirmed since the obtained fluxes were found to be in good agreement with fluxes derived from the experimentally observed crystal growth rates.

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

    PubMed

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

    2015-01-01

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

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

    PubMed

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

    2015-06-01

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

  5. Alginate hydrogel-mediated crystallization of calcium carbonate

    SciTech Connect

    Ma, Yufei; Feng, Qingling

    2011-05-15

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

  6. The ir emission features: Emission from PAH (Polycyclic Aromatic Hydrocarbons) molecules and amorphous carbon particles

    SciTech Connect

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

    1986-01-01

    PAHs can have several forms in the interstellar medium. To assess the importance of each requires the availability of a collection of high quality, complete mid-ir interstellar emission spectra, a collection of laboratory spectra of PAH samples prepared under realistic conditions and a firm understanding of the microscopic emission mechanism. Given what we currently know about PAHs, the spectroscopic data suggests that there are at least two components which contribute to the interstellar emission spectrum: free molecule sized PAHs producing the narrow features and amorphous carbon particles (which are primarily made up of an irregular ''lattice'' of PAHs) contributing to the broad underlying components. An exact treatment of the ir fluorescence from highly vibrationally excited large molecules shows that species containing between 20 and 30 carbon atoms are responsible for the narrow features, although the spectra match more closely with the spectra of amorphous carbon particles. Since little is known about the spectroscopic properties of free PAHs and PAH clusters, much laboratory work is called for in conjunction with an observational program which focuses on the spatial characteristics of the spectra. In this way the distribution and evolution of carbon from molecule to particle can be traced. 38 refs., 9 figs.

  7. Vertical electric field stimulation of neural cells on porous amorphous carbon electrodes

    NASA Astrophysics Data System (ADS)

    Jain, Shilpee; Sharma, Ashutosh; Basu, Bikramjit

    2014-03-01

    We demonstrate the efficacy of amorphous macroporous carbon substrates as electrodes to stimulate neuronal cell proliferation in presence of external electric field. The electric field was applied perpendicular to carbon electrode, while growing mouse neuroblastoma (N2a) cells in vitro. The placement of the second electrode outside of the cell culture medium allows the investigation of cell response to electric field without the concurrent complexities of submerged electrodes such as potentially toxic electrode reactions, electro-kinetic flows and charge transfer (electrical current) in the cell medium. The macroporous carbon electrodes are uniquely characterized by a higher specific charge storage capacity (0.2 mC/cm2) and low impedance (3.3 k Ω at 1 kHz). When a uniform or a gradient electric field was applied perpendicular to the amorphous carbon substrate, it was found that the N2a cell viability and neurite length were higher at low electric field strengths (<= 2.5 V/cm) compared to that measured without an applied field (0 V/cm). Overall, the results of the present study unambiguously establish the uniform/gradient vertical electric field based culture protocol to stimulate neurite outgrowth and viability of nerve cells.

  8. Effect of amorphous carbon layers on the growth of diamond in dual-frequency plasma

    NASA Astrophysics Data System (ADS)

    Reinke, P.; Klemberg-Sapieha, J. E.; Martinu, L.

    1994-11-01

    In the present work we study the growth of diamond in a dual-mode microwave/radio frequency plasma. We investigate the effect of the thickness of predeposited hydrogenated amorphous carbon (a-C:H) films and of ion bombardment of the nucleation process and on the crystal quality. The deposits are characterized by x-ray photoelectron spectroscopy (XPS) and by scanning electron microscopy. The XPS spectra of the C(1s) carbon peak and of the plasmon features confirm the presence of an amorphous, carbonaceous phase and of silicon carbide on the surface. Radio frequency biasing during the initial stage of diamond growth leads to a lower crystal quality, but to a higher nucleation density N(sub D). Without biasing, good quality, predominantly (100) oriented diamond crystals are obtained on a Si(100) surface. The N(sub D) values are found to increase with the thickness of the predeposited a-C:H layer. Evolution of the nucleus size distributions indicates that the a-C:H film contributes to the carbon supply, enhancing the nucleation efficiency and shortening the incubation time of seed crystals. Before a continuous layer is formed, the growth of crystals is determined by the interaction with the gas phase as well as by the amount of carbon available on the surface.

  9. Thermally induced transformations of amorphous carbon nanostructures fabricated by electron beam induced deposition.

    PubMed

    Kulkarni, Dhaval D; Rykaczewski, Konrad; Singamaneni, Srikanth; Kim, Songkil; Fedorov, Andrei G; Tsukruk, Vladimir V

    2011-03-01

    We studied the thermally induced phase transformations of electron-beam-induced deposited (EBID) amorphous carbon nanostructures by correlating the changes in its morphology with internal microstructure by using combined atomic force microscopy (AFM) and high resolution confocal Raman microscopy. These carbon deposits can be used to create heterogeneous junctions in electronic devices commonly known as carbon-metal interconnects. We compared two basic shapes of EBID deposits: dots/pillars with widths from 50 to 600 nm and heights from 50 to 500 nm and lines with variable heights from 10 to 150 nm but having a constant length of 6 μm. We observed that during thermal annealing, the nanoscale amorphous deposits go through multistage transformation including dehydration and stress-relaxation around 150 °C, dehydrogenation within 150-300 °C, followed by graphitization (>350 °C) and formation of nanocrystalline, highly densified graphitic deposits around 450 °C. The later stage of transformation occurs well below commonly observed graphitization for bulk carbon (600-800 °C). It was observed that the shape of the deposits contribute significantly to the phase transformations. We suggested that this difference is controlled by different contributions from interfacial footprints area. Moreover, the rate of graphitization was different for deposits of different shapes with the lines showing a much stronger dependence of its structure on the density than the dots.

  10. Silicon and aluminum doping effects on the microstructure and properties of polymeric amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoqiang; Hao, Junying; Xie, Yuntao

    2016-08-01

    Polymeric amorphous carbon films were prepared by radio frequency (R.F. 13.56 MHz) magnetron sputtering deposition. The microstructure evolution of the deposited polymeric films induced by silicon (Si) and aluminum(Al) doping were scrutinized through infrared spectroscopy, multi-wavelength Raman spectroscopy, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). The comparative results show that Si doping can enhance polymerization and Al doping results in an increase in the ordered carbon clusters. Si and Al co-doping into polymeric films leads to the formation of an unusual dual nanostructure consisting of cross-linked polymer-like hydrocarbon chains and fullerene-like carbon clusters. The super-high elasticity and super-low friction coefficients (<0.002) under a high vacuum were obtained through Si and Al co-doping into the films. Unconventionally, the co-doped polymeric films exhibited a superior wear resistance even though they were very soft. The relationship between the microstructure and properties of the polymeric amorphous carbon films with different elements doping are also discussed in detail.

  11. Epitaxial relationships between calcium carbonate and inorganic substrates.

    PubMed

    Yang, Taewook; Jho, Jae Young; Kim, Il Won

    2014-09-15

    The polymorph-selective crystallization of calcium carbonate has been studied in terms of epitaxial relationship between the inorganic substrates and the aragonite/calcite polymorphs with implication in bioinspired mineralization. EpiCalc software was employed to assess the previously published experimental results on two different groups of inorganic substrates: aragonitic carbonate crystals (SrCO3, PbCO3, and BaCO3) and a hexagonal crystal family (α-Al2O3, α-SiO2, and LiNbO3). The maximum size of the overlayer (aragonite or calcite) was calculated for each substrate based on a threshold value of the dimensionless potential to estimate the relative nucleation preference of the polymorphs of calcium carbonate. The results were in good agreement with previous experimental observations, although stereochemical effects between the overlayer and substrate should be separately considered when existed. In assessing the polymorph-selective nucleation, the current method appeared to provide a better tool than the oversimplified mismatch parameters without invoking time-consuming molecular simulation.

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

    NASA Astrophysics Data System (ADS)

    Turchyn, Alexandra V.; DePaolo, Donald J.

    2011-11-01

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

  13. Oxygen spectroscopy and polarization-dependent imaging contrast (PIC)-mapping of calcium carbonate minerals and biominerals.

    PubMed

    DeVol, Ross T; Metzler, Rebecca A; Kabalah-Amitai, Lee; Pokroy, Boaz; Politi, Yael; Gal, Assaf; Addadi, Lia; Weiner, Steve; Fernandez-Martinez, Alejandro; Demichelis, Raffaella; Gale, Julian D; Ihli, Johannes; Meldrum, Fiona C; Blonsky, Adam Z; Killian, Christopher E; Salling, C B; Young, Anthony T; Marcus, Matthew A; Scholl, Andreas; Doran, Andrew; Jenkins, Catherine; Bechtel, Hans A; Gilbert, Pupa U P A

    2014-07-17

    X-ray absorption near-edge structure (XANES) spectroscopy and spectromicroscopy have been extensively used to characterize biominerals. Using either Ca or C spectra, unique information has been obtained regarding amorphous biominerals and nanocrystal orientations. Building on these results, we demonstrate that recording XANES spectra of calcium carbonate at the oxygen K-edge enables polarization-dependent imaging contrast (PIC) mapping with unprecedented contrast, signal-to-noise ratio, and magnification. O and Ca spectra are presented for six calcium carbonate minerals: aragonite, calcite, vaterite, monohydrocalcite, and both hydrated and anhydrous amorphous calcium carbonate. The crystalline minerals reveal excellent agreement of the extent and direction of polarization dependences in simulated and experimental XANES spectra due to X-ray linear dichroism. This effect is particularly strong for aragonite, calcite, and vaterite. In natural biominerals, oxygen PIC-mapping generated high-magnification maps of unprecedented clarity from nacre and prismatic structures and their interface in Mytilus californianus shells. These maps revealed blocky aragonite crystals at the nacre-prismatic boundary and the narrowest calcite needle-prisms. In the tunic spicules of Herdmania momus, O PIC-mapping revealed the size and arrangement of some of the largest vaterite single crystals known. O spectroscopy therefore enables the simultaneous measurement of chemical and orientational information in CaCO3 biominerals and is thus a powerful means for analyzing these and other complex materials. As described here, PIC-mapping and spectroscopy at the O K-edge are methods for gathering valuable data that can be carried out using spectromicroscopy beamlines at most synchrotrons without the expense of additional equipment.

  14. On diamond, graphitic and amorphous carbons in primitive extraterrestrial solar system materials

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Frans J. M.

    1990-01-01

    Carbon is among the most abundant elements in the universe and carbon chemistry in meteorites and comets is an important key to understanding many Solar System and interstellar processes. Yet, the mineralogical properties and interrelations between various structural forms of elemental carbon remain ambiguous. Crystalline elemental carbons include rhombohedral graphite, hexagonal graphite, cubic diamond, hexagonal diamond (i.e., lonsdaleite or carbon-2H) and chaoite. Elemental carbon also occurs as amorphous carbon and poorly graphitized (or turbostratic) carbon but of all the forms of elemental carbon only graphite is stable under physical conditions that prevail in small Solar System bodies and in the interstellar medium. The recent discovery of cubic diamond in carbonaceous chondrites and hexagonal diamond in chondritic interplanetary dust particles (IDPs) have created a renewed interest in the crystalline elemental carbons that were not formed by shock processes on a parent body. Another technique, Raman spectroscopy, confirms a widespread occurrence of disordered graphite in the Allende carbonaceous chondrite and in chondritic IDPs. Elemental carbons have also been identified by their characteristic K-edge features in electron energy loss spectra (EELS). However, the spectroscopic data do not necessarily coincide with those obtained by selected area electron diffraction (SAED). In order to interpret these data in terms of rational crystalline structures, it may be useful to consider the principles underlying electron diffraction and spectroscopic analyses. Electron diffraction depends on electron scattering, on the type of atom and the distance between atoms in a crystal lattice. Spectroscopic data are a function of the type of atom and the energy of bonds between atoms. Also, SAED is a bulk sampling technique when compared to techniques such as Raman spectroscopy or EELS. Thus, it appears that combined analyses provide contradictory results and that amorphous

  15. Calcium carbonate scale control in once-through cooling systems

    SciTech Connect

    Brown, J.M.; McDowell, J.F. ); Heflin, R.F. ); Karlovich, D.N. ); Bloom, M.F. )

    1989-01-01

    This paper reports on a laboratory-scale model surface condenser used to design a successful once-through cooling water treatment program for calcium carbonate scale inhibition at Young Station. The treatment program has maintained the station's condenser cleanliness factor at approximately 100% for the duration of the treatment. The model surface condensers simulate cycled systems as well as once-through cooling systems. They are fully automated with computer-controlled chemical feed, flow, heat flux, makeup, and blowdown and data acquisition systems.

  16. Crystalline calcium carbonate and hydrogels as microenvironment for stem cells.

    PubMed

    Astachov, Liliana; Nevo, Zvi; Aviv, Moran; Vago, Razi

    2011-01-01

    Stem cell development and fate decisions are dictated by the microenvironment in which the stem cell is embedded. Among the advanced goals of tissue engineering is the creation of a microenvironment that will support the maintenance and differentiation of the stem cell--based on embryonic and adult stem cells as potent, cellular sources--for a variety of clinical applications. This review discusses some of the approaches used to create regulatory and instructive microenvironments for the directed differentiation of mesenchymal stem cells (MSCs) using three-dimensional crystalline calcium carbonate biomaterials of marine origin combined with a hydrated gel based on hyaluronan.

  17. Carbonation as a binding mechanism for coal/calcium hydroxide pellets

    SciTech Connect

    Rapp, D.M.

    1991-01-01

    Current coal mining and processing procedures produce a significant quanity of fine coal that is difficult to handle and transport. The objective of this work is to determine if these fines can be economically pelletized with calcium hydroxide, a sulfur capturing sorbent, to produce a clean-burning fuel for fluidized-bed combustors or stoker boilers. To harden these pellets, carbonation, which is the reaction of calcium hydroxide with carbon dioxide to produce a cementitious matrix of calcium carbonate, is being investigated. Previous research indicated that carbonation significantly improved compressive strength, impact and attrition resistance and weatherproofed'' pellets formed with sufficient calcium hydroxide (5 to 10% for minus 28 mesh coal fines).

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

    PubMed

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

    2015-01-01

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

  19. Crystallized nano-sized alpha-tricalcium phosphate from amorphous calcium phosphate: microstructure, cementation and cell response.

    PubMed

    Vecbiskena, Linda; Gross, Karlis Agris; Riekstina, Una; Yang, Thomas Chung-Kuang

    2015-04-17

    New insight on the conversion of amorphous calcium phosphate (ACP) to nano-sized alpha tricalcium phosphate (α-TCP) provides a faster pathway to calcium phosphate bone cements. In this work, synthesized ACP powders were treated with either water or ethanol, dried, crystallized between 700 and 800 °C, and then cooled at different cooling rates. Particle size was measured in a scanning electron microscope, but crystallite size calculated by Rietveld analysis. Phase composition and bonding in the crystallized powder was assessed by x-ray diffraction and Fourier-transform infrared spectroscopy. Results showed that 50 nm sized α-TCP formed after crystallization of lyophilized powders. Water treated ACP retained an unstable state that may allow ordering to nanoapatite, and further transition to β-TCP after crystallization and subsequent decomposition. Powders treated with ethanol, favoured the formation of pure α-TCP. Faster cooling limited the growth of β-TCP. Both the initial contact with water and the cooling rate after crystallization dictated β-TCP formation. Nano-sized α-TCP reacted faster with water to an apatite bone cement than conventionally prepared α-TCP. Water treated and freeze-dried powders showed faster apatite cement formation compared to ethanol treated powders. Good biocompatibility was found in pure α-TCP nanoparticles made from ethanol treatment and with a larger crystallite size. This is the first report of pure α-TCP nanoparticles with a reactivity that has not required additional milling to cause cementation.

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

    SciTech Connect

    V.J. Fabry, Ph.D.

    2002-07-09

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

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

    SciTech Connect

    V.J. Fabry, Ph.D.

    2003-04-15

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

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

    SciTech Connect

    V.J. Fabry

    2005-04-29

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

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

    SciTech Connect

    V. J. Fabry

    2005-01-24

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

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

    SciTech Connect

    V. J. Fabry

    2003-10-30

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

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

    SciTech Connect

    V.J. Fabry

    2007-06-30

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

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

    SciTech Connect

    V.J. Fabry, Ph.D.

    2002-09-30

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

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

    SciTech Connect

    V.J. Fabry

    2004-04-26

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

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

    SciTech Connect

    V.J. Fabry, Ph.D.

    2002-04-05

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

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

    SciTech Connect

    V.J. Fabry

    2001-07-01

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

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

    SciTech Connect

    V.J. Fabry, Ph.D.

    2001-12-15

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

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

    SciTech Connect

    V.J. Fabry, Ph.D.

    2001-09-10

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

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

    SciTech Connect

    V. J.Fabry

    2004-01-30

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

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

    SciTech Connect

    V.J. Fabry, Ph.D.

    2002-12-15

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

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

    SciTech Connect

    V.J. Fabry

    2004-10-30

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

  15. Photovoltaic characteristics of Pd doped amorphous carbon film/SiO{sub 2}/Si

    SciTech Connect

    Ma Ming; Xue Qingzhong; Chen Huijuan; Zhou Xiaoyan; Xia Dan; Lv Cheng; Xie Jie

    2010-08-09

    The Pd doped amorphous carbon (a-C:Pd) films were deposited on n-Si substrates with or without a native SiO{sub 2} layer using magnetron sputtering. The photovoltaic characteristics of the a-C:Pd/SiO{sub 2}/Si and a-C:Pd/Si junctions were studied. It is found that under light illumination of 15 mW/cm{sup 2} at room temperature, the a-C:Pd/SiO{sub 2}/Si solar cell fabricated at 350 deg. C has a high power conversion efficiency of 4.7%, which is much better than the a-C/Si junctions reported before. The enhanced conversion efficiency is ascribed to the Pd doping and the increase in sp{sup 2}-bonded carbon clusters in the carbon film caused by the high temperature deposition.

  16. Structural properties of nitrogenated amorphous carbon films: Influence of deposition temperature and radiofrequency discharge power

    SciTech Connect

    Lazar, G.; Bouchet-Fabre, B.; Zellama, K.; Clin, M.; Ballutaud, D.; Godet, C.

    2008-10-01

    The structural properties of nitrogenated amorphous carbon deposited by radiofrequency magnetron sputtering of graphite in pure N{sub 2} plasma are investigated as a function of the substrate temperature and radiofrequency discharge power. The film composition is derived from x-ray photoemission spectroscopy, nuclear reaction analysis and elastic recoil detection measurements and the film microstructure is discussed using infrared, Raman, x-ray photoemission and near edge x-ray absorption fine structure spectroscopic results. At low deposition temperature and low radiofrequency power, the films are soft, porous, and easily contaminated with water vapor and other atmospheric components. The concentration of nitrogen in the films is very large for low deposition temperatures ({approx}33.6 at. % N at 150 deg. C) but decreases strongly when the synthesis temperature increases ({approx}15 at. % N at 450 deg. C). With increasing deposition temperature and discharge power values, the main observed effects in amorphous carbon nitride alloys are a loss of nitrogen atoms, a smaller hydrogen and oxygen contamination related to the film densification, an increased order of the aromatic sp{sup 2} phase, and a strong change in the nitrogen distribution within the carbon matrix. Structural changes are well correlated with modifications of the optical and transport properties.

  17. Resonant tunnelling assisted electrical switching in amorphous-carbon multilayer-superlattice structures

    NASA Astrophysics Data System (ADS)

    Bhattacharyya, Somnath; Silva, S. R. P.

    2007-03-01

    Negative differential resistance (NDR) in an amorphous carbon (a-C) double barrier resonant tunnel diode (DB-RTD) with an estimated cut-off frequency well into the gigahertz regime is reported [1]. Presently we extend this work in carbon multi-layer superlattice structures by showing room temperature resonant tunnelling and establish a high value of the phase coherence length of ˜10 nm for low-dimensional amorphous materials. By applying a high bias, these structures are modified with reversible current switching of up to four orders of magnitude with a NDR signature and multiple peaks representative of resonant tunnelling in the ON state. In addition to the formation of filamentary channels by applying high bias, all these features are also explained using concepts based on tunnelling through the interface of the carbon layers, quantum-dot heterostructures and the presence of a confined two dimensional electron gas. This switching behavior and its tunability have been tested by applying a microwave signal up to 100 GHz which suggest the potential for novel high-speed memory devices. [1] S. Bhattacharyya, S.J. Henley, E. Mendoza, L.G-Rojas, J. Allam and S.R.P. Silva, Nature Mater. 5, 19 (2006).

  18. Extinction due to amorphous carbon grains in red quasars from the Sloan Digital Sky Survey

    NASA Astrophysics Data System (ADS)

    Czerny, B.; Li, J.; Loska, Z.; Szczerba, R.

    2004-03-01

    We construct a quasar extinction curve based on the blue and red composite quasar spectra of Richards et al. prepared from the Sloan Digital Sky Survey. This extinction curve does not show any traces of the 2200-Å feature characteristic of the interstellar medium, and this indicates that graphite grains are likely to be absent close to quasar nuclei. The extinction is best modelled by an AC sample of amorphous carbon grains, assuming a standard distribution of grain sizes (p= 3.5) but slightly larger minimum grain size (amin= 0.016 μm) and lower maximum grain size (amin= 0.12 μm) than the respective canonical values for the interstellar medium. The dust composition is thus similar to that of the dust in carbon reach asymptotic giant branch stars. Since graphite grains form from amorphous carbon exposed to strong ultraviolet irradiation, the results indicate that the dust forms either surprisingly far from the active nucleus or in a wind that leaves the nucleus quickly enough to avoid crystallization into graphite.

  19. Raman Spectroscopy Characterization of amorphous carbon coatings for computer hard disks

    SciTech Connect

    Ager III, Joel W.

    1998-05-07

    Amorphous carbon films are used as protective coatings on magnetic media to protect the magnetic layer from wear and abrasion caused by the read/write head during hard disk drive start-up and operation. A key requirement in increasing the storage capacity and reliability of hard-disk drives is improving the performance of these coatings. This cooperative agreement used optical characterization techniques developed at LBNL to study thin-film hard disk media produced by Seagate Technology, major US hard drive manufacturer. The chief scientific goal was relating quantitatively the results of the optical characterization to the underlying chemical structure of the overcoat. In a collaboration with Seagate, LBNL, and Cambridge University, optical and electron-based characterization were used to evaluate the chemical structure of overcoats. The sp3 fraction of the sputtered amorphous carbon films was measured quantitatively for the first time and related to the optical spectroscopy results. This work and other selected aspects of the research performed under the agreement were presented at technical meetings and published in the open literature. The chief technical goal was designing manufacturing processes for the protective carbon overcoat for use in new generations of Seagate disk drives. To this end, joint research carried out under this agreement enabled Seagate to speed development of new coatings which are currently being used in the production of disk media in Seagate's disk-media manufacturing plants in Fremont, CA.

  20. Amorphous calcium phosphate nanospheres/polylactide composite coated tantalum scaffold: facile preparation, fast biomineralization and subchondral bone defect repair application.

    PubMed

    Zhou, Rong; Xu, Wei; Chen, Feng; Qi, Chao; Lu, Bing-Qiang; Zhang, Hao; Wu, Jin; Qian, Qi-Rong; Zhu, Ying-Jie

    2014-11-01

    Calcium phosphate (CaP) materials are widely used in various biomedical areas such as drug/gene delivery and bone repair/tissue engineering. In this study, amorphous CaP nanospheres synthesized by a simple co-precipitation method are used to prepare the CaP-polylactide (CaP-PLA) composite. Then, the as-prepared CaP-PLA composite is used to coat tantalum (Ta) plates and porous scaffolds. Compared with bare Ta plate, CaP-PLA coated Ta plates show a high performance of surface biomineralization in simulated body fluid (SBF). In addition, the hydrophilicity of the CaP-PLA coated Ta plates is significantly improved. CaP-PLA coated Ta plates with bovine serum albumin (BSA) are prepared and used for the investigation of BSA release in vitro. The experimental results indicate a sustained BSA release property and simultaneous biomineralization of the as-prepared BSA-containing CaP-PLA coated Ta plates. Furthermore, CaP-PLA coated Ta scaffolds are favorable for the human osteoblast-like MG63 cells adhesion and spreading. The vascular endothelial growth factor (VEGF) and transforming growth factor (TGF)-containing CaP-PLA coated porous Ta scaffolds are used for the study of rabbit subchondral bone defect repair, covering with autogeneic periosteums. The as-prepared CaP-PLA composite coated Ta scaffolds are useful to guide the bone regeneration in vivo.

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

    PubMed Central

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Djogbenou, Nancy

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

  3. Preliminary study of a novel in-office bleaching therapy modified with a casein phosphopeptide-amorphous calcium phosphate.

    PubMed

    Borges, Boniek Castillo Dutra; Pinheiro, Mônica Heloisa Morais; Feitosa, Diala Aretha De Sousa; Correia, Tereza Cristina; Braz, Rodivan; Montes, Marcos Antônio Japiassú Resende; Pinheiro, Isauremi Vieira De Assunção

    2012-11-01

    Although in-office bleaching has been proven successful for bleaching teeth, controversy exists from morphological alterations in enamel morphology due to mineral loss and tooth sensitivity. This preliminary study aimed to evaluate the efficacy of a novel in-office tooth bleaching technique modified with a casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) paste (MI paste-MI) and its effect on the enamel morphology and tooth sensitivity. Three patients received a 35% hydrogen peroxide (Whiteness HP-HP) dental bleaching system. HP was prepared and applied on the teeth on one of the hemiarches, whilst teeth on the other hemiarch were bleached with a mixture of HP and MI. Tooth color, epoxy resin replicas, and sensitivity levels were evaluated in the upper incisors. The results were analyzed descriptively. Right and left incisors showed similar color change after bleaching. Incisors bleached with the mixture of HP and MI presented unaltered enamel surfaces and lower sensitivity levels. The currently tested tooth bleaching technique did not reduce the gel effectiveness while decreasing hypersensitivity levels and protecting the enamel against surface alterations caused by the high-concentration bleaching peroxide tested. The concomitant use of MI Paste and high-concentration hydrogen peroxide might be a successful method for decreasing tooth sensitivity and limiting changes in the enamel morphology during in-office bleaching.

  4. Evaluation of remineralization capacity of casein phosphopeptide-amorphous calcium phosphate on the carbamide peroxide treated enamel

    PubMed Central

    Penumatsa, Narendra Varma; Kaminedi, Raja Rajeswari; Baroudi, Kusai; Barakath, Ola

    2015-01-01

    Objective: The aim of this study was to evaluate the potential of casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) in remineralizing the bleached enamel surface using micro-hardness. Materials and Methods: Thirty human enamel slabs were randomly divided into three groups (n = 10). Groups A and B were exposed to 20% carbamide peroxide and 35% carbamide peroxide gel, respectively. After the exposure to the bleaching agent, the slabs were kept in artificial saliva for 1-week. Group C (control group) were kept in artificial saliva for 1-week. Vickers micro-hardness test was performed by Leica VMHT-Mot micro-hardness tester. CPP-ACP (Gc Tooth Mousse, Melbourne, Australia) was then applied to specimens of Groups A and B for 3 min for 2 weeks. Micro-hardness values of postbleach Group A (Ar) and Group B (Br) were recorded and statistically analyzed by paired t-test and one-way analysis of variance at the significance level of α =0.05. Results: There was a significant decrease in micro-hardness of enamel in carbamide peroxide bleached groups. However, there was a significant increase in micro-hardness after the remineralization by CPP-ACP and the extent of remineralization is more for the Group B. Conclusions: That bleaching agents reduced enamel micro-hardness and the use of CPP-ACP after bleaching can significantly enhance the micro-hardness of bleached enamel. PMID:26538923

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

    PubMed

    Saber-Samandari, Saeed; Gross, Karlis A

    2013-03-01

    Fatigue testing of load-bearing coated implants is usually very time-consuming and so a new contact nanofatigue test using a nanoindenter has been evaluated. A cube corner indenter provided the fastest indication of failure, through crack formation, compared to a spherical indenter. Contact nanofatigue was performed on a sintered hydroxyapatite and then on amorphous calcium phosphate splats produced on titanium, stainless steel and Co-Cr surfaces, made either at room temperature or on 250°C preheated surfaces. Sintered hydroxyapatite showed continual plastic deformation, but this is not that apparent for splats on metal surfaces. Substrate preheating was found to induce cracking in splats, explained by greater thermal residual stresses. Endurance during contact nanofatigue, measured as time to crack formation, was the lowest for splats on titanium followed by Co-Cr and stainless steel. The splat on titanium showed both cracking and plastic deformation during testing. Good agreement has been reached with previous studies with cracking directed to the substrate without splat delamination. Contact nanofatigue with the nanoindenter easily and quickly identifies cracking events that previously required detection with acoustic emission, and shows good feasibility for mechanical testing of discs and splats produced by thermal spraying, spray forming, laser-ablation, aerosol jet and ink jet printing.

  6. A near-frictionless and extremely elastic hydrogenated amorphous carbon film with self-assembled dual nanostructure.

    PubMed

    Liu, Xiaoqiang; Yang, Jun; Hao, Junying; Zheng, Jianyun; Gong, Qiuyu; Liu, Weimin

    2012-09-04

    A highly crosslinking network combined with a fullerene-like structure is disclosed in a hydrogenated amorphous carbon film. The very soft carbon film exhibits super-low friction and excellent wear resistance even under a Hertzian contact pressure comparable to its hardness under vacuum, which is an extraordinary tribological behavior in the filed of solid lubrication films or coatings.

  7. Subsurface defect of amorphous carbon film imaged by near field acoustic microscopy

    NASA Astrophysics Data System (ADS)

    Zeng, J. T.; Zhao, K. Y.; Zeng, H. R.; Song, H. Z.; Zheng, L. Y.; Li, G. R.; Yin, Q. R.

    2008-05-01

    Amorphous carbon films were examined by low frequency scanning-probe acoustic microscopy (LF-SPAM). Local elastic properties as well as topography were imaged in the acoustic mode. Two kinds of subsurface defects were revealed by the LF-SPAM method. The influence of the subsurface defects on the elastic properties was also discussed. The ability to image subsurface defects was dependent on the scan area and the scan speed. Our results showed that the low frequency scanning-probe acoustic microscopy is a useful method for imaging subsurface defects with high resolution.

  8. Constitutive modeling of calcium carbonate supersaturated seawater mixtures

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

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

    USGS Publications Warehouse

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

    1998-01-01

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

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

    SciTech Connect

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

    2012-08-15

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

  11. Precipitation of Co(2+) carbonates from aqueous solution: insights on the amorphous to crystalline transformation.

    NASA Astrophysics Data System (ADS)

    González-López, Jorge; Fernández-González, Ángeles; Jiménez, Amalia

    2016-04-01

    Cobalt is toxic metal that is present only as a trace in the Earth crust. However, Co might concentrate on specific areas due to both natural and anthropogenic factors and thus, soils and groundwater can be contaminated. It is from this perspective that we are interested in the precipitation of cobalt carbonates, since co-precipitation with minerals phases is a well-known method for metal immobilization in the environment. In particular, the carbonates are widely used due to its reactivity and natural abundance. In order to evaluate the cobalt carbonate precipitation at room temperature, a simple experimental work was carried out in this work. The precipitation occurred via reaction of two common salts: 0.05M of CoCl2 and 0.05M of Na2CO3 in aqueous solution. After reaction, the precipitated solid was kept in the remaining water at 25 oC and under constant stirring for different aging times of 5 min, 1 and 5 hours, 1, 2, 4, 7, 30 and 60 days. In addition to the aging and precipitation experiments, we carried out experiments to determine the solubility of the solids. In these experiments each precipitate was dissolved in Milli-Q water until equilibrium was reached and then the aqueous solution was analyzed regarding Co2+ and total alkalinity. Furthermore, acid solution calorimetry of the products were attained. Finally, we modeled the results using the PHREEQC code. Solid and aqueous phase identification and characterization have been extensively reported in a previous work (González-López et al., 2015). The main results of our investigation were the initial precipitation of an amorphous cobalt carbonate that evolve towards a poorly crystalline cobalt hydroxide carbonate with aging treatment. Solubility of both phases have been calculated under two different approaches: precipitation and dissolution. Values of solubility from each approach were obtained with a general error due to differences in experiment conditions, for instance, ionic strength, temperature and

  12. Vertical electric field stimulated neural cell functionality on porous amorphous carbon electrodes.

    PubMed

    Jain, Shilpee; Sharma, Ashutosh; Basu, Bikramjit

    2013-12-01

    We demonstrate the efficacy of amorphous macroporous carbon substrates as electrodes to support neuronal cell proliferation and differentiation in electric field mediated culture conditions. The electric field was applied perpendicular to carbon substrate electrode, while growing mouse neuroblastoma (N2a) cells in vitro. The placement of the second electrode outside of the cell culture medium allows the investigation of cell response to electric field without the concurrent complexities of submerged electrodes such as potentially toxic electrode reactions, electro-kinetic flows and charge transfer (electrical current) in the cell medium. The macroporous carbon electrodes are uniquely characterized by a higher specific charge storage capacity (0.2 mC/cm(2)) and low impedance (3.3 kΩ at 1 kHz). The optimal window of electric field stimulation for better cell viability and neurite outgrowth is established. When a uniform or a gradient electric field was applied perpendicular to the amorphous carbon substrate, it was found that the N2a cell viability and neurite length were higher at low electric field strengths (≤ 2.5 V/cm) compared to that measured without an applied field (0 V/cm). While the cell viability was assessed by two complementary biochemical assays (MTT and LDH), the differentiation was studied by indirect immunostaining. Overall, the results of the present study unambiguously establish the uniform/gradient vertical electric field based culture protocol to either enhance or to restrict neurite outgrowth respectively at lower or higher field strengths, when neuroblastoma cells are cultured on porous glassy carbon electrodes having a desired combination of electrochemical properties.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  14. Computational Evaluation of Amorphous Carbon Coating for Durable Silicon Anodes for Lithium-Ion Batteries

    PubMed Central

    Hwang, Jeongwoon; Ihm, Jisoon; Lee, Kwang-Ryeol; Kim, Seungchul

    2015-01-01

    We investigate the structural, mechanical, and electronic properties of graphite-like amorphous carbon coating on bulky silicon to examine whether it can improve the durability of the silicon anodes of lithium-ion batteries using molecular dynamics simulations and ab-initio electronic structure calculations. Structural models of carbon coating are constructed using molecular dynamics simulations of atomic carbon deposition with low incident energies (1–16 eV). As the incident energy decreases, the ratio of sp2 carbons increases, that of sp3 decreases, and the carbon films become more porous. The films prepared with very low incident energy contain lithium-ion conducting channels. Also, those films are electrically conductive to supplement the poor conductivity of silicon and can restore their structure after large deformation to accommodate the volume change during the operations. As a result of this study, we suggest that graphite-like porous carbon coating on silicon will extend the lifetime of the silicon anodes of lithium-ion batteries.

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

    USGS Publications Warehouse

    Reddy, M.M.; Hoch, A.

    2012-01-01

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

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

    USGS Publications Warehouse

    Reddy, Michael M.; Hoch, Anthony

    2012-01-01

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

  17. Structure and mechanical properties of low stress tetrahedral amorphous carbon films prepared by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Bonelli, M.; Ferrari, A. C.; Fioravanti, A.; Li Bassi, A.; Miotello, A.; Ossi, P. M.

    2002-02-01

    Tetrahedral amorphous carbon films have been produced by pulsed laser deposition, at a wavelength of 248 nm, ablating highly oriented pyrolytic graphite at room temperature, in a 10-2 Pa vacuum, at fluences ranging between 0.5 and 35 Jcm-2. Both (100) Si wafers and wafers covered with a SiC polycrystalline interlayer were used as substrates. Film structure was investigated by Raman spectroscopy at different excitation wavelength from 633 nm to 229 nm and by transmission Electron Energy Loss Spectroscopy. The films, which are hydrogen-free, as shown by Fourier Transform Infrared Spectroscopy, undergo a transition from mainly disordered graphitic to up to 80% tetrahedral amorphous carbon (ta-C) above a threshold laser fluence of 5 J cm-2. By X-ray reflectivity roughness, density and cross-sectional layering of selected samples were studied. Film hardness as high as 70 GPa was obtained by nanoindentation on films deposited with the SiC interlayer. By scratch test film adhesion and friction coefficients between 0.06 and 0.11 were measured. By profilometry we obtained residual stress values not higher than 2 GPa in as-deposited 80% sp3 ta-C films.

  18. Formation of Ultrananocrystalline Diamond/Amorphous Carbon Composite Films in Vacuum Using Coaxial Arc Plasma Gun

    NASA Astrophysics Data System (ADS)

    Hanada, Kenji; Yoshida, Tomohiro; Nakagawa, You; Yoshitake, Tsuyoshi

    2010-12-01

    Ultrananocrystalline diamond (UNCD)/nonhydrogenated amorphous carbon (a-C) composite films were grown in vacuum using a coaxial arc plasma gun. From the X-ray diffraction measurement, the UNCD crystallite size was estimated to be 1.6 nm. This size is dramatically reduced from that (2.3 nm) of UNCD/hydrogenated amorphous carbon (a-C:H) composite films grown in a hydrogen atmosphere. The sp3/(sp3 + sp2) value, which was estimated from the X-ray photoemission spectrum, was also reduced to be 41%. A reason for it might be the reduction in the UNCD crystallite size. From the near-edge X-ray absorption fine-structure (NEXAFS) spectrum, it was found that the π*C=C and π*C≡C bonds are preferentially formed instead of the σ*C-H bonds in the UNCD/a-C:H films. Since the extremely small UNCD crystallites (1.6 nm) correspond to the nuclei of diamond, we consider that UNCD crystallite formation should be due predominantly to nucleation. The supersaturated condition required for nucleation is expected to be realized in the deposition using the coaxial arc plasma gun.

  19. AFM investigation on surface evolution of amorphous carbon during ion-beam-assisted deposition

    NASA Astrophysics Data System (ADS)

    Zhu, X. D.; Ding, F.; Naramoto, H.; Narumi, K.

    2006-11-01

    Hydrogen-free amorphous carbons (a-C) have been prepared on mirror-polished Si(1 1 1) wafers through thermally evaporated C 60 with simultaneous bombardments of Ne + ions. The time evolution of film surfaces has been characterized by atomic force microscopy (AFM) at two temperatures of 400 and 700 °C, respectively. Based on the topography images and the root-mean-square (rms) roughness analysis, it is found that the a-C surfaces present roughening growth at the initial stage. With increasing growth time, the cooperative nucleation of the islands and pits appears on the surfaces, suggesting three-dimensional growth, and then they continue to evolve to irregular mounds at 400 °C, and elongated mounds at 700 °C. At the steady growth stage, these surfaces further develop to the structures of bamboo joints and ripples corresponding to these two temperatures, respectively. It is believed that besides ion sputtering effect, the chemical bonding configurations in the amorphous carbon films should be taken into considerations for elucidating the surface evolutions.

  20. B-spline parametrization of the dielectric function applied to spectroscopic ellipsometry on amorphous carbon

    SciTech Connect

    Weber, J. W.; Hansen, T. A. R.; Sanden, M. C. M. van de; Engeln, R.

    2009-12-15

    The remote plasma deposition of hydrogenated amorphous carbon (a-C:H) thin films is investigated by in situ spectroscopic ellipsometry (SE). The dielectric function of the a-C:H film is in this paper parametrized by means of B-splines. In contrast with the commonly used Tauc-Lorentz oscillator, B-splines are a purely mathematical description of the dielectric function. We will show that the B-spline parametrization, which requires no prior knowledge about the film or its interaction with light, is a fast and simple-to-apply method that accurately determines thickness, surface roughness, and the dielectric constants of hydrogenated amorphous carbon thin films. Analysis of the deposition process provides us with information about the high deposition rate, the nucleation stage, and the homogeneity in depth of the deposited film. Finally, we show that the B-spline parametrization can serve as a stepping stone to physics-based models, such as the Tauc-Lorentz oscillator.

  1. Characterization of amorphous carbon films grown by pulsed-laser deposition

    SciTech Connect

    Siegal, M.P.; Tallant, D.R.; Barbour, J.C.; Provencio, P.N.; Martinez-Miranda, L.J.; DiNardo, N.J.

    1998-09-01

    Amorphous carbon (a-C) films grow via energetic processes such as pulsed-laser deposition (PLD). The cold-cathode electron emission properties of a-C are promising for flat-panel display and vacuum microelectronics technologies. These ultrahard films consist of a mixture of 3-fold and 4-fold coordinated carbon atoms, resulting in an amorphous material with diamond-like properties. The authors study the structures of a-C films grown at room temperature as a function of PLD energetics using x-ray reflectivity, Raman spectroscopy, high-resolution transmission electron microscopy, and Rutherford backscattering spectrometry. While an understanding of the electron emission mechanism in a-C films remains elusive, the onset of emission is typically preceded by conditioning where the material is stressed by an applied electric field. To simulate conditioning and assess its effect, the authors use the spatially-localized field and current of a scanning tunneling microscope tip. Scanning force microscopy shows that conditioning alters surface morphology and electronic structure. Spatially-resolved electron energy loss spectroscopy indicates that the predominant bonding configuration changes from predominantly 4-fold to 3-fold coordination.

  2. Structural disorder in hard amorphous carbon films implanted with nitrogen ions

    SciTech Connect

    Freire, F.L. Jr.; Franceschini, D.F.; Achete, C.A.; Brusa, R.S.; Mariotto, G.; Karwasz, G.P.; Canteri, R.

    1996-12-31

    Hard amorphous hydrogenated carbon films deposited by self-bias glow discharge were implanted at room temperature with 70 keV-nitrogen ions at fluences between 2.0 and 9.0 {times} 10{sup 16} N/cm{sup 2}. The implanted samples were analyzed by Raman spectroscopy, SIMS and positron annihilation spectroscopy (Doppler broadening technique with the determination of the parameter S). For samples implanted with 2.0 {times} 10{sup 16} N/cm{sup 2} the S parameter follows the vacancies depth profile predicted by Monte Carlo simulation. For higher fluences the authors observed a reduction in the measured value of S. This result is discussed in terms of both hydrogen loss and structural modifications (increase of disorder at local scale and of the number of graphitic domains) induced in the carbon film by ion implantation.

  3. Identification of infrared absorption peaks of amorphous silicon-carbon alloy by thermal annealing

    NASA Astrophysics Data System (ADS)

    Lin, Wei-Liang; Tsai, Hsiung-Kuang; Lee, Si-Chen; Sah, Wen-Jyh; Tzeng, Wen-Jer

    1987-12-01

    Amorphous silicon-carbon hydrogen alloy was prepared by radio frequency glow discharge decomposition of a silane-methane mixture. The infrared absorption spectra were measured at various stages of thermal annealing. By observing the change of relative intensities between these peaks the hydrogen bonding responsible for the absorption peaks could be assigned more accurately, for example, the stretching mode of monohydride Si-H is determined by its local environment, which supports H. Wagner's and W. Beyer's results [Solid State Commun. 48, 585 (1983)] but is inconsistent with the commonly believed view. It is also found that a significant fraction of carbon atoms are introduced into the film in -CH3 configuration which forms a local void and enhances the formation of polysilane chain and dangling bond defects. Only after high-temperature annealing are the hydrogen atoms driven out, and Si and C start to form a better silicon carbide network.

  4. Shear-induced lamellar ordering and interfacial sliding in amorphous carbon films: A superlow friction regime

    NASA Astrophysics Data System (ADS)

    Ma, Tian-Bao; Hu, Yuan-Zhong; Xu, Liang; Wang, Lin-Feng; Wang, Hui

    2011-10-01

    A shear-induced phase transition from disorder to lamellar ordering in amorphous carbon films are investigated by molecular dynamics simulations. Formation of well-separated graphene-like interfacial layers is observed with large interlayer distances, diminishing and ultimately vanishing interlayer bonds, which provides a near-frictionless sliding plane. The steady-state velocity accommodation mode after the running-in stage is interfacial sliding between the graphene-like layers, which explains the experimentally observed graphitization and formation of carbon-rich transfer layers. A superlow friction or superlubricity regime with friction coefficient of approximately 0.01 originates from the extremely large repulsive and low shear interactions across the sliding interface.

  5. Effect of Strength Enhancement of Soil Treated with Environment-Friendly Calcium Carbonate Powder

    PubMed Central

    Park, Kyungho; Jun, Sangju; Kim, Daehyeon

    2014-01-01

    This study aims to investigate the effects of the strength improvement of soft ground (sand) by producing calcium carbonate powder through microbial reactions. To analyze the cementation effect of calcium carbonate produced through microbial reaction for different weight ratios, four different types of specimens (untreated, calcium carbonate, cement, and calcium carbonate + cement) with different weight ratios (2%, 4%, 6%, and 8%) were produced and cured for a period of 3 days, 7 days, 14 days, 21 days, and 28 days to test them. The uniaxial compression strength of specimens was measured, and the components in the specimen depending on the curing period were analyzed by means of XRD analysis. The result revealed that higher weight ratios and longer curing period contributed to increased strength of calcium carbonate, cement, and calcium carbonate + cement specimens. The calcium carbonate and the calcium carbonate + cement specimens in the same condition showed the tendency of decreased strength approximately 3 times and two times in comparison with the 8% cement specimens cured for 28 days, but the tendency of increased strength was approximately 4 times and 6 times in comparison with the untreated specimen. PMID:24688401

  6. Effect of strength enhancement of soil treated with environment-friendly calcium carbonate powder.

    PubMed

    Park, Kyungho; Jun, Sangju; Kim, Daehyeon

    2014-01-01

    This study aims to investigate the effects of the strength improvement of soft ground (sand) by producing calcium carbonate powder through microbial reactions. To analyze the cementation effect of calcium carbonate produced through microbial reaction for different weight ratios, four different types of specimens (untreated, calcium carbonate, cement, and calcium carbonate + cement) with different weight ratios (2%, 4%, 6%, and 8%) were produced and cured for a period of 3 days, 7 days, 14 days, 21 days, and 28 days to test them. The uniaxial compression strength of specimens was measured, and the components in the specimen depending on the curing period were analyzed by means of XRD analysis. The result revealed that higher weight ratios and longer curing period contributed to increased strength of calcium carbonate, cement, and calcium carbonate + cement specimens. The calcium carbonate and the calcium carbonate + cement specimens in the same condition showed the tendency of decreased strength approximately 3 times and two times in comparison with the 8% cement specimens cured for 28 days, but the tendency of increased strength was approximately 4 times and 6 times in comparison with the untreated specimen.

  7. Probing the intrinsic failure mechanism of fluorinated amorphous carbon film based on the first-principles calculations

    PubMed Central

    Zhang, Ren-hui; Wang, Li-ping; Lu, Zhi-bin

    2015-01-01

    Fluorinated amorphous carbon films exhibit superlow friction under vacuum, but are prone to catastrophic failure. Thus far, the intrinsic failure mechanism remains unclear. A prevailing view is that the failure of amorphous carbon film results from the plastic deformation of substrates or strong adhesion between two contacted surfaces. In this paper, using first-principles and molecular dynamics methodology, combining with compressive stress-strain relation, we firstly demonstrate that the plastic deformation induces graphitization resulting in strong adhesion between two contacted surfaces under vacuum, which directly corresponds to the cause of the failure of the films. In addition, sliding contact experiments are conducted to study tribological properties of iron and fluorinated amorphous carbon surfaces under vacuum. The results show that the failure of the film is directly attributed to strong adhesion resulting from high degree of graphitization of the film, which are consistent with the calculated results. PMID:25803202

  8. The effect of ultrasonication on calcium carbonate crystallization in the presence of biopolymer

    NASA Astrophysics Data System (ADS)

    Kirboga, Semra; Oner, Mualla; Akyol, Emel

    2014-09-01

    Synthesis of calcium carbonate (CaCO3) was carried out using sonication in aqueous solution medium. The effect of the probe immersion depth (PID) and the amplitude of sonicator on calcium carbonate crystallization were studied in the absence and presence of biopolymer, carboxymethyl inulin (CMI). Calcium carbonate crystals synthesized with and without ultrasound were compared. X-ray diffraction (XRD) analysis showed that calcium carbonate obtained in the presence of biopolymer was a mixture of calcite and vaterite whereas there was only calcite polymorph in the absence of biopolymer. In the presence of biopolymer, the relative fraction of vaterite increased with the application of sonication process. The higher amplitude resulted in the higher relative vaterite fraction. The results showed that the probe immersion depth and the amplitude affected the morphology of calcium carbonate.

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

    SciTech Connect

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

    1988-01-01

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

  10. Calcium

    MedlinePlus

    ... You'll also find calcium in broccoli and dark green, leafy vegetables (especially collard and turnip greens, ... can enjoy good sources of calcium such as dark green, leafy vegetables, broccoli, chickpeas, and calcium-fortified ...

  11. Casein Phosphopeptide-Amorphous Calcium Phosphate Reduces Streptococcus mutans Biofilm Development on Glass Ionomer Cement and Disrupts Established Biofilms

    PubMed Central

    Liu, Sze-Wei; Myroforidis, Helen; Zalizniak, Ilya; Palamara, Joseph E. A.; Huq, N. Laila; Reynolds, Eric C.

    2016-01-01

    Glass ionomer cements (GIC) are dental restorative materials that are suitable for modification to help prevent dental plaque (biofilm) formation. The aim of this study was to determine the effects of incorporating casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) into a GIC on the colonisation and establishment of Streptococcus mutans biofilms and the effects of aqueous CPP-ACP on established S mutans biofilms. S. mutans biofilms were either established in flow cells before a single ten min exposure to 1% w/v CPP-ACP treatment or cultured in static wells or flow cells with either GIC or GIC containing 3% w/w CPP-ACP as the substratum. The biofilms were then visualised using confocal laser scanning microscopy after BacLight LIVE/DEAD staining. A significant decrease in biovolume and average thickness of S. mutans biofilms was observed in both static and flow cell assays when 3% CPP-ACP was incorporated into the GIC substratum. A single ten min treatment with aqueous 1% CPP-ACP resulted in a 58% decrease in biofilm biomass and thickness of established S. mutans biofilms grown in a flow cell. The treatment also significantly altered the structure of these biofilms compared with controls. The incorporation of 3% CPP-ACP into GIC significantly reduced S. mutans biofilm development indicating another potential anticariogenic mechanism of this material. Additionally aqueous CPP-ACP disrupted established S. mutans biofilms. The use of CPP-ACP containing GIC combined with regular CPP-ACP treatment may lower S. mutans challenge. PMID:27589264

  12. Effect of Chemical Structure and Composition of the Resin Phase on Vinyl Conversion of Amorphous Calcium Phosphate-filled Composites

    PubMed Central

    Skrtic, D.; Antonucci, J.M.

    2008-01-01

    The objective of this study was to elucidate the effect of chemical structure and composition of the polymer matrix on the degree of vinyl conversion (DC) of copolymers (unfilled resins) and their amorphous calcium phosphate (ACP) composites attained upon photo-polymerization. The DC can also be an indicator of the relative potential of these polymeric materials to leach out into the oral environment un-reacted monomers that could adversely affect their biocompatibility. The following resins were examined: 1) 2,2-bis[p-(2′-hydroxy-3′-methacryloxypropoxy)phenyl]propane (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA) (1:1 mass ratio; BT resin) combined with hydroxyethyl methacrylate (HEMA; BTH resin) and with HEMA and zirconyl dimethacrylate (BTHZ resin), 2) urethane dimethacrylate (UDMA)/HEMA resins, and 3) pyromellitic glycerol dimethacrylate (PMGDMA)/TEGDMA (PT resin). To make composite specimens, resins were mixed with a mass fraction of 40 % zirconia-hybridized ACP. Copolymers and their composites were evaluated by near infra-red spectroscopy for DC after 1 d and 28 d post-cure at 23 °C. Inclusion of HEMA into the BT and UDMA resins yielded copolymers and composites with the highest DCs. The significantly lower DCs of PT copolymers and their composites are attributed to the rigid aromatic core structure, tetra-vinyl functionality and limited methacrylate side-chain flexibility of the surface-active PMGDMA monomer. There was, however, an increase in the 28 d DC for the PT materials as there was for the BTHZ system. Surprisingly, the usual decrease observed in DC in going from unfilled polymer to composite was reversed for the PT system. PMID:18714369

  13. Casein Phosphopeptide-Amorphous Calcium Phosphate Reduces Streptococcus mutans Biofilm Development on Glass Ionomer Cement and Disrupts Established Biofilms.

    PubMed

    Dashper, Stuart G; Catmull, Deanne V; Liu, Sze-Wei; Myroforidis, Helen; Zalizniak, Ilya; Palamara, Joseph E A; Huq, N Laila; Reynolds, Eric C

    2016-01-01

    Glass ionomer cements (GIC) are dental restorative materials that are suitable for modification to help prevent dental plaque (biofilm) formation. The aim of this study was to determine the effects of incorporating casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) into a GIC on the colonisation and establishment of Streptococcus mutans biofilms and the effects of aqueous CPP-ACP on established S mutans biofilms. S. mutans biofilms were either established in flow cells before a single ten min exposure to 1% w/v CPP-ACP treatment or cultured in static wells or flow cells with either GIC or GIC containing 3% w/w CPP-ACP as the substratum. The biofilms were then visualised using confocal laser scanning microscopy after BacLight LIVE/DEAD staining. A significant decrease in biovolume and average thickness of S. mutans biofilms was observed in both static and flow cell assays when 3% CPP-ACP was incorporated into the GIC substratum. A single ten min treatment with aqueous 1% CPP-ACP resulted in a 58% decrease in biofilm biomass and thickness of established S. mutans biofilms grown in a flow cell. The treatment also significantly altered the structure of these biofilms compared with controls. The incorporation of 3% CPP-ACP into GIC significantly reduced S. mutans biofilm development indicating another potential anticariogenic mechanism of this material. Additionally aqueous CPP-ACP disrupted established S. mutans biofilms. The use of CPP-ACP containing GIC combined with regular CPP-ACP treatment may lower S. mutans challenge.

  14. Casein phosphopeptide-amorphous calcium phosphate incorporated into sugar confections inhibits the progression of enamel subsurface lesions in situ.

    PubMed

    Walker, G D; Cai, F; Shen, P; Adams, G G; Reynolds, C; Reynolds, E C

    2010-01-01

    Casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) has been demonstrated to exhibit anticariogenic activity in randomized, controlled clinical trials of sugar-free gum and a tooth cream. Two randomized, double-blind, crossover studies were conducted to investigate the potential of CPP-ACP added to hard candy confections to slow the progression of enamel subsurface lesions in an in situ model. The confections studied were: (1) control sugar (65% sucrose + 33% glucose syrup); (2) control sugar-free; (3) sugar + 0.5% (w/w) CPP-ACP; (4) sugar + 1.0% (w/w) CPP-ACP; (5) sugar-free + 0.5% (w/w) CPP-ACP. Participants (10 and 14 in study 1 and 2) wore a removable palatal appliance containing enamel half-slabs with subsurface lesions, except for meals and oral hygiene procedures, and consumed 1 confection 6 times a day for 10 days. The enamel half-slabs were inset to allow the development of plaque on the enamel surface. Participants rested for 1 week before crossing over to another confection. The appliances were stored in a humid container at 37 degrees C when not in the mouth. After each treatment period, the enamel half-slabs were removed, paired with their demineralized control half-slabs, embedded, sectioned and then analysed using transverse microradiography. In both studies consumption of the control sugar confection resulted in significant demineralization (progression) of the enamel subsurface lesions. However, consumption of the sugar confections containing CPP-ACP did not result in lesion progression, but in fact in significant remineralization (regression) of the lesions. Remineralization by consumption of the sugar + 1.0% CPP-ACP confection was significantly greater than that obtained with the sugar-free confection.

  15. In-Vitro Effect of Casein Phosphopeptide Amorphous Calcium Phosphate on Enamel Susceptibility to Staining by Tea during Bleaching Treatment

    PubMed Central

    Alaghemand, Homayoom; Hashemi Kamangar, Sedighe Sadat; Zarenegad, Nafiseh; Tabari, Negin; Khafri, Soraya

    2015-01-01

    Objectives: Bleached enamel is more susceptible to staining, and application of remineralizing agents may decrease enamel susceptibility to staining. This study sought to assess the effect of casein phosphopeptide amorphous calcium phosphate (CPP-ACP) on enamel susceptibility to staining during bleaching treatment. Materials and Methods: Forty central and lateral incisors and first premolar teeth were evaluated in four groups of 10. Group one specimens were subjected to in-office bleaching. Group two underwent in-office bleaching followed by surface treatment with CPP-ACP. Group three specimens received home bleaching and group four underwent home bleaching followed by CPP-ACP surface treatment. After each course of daily bleaching, specimens were immersed in tea solution. Home bleaching (15% carbamide peroxide) was performed for 14 days and in-office bleaching (40% hydrogen peroxide) was carried out in two sessions with an eight-day interval. The color of specimens was analyzed at baseline and post-intervention using Easy Shade Shade-Selection Device. Two-way ANOVA was used to evaluate the effects of bleaching type and surface treatment on color change. Then, the means were compared by Tukey’s HSD test (P=0.05). Results: The interaction effect of surface treatment and type of bleaching was not significant on any color parameter (P>0.05). Surface treatment had significant effects on ΔL (P=0.004). Type of bleaching had a significant effect on “b” parameter (P=0.00). The effect of bleaching type on ΔE was significant (P=0.00) but the effect of surface treatment was not (P=0.34). Conclusion: CPP-ACP had no significant effect on preventing enamel staining by tea during bleaching treatment. PMID:27123021

  16. Antimicrobial Capacity of Casein Phosphopeptide/Amorphous Calcium Phosphate and Enzymes in Glass Ionomer Cement in Dentin Carious Lesions

    PubMed Central

    PINHEIRO, SÉRGIO LUIZ; AZENHA, GIULIANA RODRIGUES; DE MILITO, FLÁVIA; DEMOCH, YASMIN MARIALVA

    2015-01-01

    Objective To evaluate the ability of casein phosphopeptide/amorphous calcium phosphate (CPP/ACP) and lysozyme, lactoferrin, and lactoperoxidase (LLL) added to glass ionomer cement (GIC) to inhibit the growth of S. mutans in a caries model. Material and methods Eighty permanent third molars were selected. The dentin of these teeth was exposed and flattened. Except for the coronal dentin, the specimens were waterproofed, autoclaved, and submitted to cariogenic challenge with standard strain of S. mutans. The carious lesions were sealed as follows: group 1 (n=20): GIC without additives; group 2 (n=20): GIC + CPP/ACP; group 3 (n=20): GIC + LLL; group 4 (n=20): GIC + CPP/ACP + LLL. S. mutans counts were performed before the caries were sealed (n=5), after 24 hours (n=5), at 1 month (n=5), and at 6 months (n=5). The results were analyzed using descriptive statistical analysis and the Kruskal-Wallis test (Student-Newman-Keuls test). Results GIC + LLL caused a significant reduction of S. mutans 1 month after sealing (p<0.01); however, there was a significant growth of S. mutans 6 months after sealing. GIC, GIC + CPP/ACP, and GIC + CPP/ACP + LLL showed similar behavior with significant reduction of S. mutans after 24 hours (p<0.05) and increase after 1 and 6 months. Conclusion The addition of LLL to GIC increases the antimicrobial action of GIC on S. mutans. This leads to control of bacterial biofilm for 1 month, thus stopping the progression of carious lesions. PMID:27688392

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    PubMed

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

    2013-03-01

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

  19. Fabrication of calcium lanthanum sulfide ceramic by carbonate coprecipitating method

    SciTech Connect

    Tsai, M.S.; Hon, M.H. . Dept. of Materials Science and Engineering)

    1995-03-01

    Translucent CLS (calcium lanthanum sulfide) pellets were formed by the carbonate coprecipitation method, CS[sub 2] sulfurization, and hot press sintering. For a La/Ca = 2.5 pellet with 1.3 mm in thickness, the transmittance at 13 [mu]m is about 25% after sintering at 1,150 C for 30 minutes and resulfurizing at 950 C for 1 hour. For a La/Ca = 15 pellet with 0.9 mm in thickness the IR transmittance is about 51% at 13 [mu]m after sintering at 1,050 C for 2 hours and resulfurizing at 950 C for 1 hour. Beta-La[sub 2]S[sub 3] is present as a second phase after sintering at 1,150 C for 30 minutes. After resulfurization, the second phase disappears for the La/Ca = 2.5 pellet, but still exists in the La/Ca = 15 pellet.

  20. Formate Oxidation-Driven Calcium Carbonate Precipitation by Methylocystis parvus OBBP

    PubMed Central

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

    2014-01-01

    Microbially induced carbonate precipitation (MICP) applied in the construction industry poses several disadvantages such as ammonia release to the air and nitric acid production. An alternative MICP from calcium formate by Methylocystis parvus OBBP is presented here to overcome these disadvantages. To induce calcium carbonate precipitation, M. parvus was incubated at different calcium formate concentrations and starting culture densities. Up to 91.4% ± 1.6% of the initial calcium was precipitated in the methane-amended cultures compared to 35.1% ± 11.9% when methane was not added. Because the bacteria could only utilize methane for growth, higher culture densities and subsequently calcium removals were exhibited in the cultures when methane was added. A higher calcium carbonate precipitate yield was obtained when higher culture densities were used but not necessarily when more calcium formate was added. This was mainly due to salt inhibition of the bacterial activity at a high calcium formate concentration. A maximum 0.67 ± 0.03 g of CaCO3 g of Ca(CHOOH)2−1 calcium carbonate precipitate yield was obtained when a culture of 109 cells ml−1 and 5 g of calcium formate liter−1 were used. Compared to the current strategy employing biogenic urea degradation as the basis for MICP, our approach presents significant improvements in the environmental sustainability of the application in the construction industry. PMID:24837386

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

    PubMed

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

    2014-08-01

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

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

    PubMed

    Szcześ, A

    2013-01-01

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

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

    USGS Publications Warehouse

    Leenheer, Jerry A.; Reddy, Michael M.

    2008-01-01

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

  4. Calcium carbonate antacids alter esophageal motility in heartburn sufferers.

    PubMed

    Rodriguez-Stanley, Sheila; Ahmed, Tanveer; Zubaidi, Sattar; Riley, Susan; Akbarali, Hamid I; Mellow, Mark H; Miner, Philip B

    2004-01-01

    Chewed calcium carbonate (CaCO3) rapidly neutralizes esophageal acid and may prevent reflux, suggesting another mechanism of action independent of acid neutralization. Calcium is essential for muscle tone. Our aim was to determine if luminal calcium released from chewed antacids improved esophageal motor function in heartburn sufferers. Esophageal manometry and acid clearance (swallows and time to raise esophageal pH to 5 after a 15-ml 0.1 N HCl bolus) were performed in 18 heartburn sufferers before and after chewing two Tums EX (1500 mg CaCO3, 600 mg calcium). Subjects with hypertensive esophageal contractions or hypertensive lower esophageal sphincter pressure (LESP) were excluded. Subjects with normal to low LESP were included. Differences between parameters were determined by two-tailed paired t-tests, P < 0.05. Proximal esophageal contractile amplitude was significantly increased after CaCO3 (47.18 vs 52.97 mm Hg; P = 0.02), distal onset velocity was significantly decreased after CaCO3 (4.34 vs 3.71 cm/sec; P = 0.02), and acid clearance was significantly increased 30 min after CaCO3 (20.35 vs 11.7 swallows, [P < 0.005] and 12.19 vs 6.29 min [P < 0.007]). LESP was not altered after CaCO3 (22.70 vs 23.79 mm Hg; P = 0.551), however, LESP increased in 9 of 18 subjects. Depth of LES relaxation, medial and distal esophageal contractile amplitude, and duration of contractions were not altered by CaCO3. CaCO3 did not alter salivary secretion and pH in a subset of these subjects, and CaCO3 with secreted saliva did not neutralize a 15-ml acid bolus. The Ca2+ released after chewing of CaCO3 antacids may be partially responsible for the reduction of heartburn by significantly improving initiation of peristalsis and acid clearance.

  5. Spectrophotometric measurement of calcium carbonate saturation states in seawater.

    PubMed

    Easley, Regina A; Patsavas, Mark C; Byrne, Robert H; Liu, Xuewu; Feely, Richard A; Mathis, Jeremy T

    2013-02-05

    Measurements of ocean pH and carbonate ion concentrations in the North Pacific and Arctic Oceans were used to determine calcium carbonate saturation states (Ω(CaCO(3))) from spectrophotometric methods alone. Total carbonate ion concentrations, [CO(3)(2-)](T), were for the first time at sea directly measured using Pb(II) UV absorbance spectra. The basis of the method is given by the following: [formula see text] where (CO(3))β(1) is the PbCO(3)(0) formation constant, e(i) are molar absorptivity ratios, and R = (250)A/(234)A (ratio of absorbances measured at 250 and 234 nm). On the basis of shipboard and laboratory Pb(II) data and complementary carbon-system measurements, the experimental parameters were determined to be (25 °C) the following: [formula see text]. The resulting mean difference between the shipboard spectrophotometric and conventional determinations of [CO(3)(2-)](T) was ±2.03 μmol kg(-1). The shipboard analytical precision of the Pb(II) method was ∼1.71 μmol kg(-1) (2.28%). Spectrophotometric [CO(3)(2-)](T) and pH(T) were then combined to calculate Ω(CaCO(3)). For the case of aragonite, 95% of the spectrophotometric aragonite saturation states (Ω(Aspec)) were within ±0.06 of the conventionally calculated values (Ω(Acalc)) when 0.5 ≤ Ω(A) ≤ 2.0. When Ω(A) > 2.0, 95% of the Ω(Aspec) values were within ±0.18 of Ω(Acalc). Our shipboard experience indicates that spectrophotometric determinations of [CO(3)(2-)](T) and Ω(CaCO(3)) are straightforward, fast, and precise. The method yields high-quality measurements of two important, rapidly changing aspects of ocean chemistry and offers capabilities suitable for long-term automated in situ monitoring.

  6. Particle size of calcium carbonate does not affect apparent and standardized total tract digestibility of calcium, retention of calcium, or growth performance of growing pigs.

    PubMed

    Merriman, L A; Stein, H H

    2016-09-01

    Two experiments were conducted to evaluate particle size of calcium carbonate used in diets fed to growing pigs. Experiment 1 was conducted to determine apparent total tract digestibility (ATTD), standardized total tract digestibility (STTD), and retention of Ca among diets containing calcium carbonate produced to different particle sizes, and Exp. 2 was conducted to determine if growth performance of weanling pigs is affected by particle size of calcium carbonate. In Exp. 1, 4 diets based on corn and potato protein isolate were formulated to contain 0.70% Ca and 0.33% standardized total tract digestible P, but the calcium carbonate used in the diets was ground to 4 different particle sizes (200, 500, 700, or 1,125 μm). A Ca-free diet was formulated to determine basal endogenous losses of Ca. In Exp. 2, 4 diets were based on corn and soybean meal and the only difference among diets was that each diet contained calcium carbonate ground to the 4 particle sizes used in Exp. 1. In Exp. 1, 40 barrows (15.42 ± 0.70 kg initial BW) were allotted to the 5 diets with 8 replicate pigs per diet using a randomized complete block design, and in Exp. 2, 128 pigs with an initial BW of 9.61 ± 0.09 kg were randomly allotted to 4 experimental diets. Results of Exp. 1 indicated that basal endogenous losses of Ca were 0.329 g/kg DMI. The ATTD of Ca was 70.0 ± 3.2, 74.3 ± 2.7, 70.0 ± 2.9, and 72.1 ± 2.7 and the STTD of Ca was 74.2 ± 3.2, 78.5 ± 2.7, 74.1 ± 2.9, and 76.2 ± 2.7 for calcium carbonate ground to 200, 500, 700, or 1,125 μm, respectively. Retention of Ca was 67.4 ± 3.1, 70.4 ± 2.6, 63.9 ± 2.8, and 67.2 ± 2.2 for diets containing calcium carbonate ground to 200, 500, 700, or 1,125 μm, respectively. There were no differences among diets for ATTD of Ca, STTD of Ca, or retention of Ca. The ATTD of P was 64.5 ± 1.7, 66.8 ± 2.6, 64.2 ± 3.0, and 63.2 ± 1.7% and retention of P was 61.4 ± 1.4, 63.8 ± 2.8, 61.9 ± 2.8, and 60.9 ± 1.5 for diets containing calcium

  7. Porous calcium carbonate as a carrier material to increase the dissolution rate of poorly soluble flavouring compounds.

    PubMed

    Lundin Johnson, Maria; Noreland, David; Gane, Patrick; Schoelkopf, Joachim; Ridgway, Cathy; Millqvist Fureby, Anna

    2017-03-15

    Two different food grade functionalised porous calcium carbonates (FCC), with different pore size and pore size distributions, were characterised and used as carrier materials to increase the dissolution rate of poorly soluble flavouring compounds in aqueous solution. The loading level was varied between 1.3% by weight (wt%) and 35 wt%, where the upper limit of 35 wt% was the total maximum loading capacity of flavouring compound in FCC based on the fraction of the total weight of FCC plus flavouring compound. Flavouring compounds (l-carvone, vanillin, and curcumin) were selected based on their difference in hydrophilicity and capacity to crystallise. Release kinetic studies revealed that all flavouring compounds showed an accelerated release when loaded in FCC compared to dissolution of the flavouring compound itself in aqueous medium. The amorphous state and/or surface enlargement of the flavouring compound inside or on FCC explains the faster release. The flavouring compounds capable of crystallising (vanillin and curcumin) were almost exclusively amorphous within the porous FCC material as determined by X-ray powder diffraction one week after loading and after storing the loaded FCC material for up to 9 months at room temperature. A small amount of crystalline vanillin and curcumin was detected in the FCC material with large pores and high flavouring compound loading (≥30 wt%). Additionally, two different loading strategies were evaluated, loading by dissolving the flavouring compound in acetone or loading by a hot melt method. Porosimetry data showed that the melt method was more efficient in filling the smallest pores (<100 nm). The main factor influencing the release rate appears to be the amorphous state of the flavouring compound and the increase in exposed surface area. The confinement in small pores prevents crystallisation of the flavouring compounds during storage, providing a stable amorphous form retaining high release rate also after storage.

  8. Correlation between substrate bias, growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Liu, Aiping; Zhu, Jiaqi; Han, Jiecai; Wu, Huaping; Jia, Zechun

    2007-09-01

    We investigate the growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon (ta-C:P) films which are deposited at different substrate biases by filtered cathodic vacuum arc technique with PH 3 as the dopant source. The films are characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, Raman spectroscopy, residual stress measurement, UV/VIS/NIR absorption spectroscopy and temperature-dependent conductivity measurement. The atomic fraction of phosphorus in the films as a function of substrate bias is obtained by XPS analysis. The optimum bias for phosphorus incorporation is about -80 V. Raman spectra show that the amorphous structures of all samples with atomic-scaled smooth surface are not remarkably changed when PH 3 is implanted, but some small graphitic crystallites are formed. Moreover, phosphorus impurities and higher-energetic impinging ions are favorable for the clustering of sp 2 sites dispersed in sp 3 skeleton and increase the level of structural ordering for ta-C:P films, which further releases the compressive stress and enhances the conductivity of the films. Our analysis establishes an interrelationship between microstructure, stress state, electrical properties, and substrate bias, which helps to understand the deposition mechanism of ta-C:P films.

  9. Carbon-assisted growth and high visible-light optical reflectivity of amorphous silicon oxynitride nanowires

    PubMed Central

    2011-01-01

    Large amounts of amorphous silicon oxynitride nanowires have been synthesized on silicon wafer through carbon-assisted vapor-solid growth avoiding the contamination from metallic catalysts. These nanowires have the length of up to 100 μm, with a diameter ranging from 50 to 150 nm. Around 3-nm-sized nanostructures are observed to be homogeneously distributed within a nanowire cross-section matrix. The unique configuration might determine the growth of ternary amorphous structure and its special splitting behavior. Optical properties of the nanowires have also been investigated. The obtained nanowires were attractive for their exceptional whiteness, perceived brightness, and optical brilliance. These nanowires display greatly enhanced reflection over the whole visible wavelength, with more than 80% of light reflected on most of the wavelength ranging from 400 to 700 nm and the lowest reflectivity exceeding 70%, exhibiting performance superior to that of the reported white beetle. Intense visible photoluminescence is also observed over a broad spectrum ranging from 320 to 500 nm with two shoulders centered at around 444 and 468 nm, respectively. PMID:21787429

  10. The Infrared Spectra and Absorption Intensities of Amorphous Ices: Methane and Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Gerakines, Perry A.; Hudson, Reggie L.; Loeffler, Mark J.

    2015-11-01

    Our research group is carrying out new IR measurements of icy solids relevant to the outer solar system and the interstellar medium, with an emphasis on amorphous and crystalline ices below ~70 K. Our goal is to add to the relatively meager literature on this subject and to provide electronic versions of state-of-the-art data, since the abundances of such molecules cannot be deduced without accurate reference spectra and IR band strengths. In the past year, we have focused on two of the simplest and most abundant components of icy bodies in the solar system - methane (CH4) and carbon dioxide (CO2). Infrared spectra from ˜ 4500 to 500 cm-1 have been measured for each of these molecules in μm-thick films at temperatures from 10 to 70 K. All known amorphous and crystalline phases have been reproduced and, for some, presented for the first time. We also report measurements of the index of refraction at 670 nm and the mass densities for each ice phase. Comparisons are made to earlier work where possible. Electronic versions of our new results are available at http://science.gsfc.nasa.gov/691/cosmicice/ constants.html.

  11. Conversion of calcium sulphide to calcium carbonate during the process of recovery of elemental sulphur from gypsum waste.

    PubMed

    de Beer, M; Maree, J P; Liebenberg, L; Doucet, F J

    2014-11-01

    The production of elemental sulphur and calcium carbonate (CaCO3) from gypsum waste can be achieved by thermally reducing the waste into calcium sulphide (CaS), which is then subjected to a direct aqueous carbonation step for the generation of hydrogen sulphide (H2S) and CaCO3. H2S can subsequently be converted to elemental sulphur via the commercially available chemical catalytic Claus process. This study investigated the carbonation of CaS by examining both the solution chemistry of the process and the properties of the formed carbonated product. CaS was successfully converted into CaCO3; however, the reaction yielded low-grade carbonate products (i.e. <90 mass% as CaCO3) which comprised a mixture of two CaCO3 polymorphs (calcite and vaterite), as well as trace minerals originating from the starting material. These products could replace the Sappi Enstra CaCO3 (69 mass% CaCO3), a by-product from the paper industry which is used in many full-scale AMD neutralisation plants but is becoming insufficient. The insight gained is now also being used to develop and optimize an indirect aqueous CaS carbonation process for the production of high-grade CaCO3 (i.e. >99 mass% as CaCO3) or precipitated calcium carbonate (PCC).

  12. Effects of iron and calcium carbonate on the variation and cycling of carbon source in integrated wastewater treatments.

    PubMed

    Zhimiao, Zhao; Xinshan, Song; Yufeng, Zhao; Yanping, Xiao; Yuhui, Wang; Junfeng, Wang; Denghua, Yan

    2017-02-01

    Iron and calcium carbonate were added in wastewater treatments as the adjusting agents to improve the contaminant removal performance and regulate the variation of carbon source in integrated treatments. At different temperatures, the addition of the adjusting agents obviously improved the nitrogen and phosphorous removals. TN and TP removals were respectively increased by 29.41% and 23.83% in AC-100 treatment under 1-day HRT. Carbon source from dead algae was supplied as green microbial carbon source and Fe(2+) was supplied as carbon source surrogate. COD concentration was increased to 30mg/L and above, so the problem of the shortage of carbon source was solved. Dead algae and Fe(2+) as carbon source supplement or surrogate played significant role, which was proved by microbial community analysis. According to the denitrification performance in the treatments, dead algae as green microbial carbon source combined with iron and calcium carbonate was the optimal supplement carbon source in wastewater treatment.

  13. Dissolution kinetics of calcium carbonate in equatorial Pacific sediments

    NASA Astrophysics Data System (ADS)

    Berelson, William M.; Hammond, Douglas E.; McManus, James; Kilgore, Tammy E.

    1994-06-01

    Benthic chambers were deployed in the equatorial eastern Pacific Ocean on a transect along the equator between 103°W and 140°W and on a transect across the equator at 140°W in order to establish the rate of calcium carbonate dissolution on the seafloor. Dissolution was determined from the rate of alkalinity increase within an incubation chamber, measured over an 80-120 hour incubation period. Dissolution rates were lowest at eastern Pacific sites (0.2-0.4 mmol CaCO3/m2/d) and highest at the equatorial, 140°W sites (0.5-0.7 mmol/m2/d). Both oxygen consumption rates and the degree of bottom water saturation govern dissolution rates. Measured dissolution and oxygen consumption rates are used with a numerical model to constrain the value of the dissolution rate constant k, formulated according to the equation developed by Keir [1980]: dissolution rate = kγ(1-Ω)n. The observed dissolution fluxes are predicted by the model when k = 5 to 100%/d and n = 4.5. This range of k values has important implications regarding the type of carbonate dissolving and its location within the sediment column. At low values of k, organic carbon rain rates to the seafloor become the dominant driving force of carbonate dissolution. At higher values of k, the degree of bottom water undersaturation becomes more important. Dissolution of carbonate within equatorial Pacific sediments can be adequately described with k = 20 ± 10%/d, a rate constant much lower than some previously used values. Dissolution rates do not vary significantly over chamber boundary layer thicknesses between 200 and 800 μm, indicating that dissolution is not controlled by hydrodynamic conditions. Chambers acidified with HCl yield very large dissolution rates, but for a given degree of acidification the dissolution rate was constant for sites ranging from water depths of 3300-4400 m. This implies that there are not more and less easily dissolved forms of CaCO3 arriving on the seafloor between these depths. A budget

  14. Effect of tetrahedral amorphous carbon coating on the resistivity and wear of single-walled carbon nanotube network

    NASA Astrophysics Data System (ADS)

    Iyer, Ajai; Kaskela, Antti; Novikov, Serguei; Etula, Jarkko; Liu, Xuwen; Kauppinen, Esko I.; Koskinen, Jari

    2016-05-01

    Single walled carbon nanotube networks (SWCNTNs) were coated by tetrahedral amorphous carbon (ta-C) to improve the mechanical wear properties of the composite film. The ta-C deposition was performed by using pulsed filtered cathodic vacuum arc method resulting in the generation of C+ ions in the energy range of 40-60 eV which coalesce to form a ta-C film. The primary disadvantage of this process is a significant increase in the electrical resistance of the SWCNTN post coating. The increase in the SWCNTN resistance is attributed primarily to the intrinsic stress of the ta-C coating which affects the inter-bundle junction resistance between the SWCNTN bundles. E-beam evaporated carbon was deposited on the SWCNTNs prior to the ta-C deposition in order to protect the SWCNTN from the intrinsic stress of the ta-C film. The causes of changes in electrical resistance and the effect of evaporated carbon thickness on the changes in electrical resistance and mechanical wear properties have been studied.

  15. Response to visible light in amorphous carbon nitride films prepared by reactive sputtering

    NASA Astrophysics Data System (ADS)

    Aono, Masami; Harata, Tomo; Kitazawa, Nobuaki; Watanabe, Yoshihisa

    2016-01-01

    Amorphous carbon nitride (a-CNx) deposited by reactive sputtering shows deformation, photoconductive behavior, and thermal radiation by visible light irradiation. In this study, we investigated these photoresponse behaviors of a-CNx. To obtain films with different bonding structures, the films were deposited at various temperatures from 473 to 873 K. A reduction in N/C ratio led to a decrease in C-N bonding fraction and an increase in graphite component. The optical band gaps decreased with increasing temperature. Under white light illumination, the surface temperature of a-CNx increased with the narrowing of the band gap owing to the conversion of photon energy primarily into thermal energy. On the photoconductivity and deformation, a nonlinear relationship to the band gap energy was observed. In addition, both these photoresponses showed opposite trends in relation to the deposition temperature. The photoinduced deformation was suppressed by increasing the graphite component and decreasing the C-N bonding fraction.

  16. Highly photoconductive amorphous carbon nitride films prepared by cyclic nitrogen radical sputtering

    NASA Astrophysics Data System (ADS)

    Katsuno, T.; Nitta, S.; Habuchi, H.; Stolojan, V.; Silva, S. R. P.

    2004-10-01

    We report on the growth of amorphous carbon nitride films (a-CNx) showing the highest conductivity to date. The films were prepared using a layer-by-layer method (a-CNx:LL), by the cyclical nitrogen radical sputtering of a graphite radical, alternated with a brief hydrogen etch. The photosensitivity S of these films is 105, defined as the ratio of the photoconductivity σp to the dark conductivity σd and is the highest value reported thus far. We believe that the carriers generated by the monochromatic light (photon energy 6.2eV) in the a-CNx:LL films are primarily electrons, with the photoconductivity shown to increase with substrate deposition temperature.

  17. Study of nitrogen implanted amorphous hydrogenated carbon thin films by variable-energy positron annihilation spectroscopy

    SciTech Connect

    Freire, F.L. Jr.; Franceschini, D.F.; Brusa, R.S.; Karwasz, G.R.; Mariotto, G.; Zecca, A.; Achete, C.A.

    1997-03-01

    Hard amorphous hydrogenated carbon ({ital a}-C:H) films deposited by self-bias glow discharge were implanted at room temperature with 70 keV nitrogen ions at fluences between 2.0 and 9.0{times}10{sup 16} N/cm{sup 2}. The implanted samples were analyzed by positron Doppler broadening annihilation spectroscopy to determine the voids distribution. For samples implanted with 2.0{times}10{sup 16} N/cm{sup 2} the defect distribution is broader than the vacancies depth profile predicted by Monte Carlo simulation. For higher fluences we observed a reduction of the defect density. These results are discussed in terms of a competition between two processes: ion induced defects and structural modifications induced in the films due to ion implantation. {copyright} {ital 1997 American Institute of Physics.}

  18. Mechanism of wiggling enhancement due to HBr gas addition during amorphous carbon etching

    NASA Astrophysics Data System (ADS)

    Kofuji, Naoyuki; Ishimura, Hiroaki; Kobayashi, Hitoshi; Une, Satoshi

    2015-06-01

    The effect of gas chemistry during etching of an amorphous carbon layer (ACL) on wiggling has been investigated, focusing especially on the changes in residual stress. Although the HBr gas addition reduces critical dimension loss, it enhances the surface stress and therefore increases wiggling. Attenuated total reflectance Fourier transform infrared spectroscopy revealed that the increase in surface stress was caused by hydrogenation of the ACL surface with hydrogen radicals. Three-dimensional (3D) nonlinear finite element method analysis confirmed that the increase in surface stress is large enough to cause the wiggling. These results also suggest that etching with hydrogen compound gases using an ACL mask has high potential to cause the wiggling.

  19. Tunable positive magnetoresistance effect of Co-doped amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Jiang, Y. C.; Wu, Z. P.; Bao, W.; Xu, S. J.; Gao, J.

    2012-04-01

    Co-doped amorphous carbon (a-C:Co) films were deposited on n-type Si substrates by pulsed-laser deposition method. A positive magnetoresistance (PMR) effect has been observed after Co doped into a-C films. Such a PMR is tuned by the bias voltage and reaches a peak at a particular voltage, as observed from the Current-voltage relations of the a-C:Co/Si junctions at various magnetic fields. MR-H characteristics were further studied at the temperatures of 65 K, which showed that under the reverse electric field the a-C:Co/Si junctions had a colossal PMR (over 100%). Raman spectra results demonstrate that Co doping favors the formation of graphitic sp2 sites. The mechanism of the PMR effect is attributed to the interactions between the applied magnetic field and Co ions, which leads to the transition from sp2 sites to sp3 sites and increase the resistance.

  20. Amorphous Vanadium Oxide/Carbon Composite Positive Electrode for Rechargeable Aluminum Battery.

    PubMed

    Chiku, Masanobu; Takeda, Hiroki; Matsumura, Shota; Higuchi, Eiji; Inoue, Hiroshi

    2015-11-11

    Amorphous vanadium oxide/carbon composite (V2O5/C) was first applied to the positive electrode active material for rechargeable aluminum batteries. Electrochemical properties of V2O5/C were investigated by cyclic voltammetry and charge-discharge tests. Reversible reduction/oxidation peaks were observed for the V2O5/C electrode and the rechargeable aluminum cell showed the maximum discharge capacity over 200 mAh g(-1) in the first discharging. The XPS analyses after discharging and the following charging exhibited that the redox of vanadium ion in the V2O5/C active material occurred during discharging and charging, and the average valence of V changed between 4.14 and 4.85.

  1. Bioactivity and hemocompatibility study of amorphous hydrogenated carbon coatings produced by pulsed magnetron discharge.

    PubMed

    Lopez-Santos, C; Colaux, J L; Laloy, J; Fransolet, M; Mullier, F; Michiels, C; Dogné, J-M; Lucas, S

    2013-06-01

    Literature contains very few data about the potential biomedical application of amorphous hydrogenated carbon (a-C:H) thin films deposited by reactive pulsed magnetron discharge even so it is one of the most scalable plasma deposition technique. In this article, we show that such a C2H2 pulsed magnetron plasma produces high quality coating with good hemocompatibility and bioactive response: no effect on hemolysis and hemostasis were observed, and proliferation of various cell types such as endothelial, fibroblast, and osteoblast-like cells was not affected when the deposition conditions were varied. Cell growth on a-C:H coatings is proposed to take place by a two-step process: the initial cell contact is affected by the smooth topography of the a-C:H coatings, whereas the polymeric-like structure, together with a moderate hydrophilicity and a high hydrogen content, directs the posterior cell spreading while preserving the hemocompatible behavior.

  2. Understanding the catalyst-free transformation of amorphous carbon into graphene by current-induced annealing

    PubMed Central

    Barreiro, Amelia; Börrnert, Felix; Avdoshenko, Stanislav M.; Rellinghaus, Bernd; Cuniberti, Gianaurelio; Rümmeli, Mark H.; Vandersypen, Lieven M. K.

    2013-01-01

    We shed light on the catalyst-free growth of graphene from amorphous carbon (a–C) by current-induced annealing by witnessing the mechanism both with in-situ transmission electron microscopy and with molecular dynamics simulations. Both in experiment and in simulation, we observe that small a–C clusters on top of a graphene substrate rearrange and crystallize into graphene patches. The process is aided by the high temperatures involved and by the van der Waals interactions with the substrate. Furthermore, in the presence of a–C, graphene can grow from the borders of holes and form a seamless graphene sheet, a novel finding that has not been reported before and that is reproduced by the simulations as well. These findings open up new avenues for bottom-up engineering of graphene-based devices.

  3. Amorphous carbon film growth on Si: Correlation between stress and generation of defects into the substrate

    SciTech Connect

    Brusa, R.S.; Macchi, C.; Mariazzi, S.; Karwasz, G.P.; Laidani, N.; Bartali, R.; Anderle, M.

    2005-05-30

    Amorphous carbon films of several thicknesses were prepared by graphite sputtering on crystalline silicon substrate. The samples were depth profiled with positron annihilation spectroscopy for open-volume measurements and characterized for their residual internal stress. It was found that after film growth the substrate presents vacancy-like defects decorated by oxygen in a layer extending in the substrate by several tens of nanometers beyond the film/Si interface. The width of the defected layer and the decoration of vacancy-like defects are directly and inversely proportional to the measured intensity of the residual stress, respectively. These findings indicate the existence of a relaxation mechanism of the stress in the films that involves deeply the substrate. The decorated vacancy-like defects are suggested to be bounded to dislocations induced in the substrate by the stress relaxation.

  4. Amorphous carbon enriched with pyridinic nitrogen as an efficient metal-free electrocatalyst for oxygen reduction reaction.

    PubMed

    Chen, Jingyan; Wang, Xin; Cui, Xiaoqiang; Yang, Guangmin; Zheng, Weitao

    2014-01-18

    An amorphous metal-free N-doped carbon film prepared by sputtering and annealing exhibits comparable electrocatalytic activity and superior stability and methanol tolerance to the commercial Pt/C catalyst via a four-electron pathway for oxygen reduction reaction (ORR). Pyridinic nitrogen in films plays a key role in electrocatalytic activity for ORR.

  5. Amorphous Molybdenum Sulfide on Graphene-Carbon Nanotube Hybrids as Highly Active Hydrogen Evolution Reaction Catalysts.

    PubMed

    Pham, Kien-Cuong; Chang, Yung-Huang; McPhail, David S; Mattevi, Cecilia; Wee, Andrew T S; Chua, Daniel H C

    2016-03-09

    In this study, we report on the deposition of amorphous molybdenum sulfide (MoSx, with x ≈ 3) on a high specific surface area conductive support of Graphene-Carbon Nanotube hybrids (GCNT) as the Hydrogen Evolution Reaction (HER) catalysts. We found that the high surface area GCNT electrode could support the deposition of MoSx at much higher loadings compared with simple porous carbon paper or flat graphite paper. The morphological study showed that MoSx was successfully deposited on and was in good contact with the GCNT support. Other physical characterization techniques suggested the amorphous nature of the deposited MoSx. With a typical catalyst loading of 3 mg cm(-2), an overpotential of 141 mV was required to obtain a current density of 10 mA cm(-2). A Tafel slope of 41 mV decade(-1) was demonstrated. Both measures placed the MoSx-deposited GCNT electrode among the best performing molybdenum sulfide-based HER catalysts reported to date. The electrode showed a good stability with only a 25 mV increase in overpotential required for a current density of 10 mA cm(-2), after undergoing 500 potential sweeps with vigorous bubbling present. The current density obtained at -0.5 V vs SHE (Standard Hydrogen Electrode potential) decreased less than 10% after the stability test. The deposition of MoSx on high specific surface area conductive electrodes demonstrated to be an efficient method to maximize the catalytic performance toward HER.

  6. Multiscale simulation of thermal disruption in resistance switching process in amorphous carbon

    NASA Astrophysics Data System (ADS)

    Popov, A. M.; Shumkin, G. N.; Nikishin, N. G.

    2015-09-01

    The switching of material atomic structure and electric conductivity is used in novel technologies of making memory on the base of phase change. The possibility of making memory on the base of amorphous carbon is shown in experiment [1]. Present work is directed to simulation of experimentally observed effects. Ab initio quantum calculations were used for simulation of atomic structure changes in amorphous carbon [2]. These simulations showed that the resistance change is connected with thermally induced effects. The temperature was supposed to be the function of time. In present paper we propose a new multiscale, self-consistent model which combines three levels of simulation scales and takes into account the space and time dependencies of the temperature. On the first level of quantum molecular dynamic we provide the calculations of phase change in atomic structure with space and time dependence of the temperature. Nose-Hover thermostats are used for MD simulations to reproduce space dependency of the temperature. It is shown that atomic structure is localized near graphitic layers in conducting dot. Structure parameter is used then on the next levels of the modeling. Modified Ehrenfest Molecular Dynamics is used on the second level. Switching evolution of electronic subsystem is obtained. In macroscopic scale level the heat conductivity equation for continuous media is used for calculation space-time dependence of the temperature. Joule heat source depends on structure parameter and electric conductivity profiles obtained on previous levels of modeling. Iterative procedure is self-consistently repeated combining three levels of simulation. Space localization of Joule heat source leads to the thermal disruption. Obtained results allow us to explain S-form of the Volt-Ampere characteristic observed in experiment. Simulations were performed on IBM Blue Gene/P supercomputer at Moscow State University.

  7. Characterization of microstructure and mechanical behavior of sputter deposited Ti-containing amorphous carbon coatings.

    SciTech Connect

    Feng, B.; Cao, D. M.; Meng, W. J.; Xu, J.; Tittsworth, R. C.; Rehn, L. E.; Baldo, P. M.; Doll, G. L.; Materials Science Division; Louisiana State Univ.; The Timken Company

    2001-12-03

    We report on the characterization of microstructure and mechanical properties of sputter deposited Ti-containing amorphous carbon (Ti-aC) coatings as a function of Ti composition. Ti-aC coatings have been deposited by unbalanced magnetron sputter deposition, in an industrial-scale four-target coating deposition system. The composition and microstructure of the Ti-aC coatings have been characterized in detail by combining the techniques of Rutherford backscattering spectrometry (RBS) and hydrogen elastic recoil detection (ERD), transmission electron microscopy (TEM), X-ray absorption near edge structure (XANES) spectroscopy and extended X-ray absorption fine structure (EXAFS) spectroscopy. At Ti compositions <4at.%, Ti atoms dissolve in an amorphous carbon (a-C) matrix. The dissolution limit of Ti atoms in an a-C matrix is determined to be between 4 and 8 at.%. At Ti compositions >8 at.%, XANES and EXAFS data indicate that the average Ti atomic bonding environment in Ti-aC coatings resembles that in cubic B1-TiC, consistent with TEM observation of precipitation of TiC nanocrystallites in the a-C matrix. Beyond the Ti dissolution limit, the Ti-aC coatings are nanocomposites with nanocrystalline TiC clusters embedded in an a-C matrix. A large scale, quasi one-dimensional composition modulation in the Ti-aC coatings was observed due to the particular coating deposition geometry. Elastic stiffness and hardness of the Ti-aC coatings were measured by instrumented nanoindentation and found to vary systematically as a function of Ti composition. Unlubricated friction coefficient of Ti-aC coatings against WC-Co balls was found to increase as the Ti composition increases. As Ti composition increases, the overall mechanical behavior of the Ti-aC coatings becomes more TiC-like.

  8. Gigahertz range electromagnetic wave absorbers made of amorphous-carbon-based magnetic nanocomposites

    NASA Astrophysics Data System (ADS)

    Liu, Jiu Rong; Itoh, Masahiro; Horikawa, Takashi; Machida, Ken-Ichi; Sugimoto, Satoshi; Maeda, Toru

    2005-09-01

    Nanocomposite magnetic materials α-Fe/C(a), Fe2B/C(a), and Fe1.4Co0.6B/C(a) were prepared by mechanically grinding α-Fe, Fe2B, or Fe1.4Co0.6B with amorphous carbon [C(a)] powders. Complex permittivity, permeability, and electromagnetic wave absorption properties of resin compacts containing 40-vol % composite powders of α-Fe/C(a), Fe2B/C(a), and Fe1.4Co0.6B/C(a) were characterized according to a conventional reflection/transmission technique. The real part (ɛr') and imaginary part (Vr'') of the relative permittivity are low and almost independent of frequency between 0.05 and 40 GHz. The Imaginary part (μr'') of the relative permeability exhibited wide peaks in the 1-9-GHz range for α-Fe/C(a), in the 2-18-GHz range for Fe2B/C(a), and in the 18-40-GHz range for Fe1.4Co0.6B/C(a) owing to their different magnetocrystalline anisotropy field (HA) values. Consequently, the resin compacts of 40-vol % α-Fe/C(a), Fe2B/C(a), and Fe1.4Co0.6B/C(a) powders provided good electromagnetic (em) wave absorption performances (reflection loss<-20 dB) in ranges of 4.3-8.2 GHz (G band), 7.5-16.0 GHz (X band), and 26.5-40 GHz (Q band) over absorber thicknesses of 1.8-3.3, 1.2-2.2, and 0.63-0.82 mm, respectively. Our experimental results demonstrate that the amorphous-carbon-based magnetic nanocomposites are promising for the application to produce thin and light EM wave absorbers.

  9. Residual stress and Raman spectra of laser deposited highly-tetrahedral-coordinated-amorphous-carbon films

    SciTech Connect

    Friedmann, T.A.; Siegal, M.P.; Tallant, D.R.; Simpson, R.L.; Dominguez, F.

    1994-05-01

    We are studying carbon thin films by using a pulsed excimer laser to ablate pyrolytic graphite targets to form highly tetrahedral coordinated amorphous carbon ({alpha}t-C) films. These films have been grown on room temperature p-type Si (100) substrates without the intentional incorporation of hydrogen. In order to understand and optimize the growth of {alpha}t-C films, parametric studies of the growth parameters have been performed. We have also introduced various background gases (H{sub 2}, N{sub 2} and Ar) and varied the background gas pressure during deposition. The residual compressive stress levels in the films have been measured and correlated to changes in the Raman spectra of the {alpha}t-C band near 1565 cm{sup {minus}1}. The residual compressive stress falls with gas pressure, indicating a decreasing atomic sp{sup 3}-bonded carbon fraction. We find that reactive gases such as hydrogen and nitrogen significantly alter the Raman spectra at higher pressures. These effects are due to a combination of chemical incorporation of nitrogen and hydrogen into the film as well as collisional cooling of the ablation plume. In contrast, films grown in non-reactive Ar background gases show much less dramatic changes in the Raman spectra at similar pressures.

  10. Biomineralization of calcium carbonate polymorphs by the bacterial strains isolated from calcareous sites.

    PubMed

    Dhami, Navdeep Kaur; Reddy, M Sudhakara; Mukherjee, Abhijit

    2013-05-01

    Microbially induced calcium carbonate precipitation (MICCP) is a naturally occurring biological process that has various applications in remediation and restoration of a range of building materials. In the present investigation, five ureolytic bacterial isolates capable of inducing calcium carbonate precipitation were isolated from calcareous soils on the basis of production of urease, carbonic anhydrase, extrapolymeric substances, and biofilm. Bacterial isolates were identified as Bacillus megaterium, B. cereus, B. thuringiensis, B. subtilis, and Lysinibacillus fusiformis based on 16S rRNA analysis. The calcium carbonate polymorphs produced by various bacterial isolates were analyzed by scanning electron microscopy, confocal laser scanning microscopy, X ray diffraction, and Fourier transmission infra red spectroscopy. A strainspecific precipitation of calcium carbonate forms was observed from different bacterial isolates. Based on the type of polymorph precipitated, the technology of MICCP can be applied for remediation of various building materials.

  11. Electrical and Electrochemical Properties of Nitrogen-Containing Tetrahedral Amorphous Carbon (ta-C) Thin Films

    NASA Astrophysics Data System (ADS)

    Yang, Xingyi

    Tetrahedral amorphous carbon (ta-C) is a diamond-like carbon (DLC) material comprised of a mixture of sp2 (˜40%) and sp3-bonded (˜60%) carbon domains. The physicochemical structure and electrochemical properties depend strongly on the sp2/sp3 bonding ratio as well as the incorporation of impurities, such as hydrogen or nitrogen. The ability to grow ta-C films at lower temperatures (25-100 °C) on a wider variety of substrates is a potential advantage of these materials as compared with diamond films. In this project, the basic structural and electrochemical properties of nitrogen-incorporated ta-C thin films will be discussed. The major goal of this work was to determine if the ta-C:N films exhibit electrochemical properties more closely aligned with those of boron-doped diamond (sp 3 carbon) or glassy carbon (amorphous sp2 carbon). Much like diamond, ta-C:N thin-film electrodes are characterized by a low background voltammetric current, a wide working potential window, relatively rapid electron-transfer kinetics for aqueous redox systems, such as Fe(CN) 6-3/-4 and Ru(NH3)6+3/+2 , and weak adsorption of polar molecules from solution. For example, negligible adsorption of methylene blue was found on the ta-C:N films in contrast to glassy carbon; a surface on which this molecule strongly adsorbs. The film microstructure was studied with x-ray photoelectron microscopy (XPS), visible Raman spectroscopy and electron-energy loss spectroscopy (EELS); all of which revealed the sp2-bonded carbon content increased with increasing nitrogen. The electrical properties of ta-C:N films were studied by four-point probe resistance measurement and conductive-probe AFM (CP-AFM). The incorporation of nitrogen into ta-C films increased the electrical conductivity primarily by increasing the sp2-bonded carbon content. CP-AFM showed the distribution of the conductive sp2-carbon on the film surface was not uniform. These films have potential to be used in field emission area. The

  12. Calcium Carbonate Formation by Genetically Engineered Inorganic Binding Peptides

    NASA Astrophysics Data System (ADS)

    Gresswell, Carolyn Gayle

    Understanding how organisms are capable of forming (synthesize, crystallize, and organize) solid minerals into complex architectures has been a fundamental question of biomimetic materials chemistry and biomineralization for decades. This study utilizes short peptides selected using a cell surface display library for the specific polymorphs of calcium carbonate, i.e., aragonite and calcite, to identify two sets of sequences which can then be used to examine their effects in the formation, crystal structure, morphology of the CaCO3 minerals. A procedure of counter selection, along with fluorescence microscopy (FM) characterization, was adapted to insure that the sequences on the cells were specific to their respective substrate, i.e., aragonite or calcite. From the resulting two sets of sequences selected, five distinct strong binders were identified with a variety of biochemical characteristics and synthesized for further study. Protein derived peptides, using the known sequences of the proteins that are associated with calcite or aragonite, were also designed using a bioinformatics-based similarity analysis of the two sets of binders. In particular, an aragonite binding protein segment, AP7, a protein found in nacre, was chosen for this design and the resulting effects of the designed peptides and the AP7 were examined. Specifically, the binding affinities of the selected and the protein derived peptides off the cells were then tested using FM; these studies resulted in different binding characteristics of the synthesized and cellular bound peptides. Two of the peptides that displayed strong binding on the cells bound to neither of the CaCO 3 substrates and both the high and low similarity protein-derived peptides bound to both polymorphs. However, two of the peptides were found to only bind to their respective polymorph showing; these results are significant in that with this study it is demonstrated that the designed peptides based on experimental library

  13. Remineralizing amorphous calcium phosphate based composite resins: the influence of inert fillers on monomer conversion, polymerization shrinkage, and microhardness

    PubMed Central

    Marović, Danijela; Šariri, Kristina; Demoli, Nazif; Ristić, Mira; Hiller, Karl-Anton; Škrtić, Drago; Rosentritt, Martin; Schmalz, Gottfried; Tarle, Zrinka

    2016-01-01

    Aim To determine if the addition of inert fillers to a bioactive dental restorative composite material affects its degree of conversion (DC), polymerization shrinkage (PS), and microhardness (HV). Methods Three amorphous calcium phosphate (ACP)-based composite resins: without added fillers (0-ACP), with 10% of barium-glass fillers (Ba-ACP), and with 10% of silica fillers (Si-ACP), as well as commercial control (Ceram•X, Dentsply DeTrey) were tested in laboratory conditions. The amount of ACP (40%) and the composition of the resin mixture (based on ethoxylated bisphenol A dimethacrylate) was the same for all ACP materials. Fourier transform infrared spectroscopy was used to determine the DC (n = 40), 20 min and 72 h after polymerization. Linear PS and Vickers microhardness (n = 40) were also evaluated. The results were analyzed by paired samples t test, ANOVA, and one-way repeated measures ANOVA with Student-Newman-Keuls or Tukey’s post-hoc test (P = 0.05). Results The addition of barium fillers significantly increased the DC (20 min) (75.84 ± 0.62%) in comparison to 0-ACP (73.92 ± 3.08%), but the addition of silica fillers lowered the DC (71.00 ± 0.57%). Ceram•X had the lowest DC (54.93 ± 1.00%) and linear PS (1.01 ± 0.24%) but the highest HV (20.73 ± 2.09). PS was significantly reduced (P < 0.010) in both Ba-ACP (1.13 ± 0.25%) and Si-ACP (1.17 ± 0.19%) compared to 0-ACP (1.43 ± 0.21%). HV was significantly higher in Si-ACP (12.82 ± 1.30) than in 0-ACP (10.54 ± 0.86) and Ba-ACP (10.75 ± 0.62) (P < 0.010). Conclusion Incorporation of inert fillers to bioactive remineralizing composites enhanced their physical-mechanical performance in laboratory conditions. Both added fillers reduced the PS while maintaining high levels of the DC. Silica fillers additionally moderately improved the HV of ACP composites. PMID:27815937

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

    EPA Science Inventory

    Single-walled carbon nanotubes (SWCNTs) with proper functionalization are desirable for applications that require dispersion in aqueous and biological environments, and functionalized SWCNTs also serve as building blocks for conjugation with specific molecules in these applicatio...

  15. Biofilm-induced calcium carbonate precipitation: application in the subsurface

    NASA Astrophysics Data System (ADS)

    Phillips, A. J.; Eldring, J.; Lauchnor, E.; Hiebert, R.; Gerlach, R.; Mitchell, A. C.; Esposito, R.; Cunningham, A. B.; Spangler, L.

    2012-12-01

    We have investigated mitigation strategies for sealing high permeability regions, like fractures, in the subsurface. This technology has the potential to, for example, improve the long-term security of geologically-stored carbon dioxide (CO2) by sealing fractures in cap rocks or to mitigate leakage pathways to prevent contamination of overlying aquifers from hydraulic fracturing fluids. Sealing technologies using low-viscosity fluids are advantageous since they potentially reduce the necessary injection pressures and increase the radius of influence around injection wells. In this technology, aqueous solutions and suspensions are used to promote microbially-induced mineral precipitation which can be applied in subsurface environments. To this end, a strategy was developed to twice seal a hydraulically fractured, 74 cm (2.4') diameter Boyles Sandstone core, collected in North-Central Alabama, with biofilm-induced calcium carbonate (CaCO3) precipitates under ambient pressures. Sporosarcina pasteurii biofilms were established and calcium and urea containing reagents were injected to promote saturation conditions favorable for CaCO3 precipitation followed by growth reagents to resuscitate the biofilm's ureolytic activity. Then, in order to evaluate this process at relevant deep subsurface pressures, a novel high pressure test vessel was developed to house the 74 cm diameter core under pressures as high as 96 bar (1,400 psi). After determining that no impact to the fracture permeability occurred due to increasing overburden pressure, the fractured core was sealed under subsurface relevant pressures relating to 457 meters (1,500 feet) below ground surface (44 bar (650 psi) overburden pressure). After fracture sealing under both ambient and subsurface relevant pressure conditions, the sandstone core withstood three times higher well bore pressure than during the initial fracturing event, which occurred prior to biofilm-induced CaCO3 mineralization. These studies suggest

  16. Development of spin-on carbon hardmasks with comparable etch resistance to Amorphous Carbon Layer (ACL)

    NASA Astrophysics Data System (ADS)

    Cheon, Hwan-Sung; Yoon, Kyong-Ho; Kim, Min-Soo; Oh, Seung Bae; Song, Jee-Yun; Tokareva, Nataliya; Kim, Jong-Seob; Chang, Tuwon

    2008-11-01

    In recent microlithography of semiconductor fabrication, spin-on hardmask (SOH) process continue to gain popularity as it replaces the traditional SiON/ACL hardmask scheme which suffers from high CoO, low productivity, particle contamination, and layer alignment issues. In the SOH process, organic polymer with high carbon content is spin-cast to form a carbon hardmask film. In the previous papers, we reported the development of organic SOH materials and their application in sub-70 nm lithography. In this paper, we describe the synthesis of organic polymers with very high carbon contents (>92 wt.%) and the evaluation of the spin-coated films for the hardmask application. The high carbon content of the polymer ensures improved etch resistance which amounts to >90% of ACL's resistance. However, as the carbon content of the polymers increases, the solubility in common organic solvents becomes lower. Here we report the strategies to improve the solubility of the high carbon content resins and optimization of the film properties for the SOH application.

  17. Crystallization kinetics of calcium carbonate at a stoichiometric ratio of components

    NASA Astrophysics Data System (ADS)

    Pochitalkina, I. A.; Kekin, P. A.; Morozov, A. N.; Petropavlovskii, I. A.; Kondakov, D. F.

    2016-12-01

    The formal kinetics of calcium carbonate crystallization in aqueous solutions is studied at a stoichiometric ratio of Ca2+ and CO3 2- ions. The kinetics of the process was monitored by convenient and reliable methods (complexometric analysis for calcium in an aqueous solution and energy dispersive and microscopic measurement of solid particle sizes). The effect the temperature and degree of supersaturation have on the periods of induction and mass crystallization and the equilibrium concentration of calcium ions in solution is estimated at continuously controlled pH and solution ionic strength. The kinetic parameters ( n, k, τ1/2, E a) of calcium carbonate crystallization are calculated. It is shown that calcium carbonate with a calcite structure formed at a stoichiometric ratio of reagents, and changes in the temperature (25-45°C) and the solution's degree of supersaturation (2-6) within the considered range had no effect on the characteristics of the solid phase.

  18. No-flash-point electrolytes applied to amorphous carbon/Li 1+ xMn 2O 4 cells for EV use

    NASA Astrophysics Data System (ADS)

    Arai, Juichi

    Use of no-flash-point electrolytes (NFEs) containing non-flammable solvent for an amorphous carbon/Li 1+ xMn 2O 4 cell has been studied. We prepared three NFEs: NFE1 was composed of 1 M (mol dm -3) of LiN[SO 2C 2F 5] 2 as supporting electrolyte, and 80 vol.% of methyl nonafluorobutyl ether (MFE) and 20 vol.% of ethyl methyl carbonate (EMC) as solvents; NFE2 was prepared by adding 0.5 M of EC (ethylene carbonate) to NFE1; and NFE3 was prepared by adding 0.1 M of LiPF 6 to NFE2. Charge-discharge performance of Li 1+ xMn 2O 4/Li cells and amorphous carbon/Li cells with NFEs were investigated. The amorphous carbon/Li 1+ xMn 2O 4 18650 cells were fabricated and investigated in terms of rate capability and cycle life. NFE2 showed good rate performance. NFE3 showed the best cycle life among the NFE electrolyte cells, though it had only fair rate performance. Electrochemical impedance spectroscopy (EIS), attenuated total reflection infrared (ATR-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) were measured to study the effect of EC and LiPF 6.

  19. Calcium carbonate corrosivity in an Alaskan inland sea

    NASA Astrophysics Data System (ADS)

    Evans, W.; Mathis, J. T.; Cross, J. N.

    2014-01-01

    Ocean acidification is the hydrogen ion increase caused by the oceanic uptake of anthropogenic CO2, and is a focal point in marine biogeochemistry, in part, because this chemical reaction reduces calcium carbonate (CaCO3) saturation states (Ω) to levels that are corrosive (i.e., Ω ≤ 1) to shell-forming marine organisms. However, other processes can drive CaCO3 corrosivity; specifically, the addition of tidewater glacial melt. Carbonate system data collected in May and September from 2009 through 2012 in Prince William Sound (PWS), a semienclosed inland sea located on the south-central coast of Alaska and ringed with fjords containing tidewater glaciers, reveal the unique impact of glacial melt on CaCO3 corrosivity. Initial limited sampling was expanded in September 2011 to span large portions of the western and central sound, and included two fjords proximal to tidewater glaciers: Icy Bay and Columbia Bay. The observed conditions in these fjords affected CaCO3 corrosivity in the upper water column (< 50 m) in PWS in two ways: (1) as spring-time formation sites of mode water with near-corrosive Ω levels seen below the mixed layer over a portion of the sound, and (2) as point sources for surface plumes of glacial melt with corrosive Ω levels (Ω for aragonite and calcite down to 0.60 and 1.02, respectively) and carbon dioxide partial pressures (pCO2) well below atmospheric levels. CaCO3 corrosivity in glacial melt plumes is poorly reflected by pCO2 or pHT, indicating that either one of these carbonate parameters alone would fail to track Ω in PWS. The unique Ω and pCO2 conditions in the glacial melt plumes enhances atmospheric CO2 uptake, which, if not offset by mixing or primary productivity, would rapidly exacerbate CaCO3 corrosivity in a positive feedback. The cumulative effects of glacial melt and air-sea gas exchange are likely responsible for the seasonal reduction of Ω in PWS, making PWS highly sensitive to increasing atmospheric CO2 and amplified Ca

  20. Low Friction Property of Diamond-Like Carbon Coating Films and Oxygen Transmission Ratio of Amorphous Carbon Films Deposited by Advanced Coating Processes

    NASA Astrophysics Data System (ADS)

    Watanabe, Toshiyuki; Kano, Makoto; Yoshida, Kentaro; Suzuki, Tetsuya

    2012-09-01

    The topics of the applied technology of amorphous carbon film to reduce friction using diamond-like carbon (DLC) coated by the vacuum arc ion plating process and to improve the gas barrier property using the amorphous carbon film by the atmospheric pressure plasma process are introduced with the basic experimental results. For reducing friction, the super low friction coefficient below 0.01 has been found when the tetrahedral amorphous carbon coating deposited by T-shape filtered arc deposition method [ta-C(T)] was evaluated the friction property under oleic acid lubrication at pure sliding condition. It was thought that the low share strength tribofilm composed of water and oleic acid mono-layer seemed to be formed on the sliding interface. For gas barrier performance, the amorphous carbon film deposited by the atmospheric pressure plasma chemical vapour deposition (CVD) technique on poly(ethylene terephthalate) (PET) substrate was improved the oxygen transmission ratio (OTR) around 30% compared with that of uncoated PET substrate. These advanced performance obtained by the optimum material combination of DLC with lubricant and the original atmospheric pressure plasma CVD technique are expected to be applied on the actual application for the different types of the industrial fields in near future.

  1. Growth Rate of Calcite Steps as a Function of Aqueous Calcium-to-Carbonate Ratio: Independent Attachment and Detachment of Calcium and Carbonate Ions

    SciTech Connect

    Stack, Andrew G; Grantham, Ms. Meg

    2010-01-01

    Growth rates of monolayer-height steps on the {1014} calcite surface have been measured as a function of the aqueous calcium-to-carbonate ratio. The maximum growth rates of the two common crystallographic orientations were found to deviate from the ideal stoichiometric ratio of 1:1, and dissolution features were observed under supersaturated solutions containing high calcium-to-carbonate ratios. To explain these phenomena, a theory is applied that treats the rates of attachment and detachment of aqueous calcium and carbonate ions separately. The resultant attachment rate constants are 1-3 orders of magnitude smaller than the water exchange rate of the constituent aqueous ions, suggesting that ligand-exchange processes may directly drive attachment. The broader implication is that the saturation state alone is not adequate to fully describe the rates of the multiple, independent reactions that occur on mineral surfaces under these conditions.

  2. Calcium in diet

    MedlinePlus

    ... of calcium dietary supplements include calcium citrate and calcium carbonate. Calcium citrate is the more expensive form of ... the body on a full or empty stomach. Calcium carbonate is less expensive. It is absorbed better by ...

  3. The flame photometric determination of calcium in phosphate, carbonate, and silicate rocks

    USGS Publications Warehouse

    Kramer, H.

    1957-01-01

    A flame photometric method of determining calcium in phosphate, carbonate, and silicate locks has been developed Aluminum and phosphate interference was overcome by the addition of a large excess of magnesium. The method is rapid and suitable for routine analysis Results obtained are within ?? 2% of the calcium oxide content. ?? 1957.

  4. Nanodiamonds on tetrahedral amorphous carbon significantly enhance dopamine detection and cell viability.

    PubMed

    Peltola, Emilia; Wester, Niklas; Holt, Katherine B; Johansson, Leena-Sisko; Koskinen, Jari; Myllymäki, Vesa; Laurila, Tomi

    2017-02-15

    We hypothesize that by using integrated carbon nanostructures on tetrahedral amorphous carbon (ta-C), it is possible to take the performance and characteristics of these bioelectrodes to a completely new level. The integrated carbon electrodes were realized by combining nanodiamonds (NDs) with ta-C thin films coated on Ti-coated Si-substrates. NDs were functionalized with mixture of carboxyl and amine groups NDandante or amine NDamine, carboxyl NDvox or hydroxyl groups NDH and drop-casted or spray-coated onto substrate. By utilizing these novel structures we show that (i) the detection limit for dopamine can be improved by two orders of magnitude [from 10µM to 50nM] in comparison to ta-C thin film electrodes and (ii) the coating method significantly affects electrochemical properties of NDs and (iii) the ND coatings selectively promote cell viability. NDandante and NDH showed most promising electrochemical properties. The viability of human mesenchymal stem cells and osteoblastic SaOS-2 cells was increased on all ND surfaces, whereas the viability of mouse neural stem cells and rat neuroblastic cells was improved on NDandante and NDH and reduced on NDamine and NDvox. The viability of C6 cells remained unchanged, indicating that these surfaces will not cause excess gliosis. In summary, we demonstrated here that by using functionalized NDs on ta-C thin films we can significantly improve sensitivity towards dopamine as well as selectively promote cell viability. Thus, these novel carbon nanostructures provide an interesting concept for development of various in vivo targeted sensor solutions.

  5. Thermodynamic properties of synthetic calcium-free carbonate cancrinite

    NASA Astrophysics Data System (ADS)

    Kurdakova, S. V.; Grishchenko, R. O.; Druzhinina, A. I.; Ogorodova, L. P.

    2014-01-01

    Calcium-free carbonate cancrinite with formula unit Na8.28[Al5.93Si6.07O24](CO3)0.93(OH)0.49·3.64H2O (CAN) has been synthesized under hydrothermal conditions. The product has been characterized by the methods of scanning electronic microscopy and energy dispersive X-ray analysis, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis with FTIR of evolved gases (TGA-FTIR), and X-ray powder diffraction. The heat capacity of CAN has been measured from 6 to 259 K via low-temperature adiabatic calorimetry. A linear combination of Einstein functions has been used to approximate the obtained data on the heat capacity. The thermal contributions to the entropy and enthalpy of CAN in the temperature range 0-300 K have been calculated from these data. The heat capacity and third-law absolute entropy of CAN at 298.15 K are 1,047 ± 30 and 1,057 ± 35 J mol-1 K-1, respectively. High-temperature oxide-melt solution calorimetry has been used to determine the enthalpy of formation from elements of CAN at 298.15 K; the value equals -14,684 ± 50 kJ mol-1. The Gibbs energy of formation from elements at 298.15 K has been calculated and totaled -13,690 ± 51 kJ mol-1.

  6. Characterization of calcium carbonate sorbent particle in furnace environment.

    PubMed

    Lee, Kang Soo; Jung, Jae Hee; Keel, Sang In; Yun, Jin Han; Min, Tai Jin; Kim, Sang Soo

    2012-07-01

    The oxy-fuel combustion system is a promising technology to control CO₂ and NO(x) emissions. Furthermore, sulfation reaction mechanism under CO₂-rich atmospheric condition in a furnace may lead to in-furnace desulfurization. In the present study, we evaluated characteristics of calcium carbonate (CaCO₃) sorbent particles under different atmospheric conditions. To examine the physical/chemical characteristics of CaCO₃, which is used as a sorbent particle for in-furnace desulfurization in the oxy-fuel combustion system, they were injected into high temperature drop tube furnace (DTF). Experiments were conducted at varying temperatures, residence times, and atmospheric conditions in a reactor. To evaluate the aerosolizing characteristics of the CaCO₃ sorbent particle, changes in the size distribution and total particle concentration between the DTF inlet and outlet were measured. Structural changes (e.g., porosity, grain size, and morphology) of the calcined sorbent particles were estimated by BET/BJH, XRD, and SEM analyses. It was shown that sorbent particles rapidly calcined and sintered in the air atmosphere, whereas calcination was delayed in the CO₂ atmosphere due to the higher CO₂ partial pressure. Instead, the sintering effect was dominant in the CO₂ atmosphere early in the reaction. Based on the SEM images, it was shown that the reactions of sorbent particles could be explained as a grain-subgrain structure model in both the air and CO₂ atmospheres.

  7. Synthesis of calcium carbonate nanocrystals and their potential application as vessels for drug delivery

    NASA Astrophysics Data System (ADS)

    Vergaro, Viviana; Carata, Elisabetta; Panzarini, Elisa; Baldassare, Francesca; Dini, Luciana; Ciccarella, Giuseppe

    2015-06-01

    Pure and stable calcium carbonate (CaCO3) nanocrystals were synthesized by spray drying method. We exploited the opportunity to use them as vessels for drug delivery studying the biocompatibility and the internalization in HeLa cells.

  8. Crystal growth of calcium carbonate in silk fibroin/sodium alginate hydrogel

    NASA Astrophysics Data System (ADS)

    Ming, Jinfa; Zuo, Baoqi

    2014-01-01

    As known, silk fibroin-like protein plays a pivotal role during the formation of calcium carbonate (CaCO3) crystals in the nacre sheets. Here, we have prepared silk fibroin/sodium alginate nanofiber hydrogels to serve as templates for calcium carbonate mineralization. In this experiment, we report an interesting finding of calcium carbonate crystal growth in the silk fibroin/sodium alginate nanofiber hydrogels by the vapor diffusion method. The experimental results indicate calcium carbonate crystals obtained from nanofiber hydrogels with different proportions of silk fibroin/sodium alginate are mixture of calcite and vaterite with unusual morphologies. Time-dependent growth study was carried out to investigate the crystallization process. It is believed that nanofiber hydrogels play an important role in the process of crystallization. This study would help in understanding the function of organic polymers in natural mineralization, and provide a novel pathway in the design and synthesis of new materials related unique morphology and structure.

  9. Organoaqueous calcium chloride electrolytes for capacitive charge storage in carbon nanotubes at sub-zero-temperatures.

    PubMed

    Gao, Yun; Qin, Zhanbin; Guan, Li; Wang, Xiaomian; Chen, George Z

    2015-07-11

    Solutions of calcium chloride in mixed water and formamide are excellent electrolytes for capacitive charge storage in partially oxidised carbon nanotubes at unprecedented sub-zero-temperatures (e.g. 67% capacitance retention at -60 °C).

  10. Clinical and histologic evaluation of calcium carbonate in sinus augmentation: a case series.

    PubMed

    Mangano, Carlo; Iaculli, Flavia; Piattelli, Adriano; Mangano, Francesco; Shibli, Jamil Awad; Perrotti, Vittoria; Iezzi, Giovanna

    2014-01-01

    The aim of this case series was a clinical, histologic, and histomorphometric evaluation of calcium carbonate in sinus elevation procedures. Sinus augmentation was performed in the atrophic maxillae of 24 subjects using calcium carbonate. Six months after the regeneration procedures, 68 implants were placed and clinically followed for 1 to 5 years, depending on the placement timing. At the last implant placement procedure, 8 bone cores were harvested and processed for histology. After a 6-month healing period, sinuses grafted with calcium carbonate showed a mean vertical bone gain of 6.93 ± 0.23 mm. The histomorphometric analysis revealed 15% ± 3% residual grafted biomaterial, 28% ± 2% newly formed bone, and 57% ± 2% marrow spaces. The implant survival rate was 98.5%. It can be concluded that calcium carbonate was shown to be clinically suitable for sinus elevation procedures after 1 to 5 years of follow-up and histologically biocompatible and osteoconductive.

  11. Formation of self-supporting porous graphite structures by Spark Plasma Sintering of nickel-amorphous carbon mixtures

    NASA Astrophysics Data System (ADS)

    Bokhonov, Boris B.; Dudina, Dina V.; Ukhina, Arina V.; Korchagin, Michail A.; Bulina, Natalia V.; Mali, Vyacheslav I.; Anisimov, Alexander G.

    2015-01-01

    Graphitization of amorphous carbon in the presence of nickel has been reported for various configurations of the metal-carbon interface; however, no study has been performed to evaluate a possibility of forming self-supporting networks by sintering of the in situ formed graphite. In this work, we have shown that Spark Plasma Sintering (SPS) of nickel-amorphous carbon mixtures containing 50 vol% of Ni at 1000 °C results in the formation of networks formed by sintered graphite platelets 50-200 nm thick and 0.3-2 μm in diameter. Upon selective dissolution of nickel, a self-supporting porous 3D skeleton was revealed in 20 mm-diameter compacts. Starting from the mechanically milled Ni-C mixture, porous graphite of uniform microstructure and containing submicron pores was obtained. A model study has been performed, in which a thin amorphous carbon film graphitized during annealing and formed a continuous graphite film with micron-sized grains covering an area of 2 cm×2 cm of the surface of a Ni foil. We discuss the role of the in situ formation of graphite by nickel-assisted graphitization in the formation of networks consisting of well sintered platelets during the SPS and the design possibilities of porous carbon materials produced by phase separation in nickel-graphite composites.

  12. Effect of calcium carbonate on hardening, physicochemical properties, and in vitro degradation of injectable calcium phosphate cements.

    PubMed

    Sariibrahimoglu, Kemal; Leeuwenburgh, Sander C G; Wolke, Joop G C; Yubao, Li; Jansen, John A

    2012-03-01

    The main disadvantage of apatitic calcium phosphate cements (CPCs) is their slow degradation rate, which limits complete bone regeneration. Carbonate (CO₃²⁻) is the common constituent of bone and it can be used to improve the degradability of the apatitic calcium phosphate ceramics. This study aimed to examine the effect of calcite (CaCO₃) incorporation into CPCs. To this end, the CaCO₃ amount (0-4-8-12 wt %) and its particle size (12.0-μm-coarse or 2.5-μm-fine) were systematically investigated. In comparison to calcite-free CPC, the setting time of the bone substitute was delayed with increasing CaCO₃ incorporation. Reduction of the CaCO₃ particle size in the initial powder increased the injectability time of the paste. During hardening of the cements, the increase in calcium release was inversely proportional to the extent of CO₃²⁻ incorporation into apatites. The morphology of the carbonate-free product consisted of large needle-like crystals, whereas small plate-like crystals were observed for carbonated apatites. Compressive strength decreased with increasing CaCO₃ content. In vitro accelerated degradation tests demonstrated that calcium release and dissolution rate from the set cements increased with increasing the incorporation of CO₃²⁻, whereas differences in CaCO₃ particle size did not affect the in vitro degradation rate under accelerated conditions.

  13. Composition and properties of the so-called 'diamond-like' amorphous carbon films

    NASA Technical Reports Server (NTRS)

    Angus, J. C.; Stultz, J. E.; Shiller, P. J.; Macdonald, J. R.; Mirtich, M. J.

    1984-01-01

    The composition of amorphous 'diamond-like' films made by direct low energy ion beam deposition, R.F. discharge and sputtering was determined by nuclear reaction analysis, IR spectroscopy and microcombustion chemical analysis. The nuclear reaction analysis showed very similar hydrogen depth profiles for all three types of samples. The atomic ratio of hydrogen to carbon was approximately 0.2 at the film surface and rose to approximately 1.0 at a depth of 500 A. The integrated intensity of the C-H stretching band at about 2900 per cm indicates that the amount of chemically bonded hydrogen is less than the total hydrogen content. Combustion analysis confirmed the overall atomic ratio of hydrogen to carbon determined by nuclear reaction analysis. The chemical state of the non-bonded hydrogen was not determined; however, the effective diffusion coefficient computed from the hydrogen depth profile was extremely low. This indicates either that the films are exceedingly impermeable or that the non-bonded hydrogen requires an additional activated step to leave the films, e.g., desorption or chemical reaction.

  14. Density and localized states' impact on amorphous carbon electron transport mechanisms

    NASA Astrophysics Data System (ADS)

    Caicedo-Dávila, S.; Lopez-Acevedo, O.; Velasco-Medina, J.; Avila, A.

    2016-12-01

    This work discusses the electron transport mechanisms that we obtained as a function of the density of amorphous carbon (a-C) ultra-thin films. We calculated the density of states (total and projected), degree of electronic states' localization, and transmission function using the density functional theory and nonequilibrium Green's functions method. We generated 25 sample a-C structures using ab-initio molecular dynamics within the isothermal-isobaric ensemble. We identified three transport regimes as a function of the density, varying from semimetallic in low-density samples ( ≤2.4 g/cm3) to thermally activated in high-density ( ≥2.9 g/cm3) tetrahedral a-C. The middle-range densities (2.4 g/cm3 ≤ρ≤ 2.9 g/cm3) are characterized by resonant tunneling and hopping transport. Our findings offer a different perspective from the tight-binding model proposed by Katkov and Bhattacharyya [J. Appl. Phys. 113, 183712 (2013)], and agree with experimental observations in low-dimensional carbon systems [see S. Bhattacharyya, Appl. Phys. Lett. 91, 21 (2007)]. Identifying transport regimes is crucial to the process of understanding and applying a-C thin film in electronic devices and electrode coating in biosensors.

  15. Hydrogen pumping in amorphous deutered carbon films irradiated by swift heavy ions

    NASA Astrophysics Data System (ADS)

    Pawlak, F.; Balanzat, E.; Dufour, Ch.; Laurent, A.; Paumier, E.; Perriere, J.; Stoquert, J. P.; Toulemonde, M.

    1997-02-01

    Deutered amorphous carbon films have been irradiated at GANIL using 5 to 10 MeV/u sulfur beam with an electronic stopping power from 1 to 1.4 keV/nm. Such films have been deposited on silicon substrates by decomposition of CD 4 gas containing 10% of CH 4 in a dc multipolar plasma. After irradiation, they were analyzed firstly using absorption infrared spectroscopy to determine the number of CD and CH bonds. Secondly, deuterium, hydroge and carbon areal density were determined by ERDA and RBS. The results analysis shows a decrease of the atomic ratio ( {D}/{C}) as well as CD bonds down to a minimum value versus the fluence without a threshold fluence and in the same time an increase of the atomic ratio ( {H}/{C}) as well as CH bonds to a maximum value. So we may conclude that the hydrogen pumped after the irradiation is stabilized on broken (or unpaired) bonds.

  16. Sandwich-lithiation and longitudinal crack in amorphous silicon coated on carbon nanofibers.

    PubMed

    Wang, Jiang Wei; Liu, Xiao Hua; Zhao, Kejie; Palmer, Andrew; Patten, Erin; Burton, David; Mao, Scott X; Suo, Zhigang; Huang, Jian Yu

    2012-10-23

    Silicon-carbon nanofibers coaxial sponge, with strong mechanical integrity and improved electronic conductivity, is a promising anode structure to apply into commercial high-capacity lithium ion batteries. We characterized the electrochemical and mechanical behaviors of amorphous silicon-coated carbon nanofibers (a-Si/CNFs) with in situ transmission electron microscopy (TEM). It was found that lithiation of the a-Si coating layer occurred from the surface and the a-Si/CNF interface concurrently, and propagated toward the center of the a-Si layer. Such a process leads to a sandwiched Li(x)Si/Si/Li(x)Si structure, indicating fast Li transport through the a-Si/CNF interface. Nanocracks and sponge-like structures developed in the a-Si layer during the lithiation-delithiation cycles. Lithiation of the a-Si layer sealed in the hollow CNF was also observed, but at a much lower speed than the counterpart of the a-Si layer coated on the CNF surface. An analytical solution of the stress field was formulated based on the continuum theory of finite deformation, explaining the experimental observation of longitudinal crack formation and general mechanical degradation mechanism in a-Si/CNF electrode.

  17. Electronic structure and conductivity of nanocomposite metal (Au,Ag,Cu,Mo)-containing amorphous carbon films

    SciTech Connect

    Endrino, Jose L.; Horwat, David; Gago, Raul; Andersson, Joakim; Liu, Y.S.; Guo, Jinghua; Anders, Andre

    2008-05-14

    In this work, we study the influence of the incorporation of different metals (Me = Au, Ag, Cu, Mo) on the electronic structure of amorphous carbon (a-C:Me) films. The films were produced at room temperature using a novel pulsed dual-cathode arc deposition technique. Compositional analysis was performed with secondary neutral mass spectroscopy whereas X-ray diffraction was used to identify the formation of metal nanoclusters in the carbon matrix. The metal content incorporated in the nanocomposite films induces a drastic increase in the conductivity, in parallel with a decrease in the band gap corrected from Urbach energy. The electronic structure as a function of the Me content has been monitored by x-ray absorption near edge structure (XANES) at the C K-edge. XANES showed that the C host matrix has a dominant graphitic character and that it is not affected significantly by the incorporation of metal impurities, except for the case of Mo, where the modifications in the lineshape spectra indicated the formation of a carbide phase. Subtle modifications of the spectral lineshape are discussed in terms of nanocomposite formation.

  18. Transformation of Graphitic and Amorphous Carbon Dust to Complex Organic Molecules in a Massive Carbon Cycle in Protostellar Nebulae

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A., III; Johnson, Natasha M.

    2012-01-01

    More than 95% of silicate minerals and other oxides found in meteorites were melted, or vaporized and recondensed in the Solar Nebula prior to their incorporation into meteorite parent bodies. Gravitational accretion energy and heating via radioactive decay further transformed oxide minerals accreted into planetesimals. In such an oxygen-rich environment the carbonaceous dust that fell into the nebula as an intimate mixture with oxide grains should have been almost completely converted to CO. While some pre-collapse, molecular-cloud carbonaceous dust does survive, much in the same manner as do pre-solar oxide grains, such materials constitute only a few percent of meteoritic carbon and are clearly distinguished by elevated D/H, N-15/N-16, C-13/C-12 ratios or noble gas patterns. Carbonaceous Dust in Meteorites: We argue that nearly all of the carbon in meteorites was synthesized in the Solar Nebula from CO and that this CO was generated by the reaction of carbonaceous dust with solid oxides, water or OH. It is probable that some fraction of carbonaceous dust that is newly synthesized in the Solar Nebula is also converted back into CO by additional thermal processing. CO processing might occur on grains in the outer nebula through irradiation of CO-containing ice coatings or in the inner nebula via Fischer-Tropsch type (FTT) reactions on grain surfaces. Large-scale transport of both gaseous reaction products and dust from the inner nebula out to regions where comets formed would spread newly formed carbonaceous materials throughout the solar nebula. Formation of Organic Carbon: Carbon dust in the ISM might easily be described as inorganic graphite or amorphous carbon, with relatively low structural abundances of H, N, O and S . Products of FTT reactions or organics produced via irradiation of icy grains contain abundant aromatic and aliphatic hydrocarbons. aldehydes, keytones, acids, amines and amides.. The net result of the massive nebular carbon cycle is to convert

  19. Efficient in vivo gene transfer by intraperitoneal injection of plasmid DNA and calcium carbonate microflowers in mice.

    PubMed

    Fumoto, Shintaro; Nakajima, Sayuri; Mine, Toyoharu; Yoshikawa, Naoki; Kitahara, Takashi; Sasaki, Hitoshi; Miyamoto, Hirotaka; Nishida, Koyo

    2012-07-02

    Gene transfer to intraperitoneal organs is thought to be a promising approach to treat such conditions as peritoneal fibrosis and peritoneal dissemination of cancers. We previously discovered that simple instillation of naked plasmid DNA (pDNA) onto intraperitoneal organs such as the liver and stomach could effectively transfer foreign genes in mice. In this study, we developed a novel nonviral method to enhance transfection efficiency of naked pDNA to intraperitoneal organs using a calcium carbonate suspension containing pDNA. Using commercially available calcium carbonate, we successfully transfected pDNA to the stomach. Handling of commercially available calcium carbonate, however, was troublesome owing to rapid precipitation and caking. To obtain slowly settling particles of calcium carbonate, we tried to synthesize novel versions of such particles and succeeded in creating flower-shaped particles, named calcium carbonate microflowers. Sedimentation of calcium carbonate microflowers was sufficiently slow for in vivo experiments. Moreover, the transfection efficiency of the suspension of calcium carbonate microflowers to the stomach was more effective than that of commercially available calcium carbonate, especially at low concentrations. Intraperitoneal injection of the suspension of calcium carbonate microflowers containing pDNA greatly enhanced naked pDNA transfer to whole intraperitoneal organs in mice. Furthermore, lactate dehydrogenase activities in intraperitoneal fluid and plasma were not raised by the suspension of calcium carbonate microflowers.

  20. Carbon Diffusion through SiO2 from a Hydrogenated Amorphous Carbon Layer and Accumulation at the SiO2/Si Interface

    NASA Astrophysics Data System (ADS)

    Krafcsik, Olga H.; Vida, György; Pócsik, István; Josepovits, Katalin V.; Deák, Péter

    2001-04-01

    Carbon diffusion in a SiO2/Si system was investigated. The source was provided by chemical vapor deposition of a hydrogenated amorphous carbon layer onto the oxide at low temperature. From layers with low oxygen content, no carbon outdiffusion was detected up to 1190°C@. If the O content was high, the diffusion would start suddenly at 1140°C, and carbon accumulation would be found on the Si side of the SiO2/Si interface in the form of SiC precipitates. These results are interpreted by assuming oxygen-assisted dissociation of carbon atoms from the carbon layer in form of CO molecules, fast CO diffusion through SiO2 and an exothermic reaction of CO with Si. No carbon segregation was found in SiO2. Consequences of carbon island formation during SiC oxidation are pointed out.

  1. Bioinspired synthesis of fluorescent calcium carbonate/carbon dot hybrid composites.

    PubMed

    Guo, Shanshan; Yang, Miao; Chen, Min; Zhang, Juan; Liu, Kang; Ye, Ling; Gu, Wei

    2015-05-07

    Herein, we report a novel method to synthesise fluorescent calcium carbonate/carbon dots (CaCO3/CDs) by simply mixing CaCl2 and Na2CO3 solutions in the presence of CDs. There are two roles of CDs in this easy and cost-effective biomimetic strategy, that is as the template to direct the formation and assembly of calcite nanocrystals into hierarchical spheres with diameters in the range of 200-300 nm and simultaneously as the phosphor to enable the CaCO3 to emit blue fluorescence under UV (365 nm) irradiation with a quantum yield of 56.2%. The CaCO3/CD hybrid composites possessing unique fluorescence properties are potentially useful in various applications.

  2. Sulfur Cycling Mediates Calcium Carbonate Geochemistry in Modern Marine Stromatolites

    NASA Technical Reports Server (NTRS)

    Visscher, P. T.; Hoeft, S. E.; Bebout, B. M.; Reid, R. P.

    2004-01-01

    Modem marine stromatolites forming in Highborne Cay, Exumas (Bahamas), contain microbial mats dominated by Schizothrix. Although saturating concentrations of Ca2+ and CO32- exist, microbes mediate CaCO3 precipitation. Cyanobacterial photosynthesis in these stromatolites aids calcium carbonate precipitation by removal of HS+ through CO2 use. Photorespiration and exopolymer production predominantly by oxygenic phototrophs fuel heterotrophic activity: aerobic respiration (approximately 60 umol/sq cm.h) and sulfate reduction (SR; 1.2 umol SO42-/sq cm.h) are the dominant C- consuming processes. Aerobic microbial respiration and the combination of SR and H2S oxidation both facilitate CaCO3 dissolution through H+ production. Aerobic respiration consumes much more C on an hourly basis, but duel fluctuating O2 and H2 depth profiles indicate that overall, SR consumes only slightly less (0.2-0.5) of the primary production. Moreover, due to low O2 concentrations when SR rates are peaking, reoxidation of the H2S formed is incomplete: both thiosulfate and polythionates are formed. The process of complete H2S oxidation yields H+. However, due to a low O2 concentration late in the day and relatively high O2 concentrations early in the following morning, a two-stage oxidation takes place: first, polythionates are formed from H2S, creating alkalinity which coincides with CaCO3 precipitation; secondly, oxidation of polythionates to sulfate yields acidity, resulting in dissolution, etc. Vertical profiles confirmed that the pH peaked late in the afternoon (greater than 8.8) and had the lowest values (less than 7.4) early in the morning. Thus, the effect of this S-cycling through alkalinity production, followed by acidification during H2S oxidation, results in a six times stronger fluctuation in acidity than photosynthesis plus aerobic respiration accomplish. This implies that anaerobic processes play a pivotal role in stromatolite formation.

  3. Comparison of flow-controlled calcium and barium carbonate precipitation patterns

    NASA Astrophysics Data System (ADS)

    Schuszter, G.; De Wit, A.

    2016-12-01

    Various precipitation patterns can be obtained in flow conditions when injecting a solution of sodium carbonate in a confined geometry initially filled with a solution of either barium or calcium chloride. We compare here the barium and calcium carbonate precipitate structures as a function of initial concentrations and injection flow rate. We show that, in some part of the parameter space, the patterns are similar and feature comparable properties indicating that barium and calcium behave similarly in the related flow-controlled precipitation conditions. For other values of parameters though, the precipitate structures are different indicating that the cohesive and microscopic properties of barium versus calcium carbonate are then important in shaping the pattern in flow conditions.

  4. Effects of switching from calcium carbonate to lanthanum carbonate on bone mineral metabolism in hemodialysis patients.

    PubMed

    Manabe, Rie; Fukami, Kei; Ando, Ryotaro; Sakai, Kazuko; Kusumoto, Takuo; Hazama, Takuma; Adachi, Takeki; Kaida, Yusuke; Nakayama, Yosuke; Ueda, Seiji; Kohno, Keisuke; Wada, Yoshifumi; Yamagishi, Sho-ichi; Okuda, Seiya

    2013-04-01

    Phosphate binders are useful for the treatment of hyperphosphatemia in hemodialysis (HD) patients. This study was performed to examine the effects of switching from calcium carbonate (CC) to lanthanum carbonate (LC) on bone mineral metabolism and inflammatory markers in HD patients. We conducted 29 stable HD patients receiving CC, which was replaced by LC and followed-up for 12 weeks. Patients underwent determinants of blood chemistries such as serum calcium (Ca), phosphorus, parathyroid hormone (PTH) and vitamin D status, and interleukin-6 (IL-6) mRNA levels in whole blood cells were evaluated by real-time PCR just before and after the treatment with LC. Corrected Ca [corrected] levels were significantly reduced, but serum phosphorus levels (P levels) were unchanged after LC treatment. Switching to LC increased whole-PTH, osteocalcin, 1,25(OH)(2) D(3) levels and 1,25(OH)(2) D(3)/25(OH)D(3) ratio. 1,25(OH)(2) D(3)/25(OH)D(3) ratio was negatively correlated with HD duration. Furthermore, whole blood cell IL-6 mRNA levels were significantly reduced by LC treatment. We provided that the switching from CC to LC improved Ca overload and ameliorated vitamin D and inflammatory status in HD patients. These observations suggest that LC may play a protective role for the progression of atherosclerosis and vascular calcification in these patients.

  5. Preparation of pure calcium carbonate by mineral carbonation using industrial byproduct FGD gypsum

    NASA Astrophysics Data System (ADS)

    Song, K.; Kim, W.; Bang, J. H.; Park, S.; Jeon, C. W.

    2015-12-01

    Mineral carbonation is one of the geological approaches for the sequestration of anthropogenic CO2 gas. Its concept is based on the natural weathering processes in which silicate minerals containing divalent cations such as Ca or Mg are carbonated to CaCO3 or MgCO3 in the reaction with CO2gas. Raw materials for the mineral carbonation have been extended to various industrial solid wastes such as steel slag, ashes, or FGD (flue gas desulfurization) gypsum which are rich in divalent cations. These materials have economic advantages when they are produced in CO2 emission sites. Flue gas desulfurization (FGD) gypsum is such a byproduct obtained in at coal-fired power plants. Recently, we carried out a research on the direct mineral carbonation of FGD gypsum for CO2sequestration. It showed high carbonation reactivity under ambient conditions and the process can be described as follows: CaSO4·2H2O + CO2(g) + 2NH4OH(aq) → CaCO3(s) + (NH4)2SO4(aq) (1) At the early stage of the process, calcium carbonate (CaCO3) exists as a dissolved ion pair during the induction period. High-purity CaCO3 could be precipitated from dissolved calcium carbonate solution extracted during the induction period. The effect of experimental parameters on pure CaCO3 was evaluated: CO2 flow rate (1-3 L/min), ammonia content (4-12%), and solid-to-liquid (S/L) ratio (5-300 g/L). FE-SEM (field-emission scanning electron microscopy) and XRD (X-ray diffraction) study revealed that the precipitated CaCO3 was round-shaped vaterite crystals. The induction time was inversely proportional to the CO2 flow rate and the yield for pure CaCO3 increased with the ammonia content. The formation efficiency for pure CaCO3 decreased with S/L (solid/liquid) ratio. It was 90% (mol/mol) when the S/L ratio was 5 g/L. However, S/L ratio didn't affect the maximum solubility limit of dissolved CaCO3.

  6. Effect of calcium carbonate combined with calcitonin on hypercalcemia in hemodialysis patients.

    PubMed

    Wei, Yong; Kong, Xiang Lei; Li, Wen Bin; Wang, Zun Song

    2014-12-01

    This short-term study assessed the efficacy and safety of calcium carbonate combined with calcitonin in the treatment of hypercalcemia in hemodialysis patients. Patients (n=64) on hemodialysis for chronic kidney disease for more than 6 months were included based on total serum calcium more than 10.5 mg/dL. All patients were randomized (1:1) to receive calcium carbonate combined with calcitonin (Group I) or lanthanum carbonate (Group II) for 12 weeks. Blood levels of calcium, phosphorus and intact parathyroid hormone (iPTH) were measured every month, bone mass density (BMD) and coronary artery calcium scores (CACS) were measured at 3 months. During the study period, serum calcium decreased from 10.72 ± 0.39 to 10.09 ± 0.28 mg/dL (P < 0.05), serum phosphorus decreased from 6.79 ± 1.05 to 5.46 ± 1.18 mg/dL (P < 0.05), and serum iPTH levels in the Group I and Group II were not significantly different from the baseline. There were no significant differences in CACS in either group. There were no significant differences in the BMD values between Group I and baseline. In Group II, the BMD values at the lumbar spine and femoral neck were significantly lower than those before the trial and significantly lower than the corresponding values of Group I (P<0.05). Calcium carbonate combined with calcitonin and lanthanum carbonate were equally effective in the suppression of hypercalcemia in hemodialysis patients. There were no serious treatment-related adverse events in treatment with calcium carbonate combined with calcitonin.

  7. Inelastic and reactive scattering of hyperthermal atomic oxygen from amorphous carbon

    NASA Technical Reports Server (NTRS)

    Minton, Timothy K.; Nelson, Christine M.; Brinza, David E.; Liang, Ranty H.

    1991-01-01

    The reaction of hyperthermal oxygen atoms with an amorphous carbon-13 surface was studied using a modified universal crossed molecular beams apparatus. Time-of-flight distributions of inelastically scattered O-atoms and reactively scattered CO-13 and CO2-13 were measured with a rotatable mass spectrometer detector. Two inelastic scattering channels were observed, corresponding to a direct inelastic process in which the scattered O-atoms retain 20 to 30 percent of their initial kinetic energy and to a trapping desorption process whereby O-atoms emerge from the surface at thermal velocities. Reactive scattering data imply the formation of two kinds of CO products, slow products whose translational energies are determined by the surface temperature and hyperthermal (Approx. 3 eV) products with translational energies comprising roughly 30 percent of the total available energy (E sub avl), where E sub avl is the sum of the collision energy and the reaction exothermicity. Angular data show that the hyperthermal CO is scattered preferentially in the specular direction. CO2 product was also observed, but at much lower intensities than CO and with only thermal velocities.

  8. Preparation of Amorphous Carbon Films and Evaluation of Its Optical Properties and Gas Barrier Property

    NASA Astrophysics Data System (ADS)

    Ohsone, Yuuki; Nishi, Hidetaka; Saito, Masanori; Suzuki, Masaki; Murakami, Hiroya; Ohtake, Naoto

    Hydrogenerated amorphous carbon (a-C:H) films can improve oxygen gas barrier characteristics of plastic food containers, by coating it on the surfaces of such containers, and is intended to enhance the preservative quality. However, it has a problem that the degradation of optical transparency in the visible light range blocks the view of the inner content. In this study, we aimed to reduce the oxygen transmission rate (OTR) as well as to improve optical transparency, and fabricated a-C:H films by the pulse plasma chemical vapor deposition (CVD) method on polyethylene terephthalate (PET) films. First, it is clarified that the gas barrier performance in the a-C:H film in the vicinity of the PET boundary surface was lower than that of bulk a-C:H film. Secondly, the OTR and optical transparency of a-C:H films deposited not only from C2H2 but also from Si(CH3)4 were investigated in detail. The a-C:H film deposited from Si(CH3)4 shows high transmittance of 87% for visible light with a relatively low OTR of 3.2 cc/(m2·atm·day).

  9. Energy band alignment and electronic states of amorphous carbon surfaces in vacuo and in aqueous environment

    SciTech Connect

    Caro, Miguel A.; Määttä, Jukka; Lopez-Acevedo, Olga; Laurila, Tomi

    2015-01-21

    In this paper, we obtain the energy band positions of amorphous carbon (a–C) surfaces in vacuum and in aqueous environment. The calculations are performed using a combination of (i) classical molecular dynamics (MD), (ii) Kohn-Sham density functional theory with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional, and (iii) the screened-exchange hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE). PBE allows an accurate generation of a-C and the evaluation of the local electrostatic potential in the a-C/water system, HSE yields an improved description of energetic positions which is critical in this case, and classical MD enables a computationally affordable description of water. Our explicit calculation shows that, both in vacuo and in aqueous environment, the a-C electronic states available in the region comprised between the H{sub 2}/H{sub 2}O and O{sub 2}/H{sub 2}O levels of water correspond to both occupied and unoccupied states within the a-C pseudogap region. These are localized states associated to sp{sup 2} sites in a-C. The band realignment induces a shift of approximately 300 meV of the a-C energy band positions with respect to the redox levels of water.

  10. Application of nitrogen-doped ultrananocrystalline diamond/hydrogenated amorphous carbon composite films for ultraviolet detection

    NASA Astrophysics Data System (ADS)

    Zkria, Abdelrahman; Gima, Hiroki; Yoshitake, Tsuyoshi

    2017-03-01

    Nitrogen-doped ultrananocrystalline diamond/hydrogenated amorphous carbon (UNCD/a-C:H) films were grown by coaxial arc plasma deposition in the ambient of nitrogen and hydrogen mixed gases. Synthesized films were structurally investigated by X-ray photoemission and near-edge X-ray absorption fine structure spectroscopies. A heterojunction with p-type Si substrate was fabricated to study the ultraviolet photodetection properties of the film. Capacitance-voltage measurements assure the expansion of a depletion region into the film side. Current-voltage curves in the dark showed a good rectifying behaviour in the bias voltages range between ±5 V. Under 254 nm monochromatic light, the heterojunction shows a capability of deep ultraviolet light detection, which can be attribute to the existence of UNCD grains. As the diode was cooled from 300 K down to 150 K, the detectivity has a notable enhancement from 1.94 × 105 cm Hz1/2 W-1 at 300 K to 5.11 × 1010 cm Hz1/2 W-1 at 150 K, which is mainly due to a remarkable reduction in the leakage current at low temperatures. It was experimentally demonstrated that nitrogen-doped UNCD/a-C:H film works as ultraviolet-range photovoltaic material.

  11. Microstructure and tribological properties of Ti-contained amorphous carbon film deposited by DC magnetron sputtering

    SciTech Connect

    Li, R. L.; Tu, J. P.; Hong, C. F.; Liu, D. G.; Zhou, D. H.; Sun, H. L.

    2009-12-15

    Pure amorphous carbon (a-C) film and that with a small amount of Ti were deposited on high speed steel (W18Cr4V) substrates by means of dc closed field unbalanced magnetron sputtering. The chemical composition and microstructure of the a-C films were performed using x-ray photoelectron spectroscopy, x-ray diffraction, Raman spectra, and transmission electron microscopy. The mechanical and tribological properties were evaluated using a nanoindentor, Rockwell and scratch tests, and a conventional ball-on-disk tribometer, respectively. The pure a-C film showed the high hardness (53 GPa), elastic modulus (289 GPa), but the poor adhesive strength. When adding a small amount of Ti to the a-C film, both the adhesive strength and the tribological properties were improved. The Ti contained a-C film had the low wear rate (1.9x10{sup -17} m{sup 3} N{sup -1} m{sup -1}) and friction coefficient in humid air.

  12. Tribological properties, corrosion resistance and biocompatibility of magnetron sputtered titanium-amorphous carbon coatings

    NASA Astrophysics Data System (ADS)

    Dhandapani, Vishnu Shankar; Subbiah, Ramesh; Thangavel, Elangovan; Arumugam, Madhankumar; Park, Kwideok; Gasem, Zuhair M.; Veeraragavan, Veeravazhuthi; Kim, Dae-Eun

    2016-05-01

    Amorphous carbon incorporated with titanium (a-C:Ti) was coated on 316L stainless steel (SS) by magnetron sputtering technique to attain superior tribological properties, corrosion resistance and biocompatibility. The morphology, topography and functional groups of the nanostructured a-C:Ti coatings in various concentrations were analyzed using atomic force microscopy (AFM), Raman, X-Ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Raman and XPS analyses confirmed the increase in sp2 bonds with increasing titanium content in the a-C matrix. TEM analysis confirmed the composite nature of the coating and the presence of nanostructured TiC for Ti content of 2.33 at.%. This coating showed superior tribological properties compared to the other a-C:Ti coatings. Furthermore, electrochemical corrosion studies were performed against stimulated body fluid medium in which all the a-C:Ti coatings showed improved corrosion resistance than the pure a-C coating. Preosteoblasts proliferation and viability on the specimens were tested and the results showed that a-C:Ti coatings with relatively high Ti (3.77 at.%) content had better biocompatibility. Based on the results of this work, highly durable coatings with good biocompatibility could be achieved by incorporation of optimum amount of Ti in a-C coatings deposited on SS by magnetron sputtering technique.

  13. Pseudo first ordered adsorption of noxious textile dyes by low-temperature synthesized amorphous carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Banerjee, D.; Bhowmick, P.; Pahari, D.; Santra, S.; Sarkar, S.; Das, B.; Chattopadhyay, K. K.

    2017-03-01

    Amorphous carbon nanotubes (a-CNTs) were synthesized by solid state reaction. The as prepared a-CNTs were characterized by X-ray diffraction, field emission scanning and high resolution transmission electron microscope and Raman spectroscopy. As-synthesized a-CNTs were used for, the first time, for removing different organic dyes from water. The dyes mainly include Rhodamine B and Methyl Orange and systematic batch mode studies of a-CNTs assisted adsorption have been executed in detail. The removing efficiency of a-CNTs has also been investigated for various sorption parameters like contact time, dosage, pH, initial dye concentration, contact time etc. It is seen that a-CNTs can be material of potential for removal of dyes. In case of Rhodamine B, the maximum time for removal was 45 min whereas for Methyl orange rapid removal was plausible in about 30 min even in ambient condition. The experimental data have been well correlated with classical Langmuir-Freundlich and Temkin adsorption models.

  14. Room temperature ferromagnetism in Co-doped amorphous carbon composites from the spin polarized semiconductor band

    SciTech Connect

    Hsu, H. S. Chien, P. C.; Chang, Y. Y.; Sun, S. J.; Lee, C. H.

    2014-08-04

    This study provides conclusive evidence of room temperature ferromagnetism in Co-doped amorphous carbon (a-C) composites from the spin polarized semiconductor band. These composites are constructed from discontinuous [Co(3 nm)/a-C(d{sub c} nm)]{sub 5} multilayers with d{sub c} = 3 nm and d{sub c} = 6 nm. Only remnant circular dichroism (CD) was observed from the d{sub c} = 3 nm sample but not when d{sub c} = 6 nm. In addition, the remnant CD peaks at 5.5 eV, which is comparable with the absorption peak associated with the C σ-σ* gap transition. We suggest that the possible mechanism for this coupling can be considered as a magnetic proximity effect in which a ferromagnetic moment in the C medium is induced by Co/C interfaces.

  15. Photoconductivity and characterization of nitrogen incorporated hydrogenated amorphous carbon thin films

    NASA Astrophysics Data System (ADS)

    Dwivedi, Neeraj; Kumar, Sushil; Carey, J. D.; Malik, Hitendra K.; Govind

    2012-12-01

    The observation and origin of photoconductivity in high base pressure (˜10-3 Torr) grown nitrogen incorporated hydrogenated amorphous carbon (a-C:H:N) thin films is reported. The magnitude of conductivity at room temperature was measured to increase by nearly two orders of magnitude and exhibits a maximum ratio of photoconductivity to dark conductivity of 1.5 as the nitrogen content increased to 15.1 at. %. X-ray photoelectron spectroscopy, micro-Raman spectroscopy, and Fourier transform infrared spectroscopy reveal enhanced sp2 bonding at higher nitrogen contents. Residual film stress, Tauc band gap, hardness, and elastic modulus are all found to decrease with addition of nitrogen. The electrical characteristics suggest the creation of a-C:H:N/p-Si heterojunction diodes having rectifying behavior. The conductivity and electrical characteristics are discussed in term of band model, and the results show that high quality a-C:H:N films can be grown at high base pressures with properties comparable to those grown at low base pressures.

  16. Hydrogenated amorphous carbon coatings on implants drastically reduce biofilm formation and water permeation

    NASA Astrophysics Data System (ADS)

    Bernsmann, Falk; Laube, Norbert; Baldsiefen, Gerhard; Castellucci, Mattia

    2014-11-01

    Inflammations and crystalline bacterial biofilms (encrustations) remain a major complication in long-term artificial urinary tract drainage. To solve this problem we present urological implants with coatings made of amorphous hydrogenated carbon (a-C:H) that show excellent protection from encrustation in-vitro as well as in-vivo. Part of the success of a-C:H coatings is attributed to their ability to act as a diffusion barrier between an implant and the body, which prevents leaching of solvents from polymeric implants. To further enhance their barrier properties a-C:H coatings are combined with parylene coatings to develop diffusion-barrier multilayer coatings with a total thickness between 0.2 μm and 0.8 μm. The combination of the two types of coatings leads to a reduction of water diffusion by a factor of up to ten with respect to uncoated 25 μm thick polyimide sub-strates. The diffusion of water vapour from a controlled atmospheric pressure chamber through coated foils to a vacuum chamber is measured in a custom-built device.

  17. Core-level photoemission from nanocluster-matrix composites: Au clusters in amorphous carbon

    NASA Astrophysics Data System (ADS)

    Calliari, L.; Minati, L.; Speranza, G.; Paris, A.; Baranov, A.; Fanchenko, S.

    2014-09-01

    We investigate a system consisting of Au nano-clusters and amorphous carbon (a-C) via core-level photoemission. While the ability of photoemission to characterize nano-sized metal clusters is well-known, still some issues deserve investigation. For example, the well-established dominance of final-state relaxation effects in core-level spectra from nano-clusters necessarily involves a crucial role of the cluster dielectric-environment. To the best of our knowledge however, a thorough discussion on this point is lacking. We thus intend to investigate dielectric-environment effects by considering several configurations for Au clusters, i.e. supported and embedded, with the latter obtained either by depositing a-C on top of supported clusters or by co-depositing a-C and Au. We analyze the Au4 f spectrum from clusters accounting for both cluster size and cluster location with respect to the a-C matrix. We show that spectral changes caused by a-C deposition are entirely explained in terms of changes in the cluster dielectric environment. Moreover, we prove that supported clusters are in a well-characterized dielectric environment, while embedded clusters are not. This is because embedded clusters, whatever the method of production, are spatially distributed over the matrix surface-region which is characterized by rapid fluctuations in the dielectric constant.

  18. Thermally induced crystallization and phase evolution in powders derived from amorphous calcium phosphate precipitates with a Ca/P ratio of 1:1

    NASA Astrophysics Data System (ADS)

    Zyman, Zoltan; Epple, Matthias; Goncharenko, Anton; Rokhmistrov, Dmytro; Prymak, Oleg; Loza, Kateryna

    2016-09-01

    Calcium phosphate powders of calcium pyrophosphate α1-CPP (the metastable phase of the high-temperature polymorph α-CPP) and the polymorph β-CPP (stable in this range), of α1-CPP, β-CPP, α1-TCP (metastable polymorph of the high-temperature phase α-tricalcium phosphate) and β-tricalcium phosphate β-TCP were prepared by heating amorphous calcium phosphate (ACP) precipitates with the nominal Ca/P ratio of 1:1 by nitrate synthesis. α1-CPP/β-CPP resulted from a crystallization at 530-640 °C and subsequent heating to 980 °C of unwashed and lyophilized ACP. α1-CPP/β-CPP/α1-TCP/β-TCP was formed by crystallization at 620-720 °C, followed by heating of six-time washed and lyophilized ACP precipitates from an ultra-short synthesis. The activation energy for the crystallization of ACP to α1-CPP was determined with 165 kJ mol-1. The reason for the occurrence of the TCP phases (Ca/P ratio=1.5) from ACP (Ca/P ratio=1) is discussed. The powders are prospective biomaterials for bone substitution because they combine effective bioactive phases with the metastable polymorphs α1-CPP and α1-TCP.

  19. A molecular dynamics analysis of ion irradiation of ultrathin amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Qi, J.; Komvopoulos, K.

    2016-09-01

    Molecular dynamics (MD) simulations provide insight into nanoscale problems where continuum description breaks down, such as the modeling of ultrathin films. Amorphous carbon (a-C) films are commonly used as protective overcoats in various contemporary technologies, including microelectromechanical systems, bio-implantable devices, optical lenses, and hard-disk drives. In all of these technologies, the protective a-C film must be continuous and very thin. For example, to achieve high storage densities (e.g., on the order of 1 Tb/in.2) in magnetic recording, the thickness of the a-C film used to protect the magnetic media and the recording head against mechanical wear and corrosion must be 2-3 nm. Inert ion irradiation is an effective post-deposition method for reducing the film thickness, while preserving the mechanical and chemical characteristics. In this study, MD simulations of Ar+ ion irradiated a-C films were performed to elucidate the effects of the ion incidence angle and ion kinetic energy on the film thickness and structure. The MD results reveal that the film etching rate exhibits a strong dependence on the ion kinetic energy and ion incidence angle, with a maximum etching rate corresponding to an ion incidence angle of ˜20°. It is also shown that Ar+ ion irradiation mainly affects the structure of the upper half of the ultrathin a-C film and that carbon atom hybridization is a strong function of the ion kinetic energy and ion incidence angle. The results of this study elucidate the effects of important ion irradiation parameters on the structure and thickness of ultrathin films and provide fundamental insight into the physics of dry etching.

  20. Novel nanometer-level uniform amorphous carbon coating for boron powders by direct pyrolysis of coronene without solvent

    NASA Astrophysics Data System (ADS)

    Ye, ShuJun; Song, MingHui; Kumakura, Hiroaki

    2015-01-01

    A 3 nm coronene coating and a 4 nm amorphous carbon coating with a uniform shell-core encapsulation structure for nanosized boron (B) powders are formed by a simple process in which coronene is directly mixed with boron particles without a solvent and heated at 520 °C for 1 h or at 630 °C for 3 h in a vacuum-sealed silica tube. Coronene has a melting point lower than its decomposition temperature, which enables liquid coronene to cover B particles by liquid diffusion and penetration without the need for a solvent. The diffusion and penetration of coronene can extend to the boundaries of particles and to inside the agglomerated nanoparticles to form a complete shell-core encapsulated structure. As the temperature is increased, thermal decomposition of coronene on the B particles results in the formation of a uniform amorphous carbon coating layer. This novel and simple nanometer-level uniform amorphous carbon coating method can possibly be applied to many other powders; thus, it has potential applications in many fields at low cost.

  1. Novel nanometer-level uniform amorphous carbon coating for boron powders by direct pyrolysis of coronene without solvent.

    PubMed

    Ye, ShuJun; Song, MingHui; Kumakura, Hiroaki

    2015-01-30

    A 3 nm coronene coating and a 4 nm amorphous carbon coating with a uniform shell-core encapsulation structure for nanosized boron (B) powders are formed by a simple process in which coronene is directly mixed with boron particles without a solvent and heated at 520 °C for 1 h or at 630 °C for 3 h in a vacuum-sealed silica tube. Coronene has a melting point lower than its decomposition temperature, which enables liquid coronene to cover B particles by liquid diffusion and penetration without the need for a solvent. The diffusion and penetration of coronene can extend to the boundaries of particles and to inside the agglomerated nanoparticles to form a complete shell-core encapsulated structure. As the temperature is increased, thermal decomposition of coronene on the B particles results in the formation of a uniform amorphous carbon coating layer. This novel and simple nanometer-level uniform amorphous carbon coating method can possibly be applied to many other powders; thus, it has potential applications in many fields at low cost.

  2. Effects of calcium carbonate and hydroxyapatite on zinc and iron retention in postmenopausal women

    SciTech Connect

    Dawson-Hughes, B.; Seligson, F.H.; Hughes, V.A.

    1986-07-01

    We measured the effect of calcium carbonate and hydroxyapatite on whole-body retention of zinc-65 in 11 and iron-59 in 13 healthy, postmenopausal women. In a single-blind, controlled, crossover study, each subject, on three occasions, ingested a standard test meal supplemented with iron-59 or zinc-65 and capsules containing placebo or 500 mg elemental calcium as calcium carbonate or hydroxyapatite. Whole-body countings were performed prior to, 30 min after, and 2 wk after each meal. Mean (SEM) zinc retention was 18.1 +/- 1.0% with placebo (control) and did not vary significantly with calcium carbonate (110.0 +/- 8.6% of control) or hydroxyapatite (106.0 +/- 7.9% of control). Iron retention, 6.3 +/- 2.0% with placebo, was significantly reduced with both calcium carbonate (43.3 +/- 8.8% of control, p = 0.002) and hydroxyapatite (45.9 +/- 10.0% of control, p = 0.003). Iron absorption may be significantly reduced when calcium supplements are taken with meals.

  3. Direct synthesis of multilayer graphene on an insulator by Ni-induced layer exchange growth of amorphous carbon

    NASA Astrophysics Data System (ADS)

    Murata, H.; Toko, K.; Saitoh, N.; Yoshizawa, N.; Suemasu, T.

    2017-01-01

    Multilayer graphene (MLG) growth on arbitrary substrates is desired for incorporating carbon wiring and heat spreaders into electronic devices. We investigated the metal-induced layer exchange growth of a sputtered amorphous C layer using Ni as a catalyst. A MLG layer uniformly formed on a SiO2 substrate at 600 °C by layer exchange between the C and Ni layers. Raman spectroscopy and electron microscopy showed that the resulting MLG layer was highly oriented and contained relatively few defects. The present investigation will pave the way for advanced electronic devices integrated with carbon materials.

  4. Mo-containing tetrahedral amorphous carbon deposited by dualfiltered cathodic vacuum arc with selective pulsed bias voltage

    SciTech Connect

    Pasaja, Nitisak; Sansongsiri, Sakon; Anders, Andre; Vilaithong,Thiraphat; Intasiri, Sawate

    2006-09-10

    Metal-containing tetrahedral amorphous carbon films were produced by dual filtered cathodic vacuum arc (FCVA) plasma sources operated in sequential pulsed mode. A negatively pulsed bias was applied to the substrate only when carbon plasma was generated. Films thickness was measured after deposition by profilometry. Glass slides with silver pads were used as substrate for the of the measurement sheet resistance. The microstructure and composition of the films were characterized by Raman spectroscopy and Rutherford backscattering, respectively. It found that the electrical resistivity decreases with an increase of the Mo content, which can be ascribed to an increase of sp2 content and an increase of the sp2 cluster size.

  5. Mo-containing tetrahedral amorphous carbon deposited by dualfiltered cathodic vacuum arc with selective pulsed bias voltage

    SciTech Connect

    Pasaja, Nitisak; Sansongsiri, Sakon; Intasiri, Sawate; Vilaithong, Thiraphat; Anders, Andre

    2007-01-24

    Metal-containing tetrahedral amorphous carbon films wereproduced by dual filtered cathodic vacuum arc plasma sources operatedinsequentially pulsed mode. Negatively pulsed bias was applied to thesubstrate when carbon plasma was generated, whereas it was absentwhen themolybdenum plasma was presented. Film thickness was measured afterdeposition by profilometry. Glass slides with silver padswere used assubstrates for the measurement of the sheet resistance. Themicrostructure and composition of the films were characterizedbyRamanspectroscopy and Rutherford backscattering, respectively. It was foundthat the electrical resistivity decreases with an increaseof the Mocontent, which can be ascribed to an increase of the sp2 content and anincrease of the sp2 cluster size.

  6. Multi proxy approach for the formation of calcium carbonates in alkaline man-made environments

    NASA Astrophysics Data System (ADS)

    Rinder, T.; Dietzel, M.; Leis, A.

    2009-04-01

    The formation of calcium carbonates, e.g. in drainage systems of tunnels, may be induced by degassing of CO2-rich groundwater which enters the building. However, the dissolution of portlandite (Ca(OH)2) from cements or the shotcrete of the tunnel wall bears an additional and immense potential for the formation of carbonates from alkaline solutions. Variations in trace element incorporation and distribution of the stable isotopes of carbon and oxygen in the precipitated calcium carbonates may represent powerful tools to identify individual mechanisms for carbonate formation. As portlandite dissolves, highly alkaline solutions are obtained. In this case, precipitation of calcium carbonate can be related to the absorption of CO2 from the atmosphere. Isotopic analyses of the calcite show that fixation of CO2 from the Earth's atmosphere leads to significantly lighter ^13Ccalcite values (down to -25 o/oo, VPDB) as expected for the fixation of groundwater carbonate (typical ^13Ccalcite values between -10 and -16o/oo, VPDB). The evolution of Sr/Ca ratios in the alkaline drainage solutions and in the corresponding calcium carbonate precipitation provides insight into the dissolution process at the concrete with respect to the amount of primarily dissolved portlandite from the cement. Moreover, an inverse relationship between Mg/Ca and Sr/Ca ratios is observed due to the liberation of aqueous strontium by the dissolution of portlandite and the formation of brucite (Mg(OH)2) at alkaline conditions. Less incorporation of magnesium in the calcite structure is a strong indicator for carbonate precipitation from highly alkaline environments. Applications of such multi proxy approaches are discussed with case studies. Main tasks are the reconstruction of the environmental conditions during primary CaCO3 formation and monitoring of ongoing precipitation of calcium carbonates and cement-water interaction in alkaline man-made environments.

  7. Biogenic nanospheres of amorphous carbonated Ca-Mg phosphate within the periostracum of the green mussel Perna viridis.

    PubMed

    Xu, Jun; Zhang, Gangsheng

    2014-12-01

    Recently there is increasing evidence that the shell biomineralization proceeds via an amorphous precursor route. Therefore, the search for and investigation of amorphous biominerals in bivalve shells are of great importance and interest. Here, using a scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffractometer (XRD), and Fourier transform infrared spectrometer (FTIR), we investigate the microstructure and mineralogy of the periostracum in Perna viridis. We find that: (1) the periostracum has three layers, of which the inner and outer layer are of proteins, while the middle layer is mineralized with nanospheres of amorphous biominerals; (2) the nanospheres are of amorphous carbonated Ca-Mg phosphate (ACCP), where the CO3(2)(-)/PO4(3)(-) weight ratio is estimated to be ∼0.3, and the Ca/P and Ca/Mg atomic ratio is ∼1.4 and 1.6, respectively; (3) the nanospheres, with a diameter of 43-106nm, are found to assemble into spherules with a diameter of 160-500nm, which are further organized into parallel microlayers separated by the proteins; and (4) the nanospheres are assumed to function as the pH stabilizer to facilitate the shell's initial mineralization. Finally, we expect that these findings will advance our understanding of the shell's biomineralization process.

  8. pH control in biological systems using calcium carbonate.

    PubMed

    Salek, S S; van Turnhout, A G; Kleerebezem, R; van Loosdrecht, M C M

    2015-05-01

    Due to its abundance, calcium carbonate (CaCO3) has high potentials as a source of alkalinity for biotechnological applications. The application of CaCO3 in biological systems as neutralizing agent is, however, limited due to potential difficulties in controlling the pH. The objective of the present study was to determine the dominant processes that control the pH in an acid-forming microbial process in the presence of CaCO3. To achieve that, a mathematical model was made with a minimum set of kinetically controlled and equilibrium reactions that was able to reproduce the experimental data of a batch fermentation experiment using finely powdered CaCO3. In the model, thermodynamic equilibrium was assumed for all speciation, complexation and precipitation reactions whereas, rate limited reactions were included for the biological fatty acid production, the mass transfer of CO2 from the liquid phase to the gas phase and the convective transport of CO2 out of the gas phase. The estimated pH-pattern strongly resembled the measured pH, suggesting that the chosen set of kinetically controlled and equilibrium reactions were establishing the experimental pH. A detailed analysis of the reaction system with the aid of the model revealed that the pH establishment was most sensitive to four factors: the mass transfer rate of CO2 to the gas phase, the biological acid production rate, the partial pressure of CO2 and the Ca(+2) concentration in the solution. Individual influences of these factors on the pH were investigated by extrapolating the model to a continuously stirred-tank reactor (CSTR) case. This case study indicates how the pH of a commonly used continuous biotechnological process could be manipulated and adjusted by altering these four factors. Achieving a better insight of the processes controlling the pH of a biological system using CaCO3 as its neutralizing agent can result in broader applications of CaCO3 in biotechnological industries.

  9. The Skeletal Organic Matrix from Mediterranean Coral Balanophyllia europaea Influences Calcium Carbonate Precipitation

    PubMed Central

    Goffredo, Stefano; Vergni, Patrizia; Reggi, Michela; Caroselli, Erik; Sparla, Francesca; Levy, Oren; Dubinsky, Zvy; Falini, Giuseppe

    2011-01-01

    Scleractinian coral skeletons are made mainly of calcium carbonate in the form of aragonite. The mineral deposition occurs in a biological confined environment, but it is still a theme of discussion to what extent the calcification occurs under biological or environmental control. Hence, the shape, size and organization of skeletal crystals from the cellular level through the colony architecture, were attributed to factors as diverse as mineral supersaturation levels and organic mediation of crystal growth. The skeleton contains an intra-skeletal organic matrix (OM) of which only the water soluble component was chemically and physically characterized. In this work that OM from the skeleton of the Balanophyllia europaea, a solitary scleractinian coral endemic to the Mediterranean Sea, is studied in vitro with the aim of understanding its role in the mineralization of calcium carbonate. Mineralization of calcium carbonate was conducted by overgrowth experiments on coral skeleton and in calcium chloride solutions containing different ratios of water soluble and/or insoluble OM and of magnesium ions. The precipitates were characterized by diffractometric, spectroscopic and microscopic techniques. The results showed that both soluble and insoluble OM components influence calcium carbonate precipitation and that the effect is enhanced by their co-presence. The role of magnesium ions is also affected by the presence of the OM components. Thus, in vitro, OM influences calcium carbonate crystal morphology, aggregation and polymorphism as a function of its composition and of the content of magnesium ions in the precipitation media. This research, although does not resolve the controversy between environmental or biological control on the deposition of calcium carbonate in corals, sheds a light on the role of OM, which appears mediated by the presence of magnesium ions. PMID:21799830

  10. The effect of pigeon yolk sac fluid on the growth behavior of calcium carbonate crystals.

    PubMed

    Song, Juan; Cheng, Haixia; Shen, Xinyu; Tong, Hua

    2015-03-01

    Previous experiments have proved that thermodynamically unstable calcium carbonate vaterite can exist for long periods in the yolk sac of a pigeon embryo. The aim of this article was to demonstrate the effect of in vitro mineralization of yolk sac fluid on calcium carbonate by direct precipitation. Experiments were conducted using pigeon yolk sac fluid and using lecithin extracted from pigeon yolk sac fluid as a control to investigate the regulating effects of the organic components in the embryo on the formation of the calcium carbonate precipitate. Multiple characterization methods were employed to study the various morphological patterns, sizes, crystal growth, and crystal phase transformations of the calcium carbonate precipitates as regulated by the yolk sac fluid extracted at different stages of incubation. The experimental results demonstrate that as the incubation proceeds towards the later stages, the composition and environmental features of the yolk sac fluid become more favorable for the formation of relatively unstable calcium carbonate phases with high energies of the vaterite state. The experiments conducted with extracted lecithin as the template for crystal growth yielded similar results. A large amount of organic molecules with polar functional groups carried by the yolk sac fluid have strong effects and can both initially induce the crystallization and regulate the aggregation of calcium carbonate. Furthermore, this regulation process is found to be closely related to the lecithin contained in yolk sac fluid. These observations confirm the changes in yolk sac fluid composition during incubation have significant effects on the production of vaterite, which implicates the calcium transport during embryo growth.

  11. Carbonation as a binding mechanism for coal/calcium hydroxide pellets. Technical report, September 1, 1991--November 30, 1991

    SciTech Connect

    Rapp, D.M.

    1991-12-31

    Current coal mining and processing procedures produce a significant quanity of fine coal that is difficult to handle and transport. The objective of this work is to determine if these fines can be economically pelletized with calcium hydroxide, a sulfur capturing sorbent, to produce a clean-burning fuel for fluidized-bed combustors or stoker boilers. To harden these pellets, carbonation, which is the reaction of calcium hydroxide with carbon dioxide to produce a cementitious matrix of calcium carbonate, is being investigated. Previous research indicated that carbonation significantly improved compressive strength, impact and attrition resistance and ``weatherproofed`` pellets formed with sufficient calcium hydroxide (5 to 10% for minus 28 mesh coal fines).

  12. Metrology and Optical Characterization of Plasma Enhanced Chemical Vapor Deposition, (PECVD), low temperature deposited Amorphous Carbon films

    NASA Astrophysics Data System (ADS)

    Ferrieu, F.; Chaton, C.; Neira, D.; Beitia, C.; Mota, L. Proenca; Papon, A. M.; Tarnowka, A.

    2007-09-01

    Amorphous Carbon films deposited by PECVD (RF) have recently been introduced as a new material for semiconductor processing, e.g. in 193 nm ARC lithography [1] and in the DRAM production [2]. A large amount of literature has already been published on with regard to the applications of this class of material [3]. Hence, it has been reported that Amorphous Carbon films undergo a hydrogen chemical desorption when deposited above 500 °C, together with an amorphous to graphite phase transition. Unfortunately, the intrinsic nature of the amorphous carbons depends strongly upon deposition techniques. Film morphology can be completely different from one case to another since there are so many deposition techniques. Optical characterization of these films has also undergone development for several decades. In Spectroscopic Ellipsometry (SE), several models have been proposed from simple Lorentz oscillators' absorption, toward the Tauc Lorentz or Forhoui Bloomer equations. Nevertheless, none of these models sufficiently quantitatively explain the experimental data. In some cases, a simple `Effective Medium Approximation', (EMA), is able to determine the sp2/sp3 bounds present in the film. However, the validity limitation of this approach remains questionable when considering films in a wide range of film thicknesses. In line, metrology for semiconductor requires robust models, which account for parameters such as temperature deposition, stress and film resistivity as well. Different solutions are investigated from our optical measurements, including a biaxial anisotropy hypothesis, which has been proposed by J. Leng et al. [3] from BPR (Beam Reflectometry Profile) and with SE measurements [4]. Our results are considered, together with other surface analysis techniques (XRD, IR and Raman) and confronted to TEM observations.

  13. Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous UIV-phosphate

    NASA Astrophysics Data System (ADS)

    Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; Boyanov, Maxim I.

    2016-02-01

    The mobility of uranium in subsurface environments depends strongly on its redox state, with UIV phases being significantly less soluble than UVI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of UVI reduction in natural systems, a nanoparticulate UO2 phase and an amorphous UIV-Ca-PO4 analog to ningyoite (CaUIV(PO4)2·1-2H2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for UIVO2 and UIV-phosphate in solutions equilibrated with atmospheric O2 and CO2 at pH 7.0 (kobs,UO2 = 0.17 ± 0.075 h-1 vs. kobs,UIVPO4 = 0.30 ± 0.25 h-1). Addition of up to 400 μM Ca and PO4 decreased the oxidation rate constant by an order of magnitude for both UO2 and UIV-phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO4, the product of UO2 oxidation is Na-uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO4 and low carbonate concentration), resulting in low concentrations of dissolved UVI (<2.5 × 10-7 M). Oxidation of UIV-phosphate produced a Na-autunite phase (Na2(UO2)PO4·xH2O), resulting in similarly low dissolved U concentrations (<7.3 × 10-8 M). When Ca and PO4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO2 and UIV-phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca-UVI-PO4 layer on the UO2 surface and suggest a passivation layer mechanism for the decreased rate of UO2 oxidation in the presence of Ca and PO4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO2 solids, suggesting that oxidized U is distributed between

  14. Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous UIV–phosphate

    DOE PAGES

    Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; ...

    2015-11-17

    The mobility of uranium in subsurface environments depends strongly on its redox state, with UIV phases being significantly less soluble than UVI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of UVI reduction in natural systems, a nanoparticulate UO2 phase and an amorphous UIV–Ca–PO4 analog to ningyoite (CaUIV(PO4)2·1–2H2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for UIVO2 and UIV–phosphate in solutions equilibrated with atmospheric O2 and CO2 at pH 7.0 (kobs,UO2 = 0.17 ± 0.075 h-1 vs. kobs,UIVPO4 = 0.30 ± 0.25 h-1). Addition ofmore » up to 400 μM Ca and PO4 decreased the oxidation rate constant by an order of magnitude for both UO2 and UIV–phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO4, the product of UO2 oxidation is Na–uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO4 and low carbonate concentration), resulting in low concentrations of dissolved UVI (<2.5 × 10-7 M). Oxidation of UIV–phosphate produced a Na-autunite phase (Na2(UO2)PO4·xH2O), resulting in similarly low dissolved U concentrations (<7.3 × 10-8 M). When Ca and PO4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO2 and UIV–phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca–UVI–PO4 layer on the UO2 surface and suggest a passivation layer mechanism for the decreased rate of UO2 oxidation in the presence of Ca and PO4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO2 solids, suggesting that

  15. Recovery of calcium carbonate from steelmaking slag and utilization for acid mine drainage pre-treatment.

    PubMed

    Mulopo, J; Mashego, M; Zvimba, J N

    2012-01-01

    The conversion of steelmaking slag (a waste product of the steelmaking process) to calcium carbonate (CaCO(3)) was tested using hydrochloric acid, ammonium hydroxide and carbon dioxide via a pH-swing process. Batch reactors were used to assess the technical feasibility of calcium carbonate recovery and its use for pre-treatment of acid mine drainage (AMD) from coal mines. The effects of key process parameters, such as the amount of acid (HCl/calcium molar ratio), the pH and the CO(2) flow rate were considered. It was observed that calcium extraction from steelmaking slag significantly increased with an increase in the amount of hydrochloric acid. The CO(2) flow rate also had a positive effect on the carbonation reaction rate but did not affect the morphology of the calcium carbonate produced for values less than 2 L/min. The CaCO(3) recovered from the bench scale batch reactor demonstrated effective neutralization ability during AMD pre-treatment compared with the commercial laboratory grade CaCO(3).

  16. Ubiquitylation functions in the calcium carbonate biomineralization in the extracellular matrix.

    PubMed

    Fang, Dong; Pan, Cong; Lin, Huijuan; Lin, Ya; Xu, Guangrui; Zhang, Guiyou; Wang, Hongzhong; Xie, Liping; Zhang, Rongqing

    2012-01-01

    Mollusks shell formation is mediated by matrix proteins and many of these proteins have been identified and characterized. However, the mechanisms of protein control remain unknown. Here, we report the ubiquitylation of matrix proteins in the prismatic layer of the pearl oyster, Pinctada fucata. The presence of ubiquitylated proteins in the prismatic layer of the shell was detected with a combination of western blot and immunogold assays. The coupled ubiquitins were separated and identified by Edman degradation and liquid chromatography/mass spectrometry (LC/MS). Antibody injection in vivo resulted in large amounts of calcium carbonate randomly accumulating on the surface of the nacreous layer. These ubiquitylated proteins could bind to specific faces of calcite and aragonite, which are the two main mineral components of the shell. In the in vitro calcium carbonate crystallization assay, they could reduce the rate of calcium carbonate precipitation and induce the calcite formation. Furthermore, when the attached ubiquitins were removed, the functions of the EDTA-soluble matrix of the prismatic layer were changed. Their potency to inhibit precipitation of calcium carbonate was decreased and their influence on the morphology of calcium carbonate crystals was changed. Taken together, ubiquitylation is involved in shell formation. Although the ubiquitylation is supposed to be involved in every aspect of biophysical processes, our work connected the biomineralization-related proteins and the ubiquitylation mechanism in the extracellular matrix for the first time. This would promote our understanding of the shell biomineralization and the ubiquitylation processes.

  17. Ubiquitylation Functions in the Calcium Carbonate Biomineralization in the Extracellular Matrix

    PubMed Central

    Fang, Dong; Pan, Cong; Lin, Huijuan; Lin, Ya; Xu, Guangrui; Zhang, Guiyou; Wang, Hongzhong; Xie, Liping; Zhang, Rongqing

    2012-01-01

    Mollusks shell formation is mediated by matrix proteins and many of these proteins have been identified and characterized. However, the mechanisms of protein control remain unknown. Here, we report the ubiquitylation of matrix proteins in the prismatic layer of the pearl oyster, Pinctada fucata. The presence of ubiquitylated proteins in the prismatic layer of the shell was detected with a combination of western blot and immunogold assays. The coupled ubiquitins were separated and identified by Edman degradation and liquid chromatography/mass spectrometry (LC/MS). Antibody injection in vivo resulted in large amounts of calcium carbonate randomly accumulating on the surface of the nacreous layer. These ubiquitylated proteins could bind to specific faces of calcite and aragonite, which are the two main mineral components of the shell. In the in vitro calcium carbonate crystallization assay, they could reduce the rate of calcium carbonate precipitation and induce the calcite formation. Furthermore, when the attached ubiquitins were removed, the functions of the EDTA-soluble matrix of the prismatic layer were changed. Their potency to inhibit precipitation of calcium carbonate was decreased and their influence on the morphology of calcium carbonate crystals was changed. Taken together, ubiquitylation is involved in shell formation. Although the ubiquitylation is supposed to be involved in every aspect of biophysical processes, our work connected the biomineralization-related proteins and the ubiquitylation mechanism in the extracellular matrix for the first time. This would promote our understanding of the shell biomineralization and the ubiquitylation processes. PMID:22558208

  18. Calcium-decorated carbon nanostructures for the selective capture of carbon dioxide.

    PubMed

    Koo, Jahyun; Bae, Hyeonhu; Kang, Lei; Huang, Bing; Lee, Hoonkyung

    2016-10-26

    The development of advanced materials for CO2 capture is of great importance for mitigating climate change. In this paper, we outline our discovery that calcium-decorated carbon nanostructures, i.e., zigzag graphene nanoribbons (ZGNRs), carbyne, and graphyne, have great potential for selective CO2 capture, as demonstrated via first-principles calculations. Our findings show that Ca-decorated ZGNRs can bind up to three CO2 molecules at each Ca atom site with an adsorption energy of ∼-0.8 eV per CO2, making them suitable for reversible CO2 capture. They adsorb CO2 molecules preferentially, compared with other gas molecules such as H2, N2, and CH4. Moreover, based on equilibrium thermodynamical simulations, we confirm that Ca-decorated ZGNRs can capture CO2 selectively from a gas mixture with a capacity of ∼4.5 mmol g(-1) under ambient conditions. Similar results have been found in other carbon nanomaterials, indicating the generality of carbon based nanostructures for selective CO2 capture under ambient conditions.

  19. How High Concentrations of Proteins Stabilize the Amorphous State of Calcium Orthophosphate: A Solid-State Nuclear Magnetic Resonance (NMR) Study of the Casein Case.

    PubMed

    De Sa Peixoto, Paulo; Silva, Juliana V C; Laurent, Guillaume; Schmutz, Marc; Thomas, Daniel; Bouchoux, Antoine; Gésan-Guiziou, Geneviève

    2017-02-07

    Understanding how proteins stabilize amorphous calcium ortho-phosphate (ACP) phases is of great importance in biology and for pharmaceutical or food applications. Until now, most of the former investigations about ACP-protein stability and equilibrium were performed under conditions where ACP colloidal nanoclusters are surrounded by low to moderate concentrations of peptides or proteins (15-30 g L(-1)). As a result, the question of ACP-protein interactions in highly concentrated protein systems has clearly been overlooked, whereas it corresponds to actual industrial conditions such as drying or membrane filtration in the dairy industry for instance. In this study, the structure of an ACP phase is monitored in association with one model phosphorylated protein (casein) using solid-state nuclear magnetic resonance (ssNMR) under two conditions of high protein concentration (300 and 400 g L(-1)). At both concentrations and at 25 °C, it is found that the caseins maintain the mineral phase in an amorphous form with no detectable influence on its structure or size. Interestingly, and in both cases, a significant amount of the nonphosphorylated side chains interacts with ACP through hydrogen bonds. The number of these interacting side chains is found to be higher at the highest casein concentration. At 45 °C, which is a destabilizing temperature of ACP under protein-free conditions, the amorphous structure of the mineral phase is partially transformed at a casein concentration of 300 g L(-1), while it remains almost intact at a casein concentration of 400 g L(-1). Therefore, these results clearly indicate that increasing the concentration of proteins favors ACP-protein interactions and stabilizes the ACP clusters more efficiently.

  20. Calcium

    MedlinePlus

    ... milligrams) of calcium each day. Get it from: Dairy products. Low-fat milk, yogurt, cheese, and cottage ... lactase that helps digest the sugar (lactose) in dairy products, and may have gas, bloating, cramps, or ...

  1. A calcium oxide sorbent process for bulk separation of carbon dioxide

    SciTech Connect

    Harrison, D.P.; Han, C.

    1994-10-01

    In this experimental investigation, a laboratory-scale fixed-bed reactor containing a calcium-based sorbent is being used to study the feasibility of combining CO{sub 2} removal with the water gas shift reaction. The sorptive properties of the calcium oxide sorbent were studied as a function of carbonation temperature and pressure, synthesis gas composition, reactor space velocity, and sorbent composition and properties.

  2. Amorphous flower-like molybdenum-sulfide-@-nitrogen-doped-carbon-nanofiber film for use in the hydrogen-evolution reaction.

    PubMed

    Zhang, Xiaoyan; Li, Libo; Guo, Yaxiao; Liu, Dong; You, Tianyan

    2016-06-15

    A novel amorphous flower-like molybdenum sulfides@nitrogen doped carbon nanofibers (MoSx@NCNFs) films are successfully synthesized by combining electrospinning, carbonization and a mild hydrothermal process. NCNFs, as a conductive substrate, can accelerate the electron transfer rate and depress the aggregation of MoSx nanoparticles. The resultant amorphous flower-like MoSx on NCNFs exposes abundant S(2-)/S2(2-) active edge sites which is of great importance for hydrogen evolution reaction (HER) catalytic performance. Electrochemical measurements demonstrate the superior electrocatalytic activity of MoSx@NCNFs toward HER deriving from the synergistic effect between NCNFs and amorphous MoSx. The overpotential is only 137 mV to reach the current density of 10 mA cm(-2) with a Tafel slope of 41 mV decade(-1) at MoSx@NCNFs. Meanwhile, MoSx@NCNFs exhibits satisfactory long-time stability for HER. Noteworthy, the obtained composites show a free-standing structure which can be directly used as electrode materials. This work provides a feasible way to design promising noble-metal free electrocatalysts in the aspect of energy conversion.

  3. Oral bacterial adhesion on amorphous carbon and titanium films: effect of surface roughness and culture media.

    PubMed

    Almaguer-Flores, A; Ximénez-Fyvie, L A; Rodil, S E

    2010-01-01

    Implant infections can cause severe problems from malfunctioning to dangerous sepsis affecting the health of the patient. For many years, titanium has been the most common material used on dental implants due to their mechanical and biocompatibility properties. Recent studies suggest that amorphous carbon (a-C) films can be possible candidates for coating dental implants, improving some important features like biocompatibility and bone formation. In the oral cavity, the risk of an implant infection is high due to multiple species are capable to colonize this site and these biofilm infections can limit the use of these medical devices. The purpose of this study was to evaluate the influence of the surface chemistry, roughness, and culture media in the bacterial colonization process. To achieve this, a-C and Ti films were deposited on rough and smooth surfaces and cultured with different microorganisms belonging to the oral microbiota with mycoplasma medium (MM) or human saliva (HS). Samples were incubated for 24 h, after this, samples were sonicated and the number of attached bacteria was determined by counting the colony-forming units (CFU's) from each sample. The proportion of the species in the biofilms was determined using checkerboard DNA-DNA hybridization. Data were analyzed by Student's t test using Bonferroni's modification of Student's t test and differences on the proportion of the bacterial species attached to each surface were determined using the Mann-Whitney test. Results show an increased number of CFU's on rough surfaces, especially on the a-C surfaces. The incubation media were an important factor on the adhesion of certain taxa, whereas other species were more sensitive to surface chemistry and others to surface roughness.

  4. Electron cyclotron resonance deposition, structure, and properties of oxygen incorporated hydrogenated diamondlike amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Adamopoulos, G.; Godet, C.; Zorba, T.; Paraskevopoulos, K. M.; Ballutaud, D.

    2004-11-01

    Oxygen-incorporated hydrogenated amorphous carbon films were grown by the integrated distributed electron cyclotron resonance plasma technique from a mixture of acetylene and oxygen. It has been found that the increase of the oxygen to acetylene gas ratio results in more oxygen incorporation up to O /(O+C)=0.2 with a decrease in the hydrogen concentration within the film as measured by the nuclear reaction analysis (NRA) and a combination of the elastic recoil detection analysis and Rutherford backscattering techniques. The spectroscopic ellipsometry in the range of 1.5-5eV showed a negligible decrease of the E04 optical band gap for increasing the oxygen content. At the same time, the decrease of the refractive index from 2.2 to 2.0 denotes the decrease of the films density, which was independently estimated by NRA. The visible (488nm) Raman spectroscopy showed that the increase of the oxygen content favors the clustering of the six-fold sp2C rings. The Fourier transform infrared spectroscopy gives evidence of both C-O and C O bonding configurations. No evidence of O-H bonds formation is found. Simultaneously, the chemisorption of CO2 seems to increased with increasing the oxygen to acetylene gas ratio, which is consistent with the lower film density. The previously trends denote the "softening" of the films, which is consistent with the significant decrease (of about 35%) of the compressive stress allowing the growth of thicker but still transparent films.

  5. Effect of Substrates on Film Hardness Measurements of Nanometer Thick Amorphous Carbon Films

    NASA Astrophysics Data System (ADS)

    Akasaka, Hiroki; Ito, Hiroki; Nakano, Masayuki; Ohshio, Shigeo; Saitoh, Hidetoshi

    Amorphous carbon film (a-C:H) applications, such as hard disks, require films with nanometer thicknesses. In an indentation test, the obtained hardness values of these films are affected by substrates. On the indentation tests, we studied the effect of substrate hardness on films less than 200 nm in thickness. a-C:H and Si doped a-C:H (a-C:Si:H) films were deposited by electron cyclotron resonance plasma chemical vapor deposition onto aluminum (Al) and silicon (Si) substrates. The film thicknesses were approximately 140 nm. The hardnesses of the a-C:H film and substrates were obtained using a high-resolution indentation tester (pico-dentor) with a Vickers tip whose depth resolution was 0.04 nm. Maximum indentation loads were varied from 0.01 to 0.5 mN. The Martens hardnesses of films on the Al and Si substrates were 600 and 7000 N/mm2, respectively. On the a-C:Si:H film deposited on the Al substrate, the hardnesses increased from 1600 to 3900 N/mm2 with decreasing indentation load. The hardnesses of the films deposited on the Si substrate decreased from 5300 to 3500 N/mm2 when the maximum indentation loads were reduced. The effect of the substrates increased with the maximum load increasing. From these findings, the actual hardness value was determined to be 3600 N/mm2. These results indicate that the high-resolution indentation test achieved hardness estimations for nanometer-thick films with certain hardnesses.

  6. A study of the chemical, mechanical, and surface properties of thin films of hydrogenated amorphous carbon

    SciTech Connect

    Vandentop, G.J.

    1990-07-01

    Amorphous hydrogenated carbon (a-C:H) films were studied with the objective of elucidating the nucleation and growth mechanisms, and the origin of their unique physical properties. The films were deposited onto Si(100) substrates both on the powered (negatively self-biased) and on the grounded electrodes from methane in an rf plasma (13.56 MHz) at 65 mTorr and 300 to 370 K. The films produced at the powered electrode exhibited superior mechanical properties, such as high hardness. A mass spectrometer was used to identify neutral species and positive ions incident on the electrodes from the plasma, and also to measure ion energies. The effect of varying ion energy flux on the properties of a-C:H films was investigated using a novel pulsed biasing technique. It was demonstrated that ions were not the dominant deposition species as the total ion flux measured was insufficient to account for the observed deposition rate. The interface between thin films of a-C:H and silicon substrates was investigated using angle resolved x-ray photoelectron spectroscopy. A silicon carbide layer was detected at the interface of a hard a-C:H film formed at the powered electrode. At the grounded electrode, where the kinetic energy is low, no interfacial carbide layer was observed. Scanning tunneling microscopy and high energy electron energy loss spectroscopy was used to investigate the initial stages of growth of a-C:H films. On graphite substrates, films formed at the powered electrode were observed to nucleate in clusters approximately 50 {Angstrom} in diameter, while at the grounded electrode no cluster formation was observed. 58 figs.

  7. Calcium Carbonate Formation by Synechococcus sp. Strain PCC 8806 and Synechococcus sp. Strain PCC 8807

    SciTech Connect

    Lee, Brady D.; William A. Apel; Michelle R. Walton

    2006-12-01

    Precipitation of CaCO3 catalyzed by the growth and physiology of cyanobacteria in the Genus Synechococcus represents a potential mechanism for sequestration of CO2 produced during the burning of coal for power generation. Microcosm experiments were performed in which Synechococcus sp. strain PCC 8806 and Synechococcus sp. strain PCC 8807 were tested for their ability to calcify when exposed to a fixed calcium concentration of 3.4 mM and bicarbonate concentrations of 0.5, 1.25 and 2.5 mM. Disappearance of soluble calcium was used as an indicator of CaCO3 formation; results from metabolically active microcosms were compared to controls with no cells or no carbonate added. Synechococcus sp. strain PCC 8806 removed calcium continuously over the duration of the experiment with approximately 18.6 mg of calcium in the solid phase. Calcium removal occurred over a two-day time period when Synechococcus sp. strain PCC 8807 was tested and only 8.9 mg of calcium was removed in the solid phase. The ability of the cyanobacteria to create an alkaline growth environment appeared to be the primary factor responsible for CaCO3 precipitation in these experiments. Removal of inorganic carbon by fixation into biomass was insignificant compared to the mass of inorganic carbon removed by incorporation into the growing CaCO3 solid.

  8. Why to synthesize vaterite polymorph of calcium carbonate on the cellulose matrix via sonochemistry process?

    PubMed

    Fu, Lian-Hua; Dong, Yan-Yan; Ma, Ming-Guo; Yue, Wen; Sun, Shao-Long; Sun, Run-Cang

    2013-09-01

    Vaterite is an important biomedical material due to its features such as high specific surface area, high solubility, high dispersion, and small specific gravity. The purposes of this article were to explore the growth mechanism of vaterite on the cellulose matrix via sonochmistry process. In the work reported herein, the influences of experimental parameters on the polymorph of calcium carbonate were investigated in detail. The calcium carbonate crystals on the cellulose matrix were characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). Experimental results revealed that all the reactants, solvent, and synthesis method played an important role in the polymorph of calcium carbonate. The pure phase of vaterite polymorph was obtained using Na2CO3 as reactant in ethylene glycol on the cellulose matrix via sonochmistry process. Based on the experimental results, one can conclude that the synthesis of vaterite polymorph is a system process.

  9. Method of forming a stress relieved amorphous tetrahedrally-coordinated carbon film

    DOEpatents

    Friedmann, Thomas A.; Sullivan, John P.

    2000-01-01

    A stress-relieved amorphous-diamond film is formed by depositing an amorphous diamond film with specific atomic structure and bonding on to a substrate, and annealing the film at sufficiently high temperature to relieve the compressive stress in said film without significantly softening said film. The maximum annealing temperature is preferably on the order of 650.degree. C., a much lower value than is expected from the annealing behavior of other materials.

  10. Study of Electrical and Optical Properties of Cu-ASSISTED Amorphous Carbon Thin Films Deposition by DC Magnetron Sputtering

    NASA Astrophysics Data System (ADS)

    Hassannia, Sara; Elahi, Seyed Mohammad; Boochani, Arash

    2013-09-01

    Cu incorporated amorphous carbon thin films have been prepared by DC-magnetron sputtering using a bi-component Cu-C composite target. The properties of the films have been investigated by X-ray diffraction, energy dispersive X-ray analysis, atomic force microscopy, FTIR, Raman and UV-vis spectroscopies. The results show that the films are amorphous with major distorted sp2 graphite bonds as well as carbon nanotubes. Sputtering simulation shows that the chemical composition of the films is Cu0.066C0.934. Cu addition results in the formation of new type of carbon nanotubes (CNT) with new radial Breathing mode located at 236 cm-1. Cu induces an increase in the density of defects due to bundles of CNT's. Moreover the films are transparent in visible range and highly reflective in mid-infrared region. Electrical characterization shows that the pure carbon deposited films are semiconductor while the copper assisted thin films behave like metal and their sheet resistance is comparable with sheet resistance of conventional conductive electrodes.

  11. Thermal breakdown of calcium carbonate and constraints on its use as a biomarker

    NASA Astrophysics Data System (ADS)

    Thompson, Stephen P.; Parker, Julia E.; Tang, Chiu C.

    2014-02-01

    Observed differences in the thermal behaviour of calcium carbonates of biogenic and abiogenic origin (phase transformation and breakdown temperatures) are widely cited as potential biomarkers for whether life once existed on Mars. Although seemingly compelling, there has been no systematic investigation into the physical mechanism behind these apparent differences and therefore no direct proof that they are uniquely diagnostic of a biogenic versus abiogenic formation. In this paper we present a laboratory investigation into the thermal behaviour of two high purity calcium carbonates, one of which was produced in the presence of an amino acid as a biomimetic carbonate. In situ synchrotron X-ray powder diffraction measurements show the aragonite-to-calcite phase transition and calcite-to-oxide breakdown temperatures are significantly lower in the biomimetic carbonate. The observed thermal differences closely match reported differences between biogenic and geological abiogenic carbonates. The biomimetic carbonate exhibits a modified crystal morphology, with a highly strained internal crystal lattice, similar to biogenic carbonate structures. Since biogenic carbonates are formed in the presence of organic macromolecules such as amino acids, the induced microstrain appears to be the defining common factor as it adds an additional energy term to the carbonate lattice energy, which lowers the activation energy required for structural transformation or decomposition. Although produced via biomimetic means, the carbonate investigated here is nevertheless abiogenic in origin and we propose that given suitable localised conditions such as pooled water and a supply of organic molecules, naturally occurring biomimetic carbonates could have similarly formed on the martian surface and could therefore exhibit the same thermal characteristics as biogenic carbonate. Thus as a limiting case - without other supporting observations - the thermal behaviour of martian calcium carbonate

  12. Enzyme-accelerated and structure-guided crystallization of calcium carbonate: role of the carbonic anhydrase in the homologous system.

    PubMed

    Müller, Werner E G; Schlossmacher, Ute; Schröder, Heinz C; Lieberwirth, Ingo; Glasser, Gunnar; Korzhev, Michael; Neufurth, Meik; Wang, Xiaohong

    2014-01-01

    The calcareous spicules from sponges, e.g. from Sycon raphanus, are composed of almost pure calcium carbonate. In order to elucidate the formation of those structural skeletal elements, the function of the enzyme carbonic anhydrase (CA), isolated from this species, during the in vitro calcium carbonate-based spicule formation, was investigated. It is shown that the recombinant sponge CA substantially accelerates calcium carbonate formation in the in vitro diffusion assay. A stoichiometric calculation revealed that the turnover rate of the sponge CA during the calcification process amounts to 25 CO2s(-1) × molecule CA(-1). During this enzymatically driven process, initially pat-like particles are formed that are subsequently transformed to rhomboid/rhombohedroid crystals with a dimension of ~50 μm. The CA-catalyzed particles are smaller than those which are formed in the absence of the enzyme. The Martens hardness of the particles formed is ~4 GPa, a value which had been determined for other biogenic calcites. This conclusion is corroborated by energy-dispersive X-ray spectroscopy, which revealed that the particles synthesized are composed predominantly of the elements calcium, oxygen and carbon. Surprising was the finding, obtained by light and scanning electron microscopy, that the newly formed calcitic crystals associate with the calcareous spicules from S. raphanus in a highly ordered manner; the calcitic crystals almost perfectly arrange in an array orientation along the two opposing planes of the spicules, leaving the other two plane arrays uncovered. It is concluded that the CA is a key enzyme controlling the calcium carbonate biomineralization process, which directs the newly formed particles to existing calcareous spicular structures. It is expected that with the given tools new bioinspired materials can be fabricated.

  13. The Influence of Calcium Carbonate Grain Coatings on Contaminant Reactivity in Vadose Zone Sediments

    SciTech Connect

    Zachara, John M.; Chambers, Scott; Brown Jr., Gordon E.; Eggleston, Carrick M.

    2001-06-01

    Calcium carbonate (CaCO3) is widely distributed through the Hanford vadose zone as a minor phase. As a result of current and past geochemical processes, CaCO3 exists as grain coatings, intergrain fill, and distinct caliche layers in select locations. Calcium carbonate may also precipitate when high-level wastes react with naturally Ca- and Mg-saturated Hanford sediments. Calcium carbonate is a very reactive mineral phase. Sorption reactions on its surface may slow the migration of certain contaminants (Co, Sr), but its surface coatings on other mineral phases may diminish contaminant retardation (for example, Cr) by blocking surface reaction sites of the substrate. This project explores the behavior of calcium carbonate grain coatings, including how they form and dissolve, their reactivity toward key Hanford contaminants, their impact (as surface coatings) on the reactivity of other mineral substrates, and on their in-ground composition and minor element enrichment. The importance of CaCO3 as a contaminant sorbent will be defined in all of its different manifestations in Hanford sediments: dispersed minor lithic fragments, pedogenic carbonate coatings on gravel and stringers in silt, and nodules in clay and paleosols. Mass action models will be developed that allow understanding and prediction of the geochemical effects of CaCO3 on contaminant retardation in Hanford sediments.

  14. Chemical analysis and molecular models for calcium-oxygen-carbon interactions in black carbon found in fertile Amazonian anthrosoils.

    PubMed

    Archanjo, Braulio S; Araujo, Joyce R; Silva, Alexander M; Capaz, Rodrigo B; Falcão, Newton P S; Jorio, Ado; Achete, Carlos A

    2014-07-01

    Carbon particles containing mineral matter promote soil fertility, helping it to overcome the rather unfavorable climate conditions of the humid tropics. Intriguing examples are the Amazonian Dark Earths, anthropogenic soils also known as "Terra Preta de Índio'' (TPI), in which chemical recalcitrance and stable carbon with millenary mean residence times have been observed. Recently, the presence of calcium and oxygen within TPI-carbon nanoparticles at the nano- and mesoscale ranges has been demonstrated. In this work, we combine density functional theory calculations, scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, Fourier transformed infrared spectroscopy, and high resolution X-ray photoelectron spectroscopy of TPI-carbons to elucidate the chemical arrangements of calcium-oxygen-carbon groups at the molecular level in TPI. The molecular models are based on graphene oxide nanostructures in which calcium cations are strongly adsorbed at the oxide sites. The application of material science techniques to the field of soil science facilitates a new level of understanding, providing insights into the structure and functionality of recalcitrant carbon in soil and its implications for food production and climate change.

  15. Synthesis of nanoporous carbon nitride using calcium carbonate as templates with enhanced visible-light photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Chen, Daimei; Yang, Jinjin; Ding, Hao

    2017-01-01

    A commercial calcium carbonate particle as hard template is employed to synthesize mesoporous carbon nitride (mpg-C3N4) by a thermal polycondensation process using dicyandiamide as a precursor, then it can be easily removed using diluted hydrochloric acid. Compare with the other hard templates, such as SiO2 and porous anodic aluminium oxides (Al2O3), the industrially available calcium carbonate particles are not only low-cost, but also environment friendly. A certain amount of carbon dopants were generated in the resulting mpg-C3N4 matrix, and the concentration of carbon dopants can be controlled by the amount of calcium carbonate particle. The synthesized mpg-C3N4 not only possesses high specific surface area, but also has the enhanced visible light absorption range from 460 nm to 800 nm. The photocatalytic activity increases as the mass ratio of template to dicyandiamide increases, when the mass ratio is 1.0, the photocatalytic performance is up to the maximum, which is 12.3 times higher than that of bulk g-C3N4. The enhancement of the photocatalytic performance of mpg-C3N4 is contributed to its improved specific surface areas and the enhancement of the visible light absorptions from 450 nm to 800 nm.

  16. Diamond Nucleation from Amorphous Carbon and Graphite with COH Fluids: an in Situ High Pressure and Temperature Laser-Heated Diamond Anvil Cell Experimental Study

    NASA Astrophysics Data System (ADS)

    Zhang, J.; Prakapenka, V.; Kubo, A.; Kavner, A.; Green, H. W.; Dobrzhinetskaya, L. F.

    2007-12-01

    Microdiamonds from orogenic belts contain nanometer size fluid inclusions suggesting diamond formation from supercritical COH fluids. Previous studies have shown that diamonds synthesized from high pressure and temperature experiments with supercritical COH fluids are characterized by skeletal morphology and solid oxide inclusions. However, mechanism and kinetics of graphite/carbon-to-diamond transformation promoted by COH fluids at high pressure and high temperature conditions are not well understood. Here we report in situ observations of diamond nucleation from COH fluids in laser-heated diamond anvil cell. Our experimental starting materials were amorphous carbon (impurity < 2ppm) and graphite (99.9% pure). Oxalic acid dihydrate (COOH)2·2H2O) was added to amorphous carbon and glucose (C6H12O6) was added to both amorphous carbon and graphite. The organic compounds (3 wt.%) provide CO2- and CH4-rich fluid environments respectively during their breakdown at high pressure and temperature. The mixtures were kept at temperature of 1400-1700 °C and pressure of 8-10 GPa for 10-30 minutes. Experiments show that only nanocrystals of diamond were nucleated from amorphous carbon in CO2-rich fluid environment. The fastest rate of diamond nucleation and growth of ~15 micron size crystals was found in the mixture of amorphous carbon with glucose (CH4-rich environment), whereas only nanocrystalline nuclei were produced in the mixture of graphite with glucose. We have also established that under anhydrous conditions, no diamond nucleation occurred in pure graphite, and only nanocrystals of diamond were observed in the amorphous carbon starting material at temperatures 1700-1900 °C. Our results revealed that the kinetics of diamond nucleation depend on the ¡°precursor¡±: diamond nucleates and grows faster from amorphous carbon than from graphite in the presence of COH fluid; in our anhydrous experiments diamond nucleates only from amorphous carbon. These results

  17. CO.sub.2 Pretreatment prevents calcium carbonate formation

    DOEpatents

    Neavel, Richard C.; Brunson, Roy J.; Chaback, Joseph J.

    1980-01-01

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by pretreatment with carbon dioxide. The carbon dioxide pretreatment is believed to convert the scale-forming components to the corresponding carbonate prior to liquefaction. The pretreatment is accomplished at a total pressure within the range from about 14 to about 68 atmospheres and a carbon dioxide partial pressure within the range from about 14 to about 34 atmospheres. Temperature during pretreatment will generally be within the range from about 100.degree. to about 200.degree. C.

  18. Factors affecting ex-situ aqueous mineral carbonation using calcium and magnesium silicate minerals

    SciTech Connect

    Gerdemann, Stephen J.; Dahlin, David C.; O'Connor, William K.; Penner, Larry R.; Rush, G.E.

    2004-01-01

    Carbonation of magnesium- and calcium-silicate minerals to form their respective carbonates is one method to sequester carbon dioxide. Process development studies have identified reactor design as a key component affecting both the capital and operating costs of ex-situ mineral sequestration. Results from mineral carbonation studies conducted in a batch autoclave were utilized to design and construct a unique continuous pipe reactor with 100% recycle (flow-loop reactor). Results from the flow-loop reactor are consistent with batch autoclave tests, and are being used to derive engineering data necessary to design a bench-scale continuous pipeline reactor.

  19. Energetic and structural studies of amorphous Ca1-xMgxCO3·nH2O (0 ⩽ x ⩽ 1)

    NASA Astrophysics Data System (ADS)

    Radha, A. V.; Fernandez-Martinez, Alejandro; Hu, Yandi; Jun, Young-Shin; Waychunas, Glenn A.; Navrotsky, Alexandra

    2012-08-01

    Early stage amorphous precursors provide a low energy pathway for carbonate mineralization. Many natural deposits of carbonate minerals and biogenic calcium carbonate (both amorphous and crystalline) include significant amounts of Mg. To understand the role of magnesium-containing amorphous precursors in carbonate mineralization, we investigated the energetics and structure of synthetic amorphous Ca-Mg carbonates with composition Ca1-xMgxCO3·nH2O (0 ⩽ x ⩽ 1) using isothermal acid solution calorimetry and synchrotron X-ray scattering experiments with pair distribution function (PDF) analysis. Amorphous magnesium carbonate (AMC with x = 1) is energetically more metastable than amorphous calcium carbonate (ACC with x = 0), but it is more persistent (crystallizing in months rather than days under ambient conditions), probably due to the slow kinetics of Mg2+ dehydration. The Ca1-xMgxCO3·nH2O (0 ⩽ x ⩽ 1) system forms a continuous X-ray amorphous series upon precipitation and all intermediate compositions are energetically more stable than a mixture of ACC and AMC, but metastable with respect to crystalline carbonates. The amorphous system can be divided into two distinct regions. For x = 0.00-0.47, thermal analysis is consistent with a homogeneous amorphous phase. The less metastable compositions of this series, with x = 0.0-0.2, are frequently found in biogenic carbonates. If not coincidental, this may suggest that organisms take advantage of this single phase low energy amorphous precursor pathway to crystalline biogenic carbonates. For x ⩾ 0.47, energetic metastability increases and thermal analysis hints at nanoscale heterogeneity, perhaps of a material near x = 0.5 coexisting with another phase near pure AMC (x = 1). The most hydrated amorphous phases, which occur near x = 0.5, are the least metastable, and may be precursors for dolomite formation.

  20. THE 217.5 nm BAND, INFRARED ABSORPTION, AND INFRARED EMISSION FEATURES IN HYDROGENATED AMORPHOUS CARBON NANOPARTICLES

    SciTech Connect

    Duley, W. W.; Hu, Anming E-mail: a2hu@uwaterloo.ca

    2012-12-20

    We report on the preparation of hydrogenated amorphous carbon nanoparticles whose spectral characteristics include an absorption band at 217.5 nm with the profile and characteristics of the interstellar 217.5 nm feature. Vibrational spectra of these particles also contain the features commonly observed in absorption and emission from dust in the diffuse interstellar medium. These materials are produced under ''slow'' deposition conditions by minimizing the flux of incident carbon atoms and by reducing surface mobility. The initial chemistry leads to the formation of carbon chains, together with a limited range of small aromatic ring molecules, and eventually results in carbon nanoparticles having an sp {sup 2}/sp {sup 3} ratio Almost-Equal-To 0.4. Spectroscopic analysis of particle composition indicates that naphthalene and naphthalene derivatives are important constituents of this material. We suggest that carbon nanoparticles with similar composition are responsible for the appearance of the interstellar 217.5 nm band and outline how these particles can form in situ under diffuse cloud conditions by deposition of carbon on the surface of silicate grains. Spectral data from carbon nanoparticles formed under these conditions accurately reproduce IR emission spectra from a number of Galactic sources. We provide the first detailed fits to observational spectra of Type A and B emission sources based entirely on measured spectra of a carbonaceous material that can be produced in the laboratory.

  1. Heterogeneous polymer modification: Polyolefin maleation in supercritical carbon dioxide and amorphous fluoropolymer surface modification

    NASA Astrophysics Data System (ADS)

    Hayes, Heather J.

    1999-11-01

    Three distinct heterogeneous polymer modification reactions are explored in this work. The first is a bulk reaction commonly conducted on polyolefins---the free radical addition of maleic anhydride. This reaction was run using supercritical carbon dioxide (SC CO2) as the solvent. The second was the chemical surface modification of an amorphous fluorocopolymer of tetrafluoroethylene and a perfluorodioxole monomer (Teflon AF). Several reactions were explored to reduce the surface of the fluorocopolymer for the enhancement of wettability. The last modification was also on Teflon AF and involved the physical modification of the surface through the transport polymerization of xylylene in order to synthesize a novel bilayer membrane. The bulk maleation of poly-4-methyl-1-pentene (PMP) was the focus of the first project. SC CO2 was utilized as both solvent and swelling agent to promote this heterogeneous reaction and led to successful grafting of anhydride groups on both PMP and linear low density polyethylene. Varying the reaction conditions and reagent concentrations allowed optimization of the reaction. The grafted anhydride units were found to exist as single maleic and succinic grafts, and the PMP became crosslinked upon maleation. The surface of a fluoropolymer can be difficult to alter. An examination of three reactions was made to determine the reactivity of Teflon AF: sodium naphthalenide treatment (Na-Nap), aluminum metal modification through deposition and dissolution, and mercury/ammonia photosensitization. The fluorocopolymer with the lower perfluorodioxole percentage was found to be more reactive towards modification with the Na-Nap treatment. The other modification reactions appeared to be nearly equally reactive toward both fluorocopolymers. The functionality of the Na-Nap-treated surface was examined in detail with the use of several derivatization reactions. In the final project, an asymmetric gas separation membrane was synthesized using Teflon AF as

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