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Sample records for crystalline aluminosilicate zeolite

  1. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    DOEpatents

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-04-29

    A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  2. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    DOEpatents

    Nicholas, Christopher P; Boldingh, Edwin P

    2013-12-17

    A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  3. Granulation of zeolite-containing aluminosilicate hydrogel

    SciTech Connect

    Galimov, Z.F.; Vinkel'man, A.P.

    1987-09-01

    The granulation of aluminosilicate hydrogel as an intermediate for the synthesis of cracking catalysts was investigated from the standpoint of eliminating the splitting cone from the granulator and eliminating coagulation directly on the cone surface. A method for forming the gel without a cone was developed by dispersion of jets of sol issuing directly from the mixer. Gel quality was considerably higher in dispersions of time-constant jets of the sol. The experimental mixer can be used as a design basis for a multijet granulator with a capacity equivalent to one or several splitting cones in commercial units.

  4. Multipolar correlations between reactants in crystalline and semiamorphous zeolites

    SciTech Connect

    Mandeville, J.B.; Golub, J.; Kozak, J.J.

    1988-03-24

    The authors study the role of multipolar correlations in influencing the efficiency of reaction between a fixed target molecule and a diffusing coreactant in zeolites that exhibit both crystalline and semiamorphous structures. They focus on zeolite A and construct a geometrical model whose framework structure and attendant channel patterns have the same topology as the 26-hedral cavities of type I of this aluminosilicate. They consider reaction partners interacting via (attractiverepulsive) ion-ion, angle-averaged ion-dipole, and angle-averaged dipole-dipole potentials V(r), and by coupling the theory of finite Markov processes with a lattice version of the Debye-Smoluchowski theory of encounter-controlled reactions, they quantify the differences in the diffusion-controlled rate constant k/sub D/ for reactions taking place in crystalline regions of finite extent (rafts) versus those occurring in crystalline regions surrounded by an amorphous aluminosilicate structure. Calculations based on the model introduced in this paper suggest that much of the marked cation-exchange activity and catalytic activity of fully crystalline zeolites is already captured by semiamorphous zeolites containing raft structures having the spatial extent of those found in recent experimental work by Thomas and Bursill

  5. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    DOEpatents

    Nicholas, Christpher P; Boldingh, Edwin P

    2013-12-17

    A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and show to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hyrdocarbons into hydrocarbons removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  6. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    DOEpatents

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-10-07

    A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and shown to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub.1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  7. Predicting Large CO2 Adsorption in Aluminosilicate Zeolites for Postcombustion Carbon Dioxide Capture

    SciTech Connect

    Kim, J; Lin, LC; Swisher, JA; Haranczyk, M; Smit, B

    2012-11-21

    Large-scale simulations of aluminosilicate zeolites were conducted to identify structures that possess large CO2 uptake for postcombustion carbon dioxide capture. In this study, we discovered that the aluminosilicate zeolite structures with the highest CO2 uptake values have an idealized silica lattice with a large free volume and a framework topology that maximizes the regions with nearest-neighbor framework atom distances from 3 to 4.5 angstrom. These predictors extend well to different Si:Al ratios and for both Na+ and Ca2+ cations, demonstrating their universal applicability in identifying the best-performing aluminosilicate zeolite structures.

  8. Zeolites

    NASA Technical Reports Server (NTRS)

    1992-01-01

    Zeolites are crystalline aluminosilicates that have complex framework structures. However, there are several features of zeolite crystals that make unequivocal structure determinations difficult. The acquisition of reliable structural information on zeolites is greatly facilitated by the availability of high-quality specimens. For structure determinations by conventional diffraction techniques, large single-crystal specimens are essential. Alternatively, structural determinations by powder profile refinement methods relax the constraints on crystal size, but still require materials with a high degree of crystalline perfection. Studies conducted at CAMMP (Center for Advanced Microgravity Materials Processing) have demonstrated that microgravity processing can produce larger crystal sizes and fewer structural defects relative to terrestrial crystal growth. Principal Investigator: Dr. Albert Sacco

  9. Analysis of the biological and chemical reactivity of zeolite-based aluminosilicate fibers and particulates.

    PubMed Central

    Fach, Estelle; Waldman, W James; Williams, Marshall; Long, John; Meister, Richard K; Dutta, Prabir K

    2002-01-01

    Environmental and/or occupational exposure to minerals, metals, and fibers can cause lung diseases that may develop years after exposure to the agents. The presence of toxic fibers such as asbestos in the environment plus the continuing development of new mineral or vitreous fibers requires a better understanding of the specific physical and chemical features of fibers/particles responsible for bioactivity. Toward that goal, we have tested aluminosilicate zeolites to establish biological and chemical structure-function correlations. Zeolites have known crystal structure, are subject to experimental manipulation, and can be synthesized and controlled to produce particles of selected size and shape. Naturally occurring zeolites include forms whose biological activity is reported to range from highly pathogenic (erionite) to essentially benign (mordenite). Thus, we used naturally occurring erionite and mordenite as well as an extensively studied synthetic zeolite based on faujasite (zeolite Y). Bioactivity was evaluated using lung macrophages of rat origin (cell line NR8383). Our objective was to quantitatively determine the biological response upon interaction of the test particulates/fibers with lung macrophages and to evaluate the efficacy of surface iron on the zeolites to promote the Fenton reaction. The biological assessment included measurement of the reactive oxygen species by flow cytometry and chemiluminescence techniques upon phagocytosis of the minerals. The chemical assessment included measuring the hydroxyl radicals generated from hydrogen peroxide by iron bound to the zeolite particles and fibers (Fenton reaction). Chromatography as well as absorption spectroscopy were used to quantitate the hydroxyl radicals. We found that upon exposure to the same mass of a specific type of particulate, the oxidative burst increased with decreasing particle size, but remained relatively independent of zeolite composition. On the other hand, the Fenton reaction

  10. Secondary Ion Mass Spectrometry of Zeolite Materials: Observation of Abundant Aluminosilicate Oligomers Using an Ion Trap

    SciTech Connect

    Groenewold, Gary Steven; Kessinger, Glen Frank; Scott, Jill Rennee; Gianotto, Anita Kay; Appelhans, Anthony David; Delmore, James Edward

    2000-12-01

    Oligomeric oxyanions were observed in the secondary ion mass spectra (SIMS) of zeolite materials. The oxyanions have the general composition AlmSinO2(m+n)H(m-1)- (m + n = 2 to 8) and are termed dehydrates. For a given mass, multiple elemental compositions are possible because (Al + H) is an isovalent and isobaric substitute for Si. Using 18 keV Ga+ as a projectile, oligomer abundances are low relative to the monomers. Oligomer abundance can be increased by using the polyatomic projectile ReO4- (~5 keV). Oligomer abundance can be further increased using an ion trap (IT-) SIMS; in this instrument, long ion lifetimes (tens of ms) and relatively high He pressure result in significant collisional stabilization and increased high-mass abundance. The dehydrates rapidly react with adventitious H2O present in the IT-SIMS to form mono-, di-, and trihydrates. The rapidity of the reaction and comparison to aluminum oxyanion hydration suggest that H2O adds to the aluminosilicate oxyanions in a dissociative fashion, forming covalently bound product ions. In addition to these findings, it was noted that production of abundant oligomeric aluminosilicates could be significantly increased by substituting the countercation (NH4+) with the larger alkali ions Rb+ and Cs+. This constitutes a useful tactic for generating large aluminosilicate oligomers for surface characterization and ion-molecule reactivity studies.

  11. Zealous zeolites

    SciTech Connect

    Hairston, D.W.

    1996-07-01

    Zeolites have made significant inroads in fluid cracking catalysts for gasoline and have pushed phosphates out of laundry detergents. But these crystalline aluminosilicate structures are just beginning to make their mark in chemical processes and environmental applications. Ideally suited for work as molecular sieves and catalysts, zeolites sport uniform surface pores and channels that are receptive only to molecules of a specific size and shape. This high selectivity makes zeolites a good alterative to some of the conventional products used for chemical reaction and filtration. One of the most potentially lucrative markets for zeolites is chemical catalyst replacements for liquid acids, such as hydrofluoric acid and sulfuric acid, and aluminum chloride in a number of alkylation and acrylation reactions. Zeolites are also being considered for oligomerization,isomerization, amination and condensation processes for the manufacture of chemical intermediates. The paper discusses the market and manufacturers of zeolites, justifying the cost of converting to zeolite catalysts, and natural zeolites.

  12. Ordered hexagonal mesoporous aluminosilicates synthesized using zeolite as precursor and the wall-thickness tuned by pH control

    NASA Astrophysics Data System (ADS)

    Wang, Chunlei; Zhu, Guangshang; Shang, Tiecun; Cai, Xiaohui; Liu, Chengzhan; Li, Nan; Wei, Yuhong; Li, Jian; Zhang, Weiwei; Qiu, Shilun

    2005-07-01

    High aluminium content mesoporous aluminosilicates MAS-X1 and MAS-X3 have been successfully synthesized using zeolite FAU-X as precursors and triblock copolymer pluronic P123 as structure directing agent. Samples have been characterized by XRD, TEM, nitrogen adsorption/desorption, 27Al MAS NMR, and ICP element analysis techniques. The salt, NaCl, which was introduced by dissolving the zeolite FAU-X, played an important role in the synthesis of high order sample. The secondary growth of the wall was considered to occur after the pH value had been increased up to five.

  13. The role of water in the elastic properties of aluminosilicate zeolites: DFT investigation.

    PubMed

    Bryukhanov, Ilya A; Rybakov, Andrey A; Larin, Alexander V; Trubnikov, Dmitry N; Vercauteren, Daniel P

    2017-03-01

    The bulk and Young moduli and heats of hydration have been calculated at the DFT level for fully optimized models of all-siliceous and cationic zeolites with and without water, and then compared to the corresponding experimental data. Upon the addition of water, the monovalent alkali ion and divalent alkaline earth ion exchanged zeolites presented opposite trends in the elastic modulus. The main contribution to the decrease in the elastic modulus of the alkali ion exchanged zeolites appeared to be a shift of cations from the framework oxygen atoms upon water addition, with the coordination number often remaining the same. The contrasting increase in elastic modulus observed for the divalent (alkaline earth) ion exchanged zeolites was explained by cation stabilization resulting from increased coordination, which cannot be achieved within a rigid zeolite framework without water.

  14. Characterization of Aluminosilicate Formation on the Surface of a Crystalline Silicotitanate Ion Exchanger

    SciTech Connect

    Young, James S.; Su, Yali; Li, Liyu; Balmer, M Lou; G W Bailey

    2001-10-30

    Millions of gallons of high-level radioactive waste are contained in underground tanks at U.S. Department of Energy sites such as Hanford and Savannah River. Most of the radioactivity is due to 137Cs and 90Sr, which must be extracted in order to concentrate the waste. An ion exchanger, crystalline silicotitanate IONSIV IE911, is being considered for separation for Cs at the Savannah River Site (SRS). While the performance of this ion exchanger has been well characterized under normal operating conditions, Cs removal at slightly elevated temperatures, such as those that may occur in a process upset, is not clear. Our recent study indicates that during exposure to SRS simulant at 55 degrees Celsius and 80 degrees Celsius, an aluminosilicate coating formed on the exchanger surface. There was concern that the coating would affect its ion exchange properties. A LEO 982 field emission scanning electron microscope (FESEM) and an Oxford ISIS energy dispersive x-ray spectrometer (EDS) were used to characterize the coating.

  15. Poorly Crystalline, Iron-Bearing Aluminosilicates and Their Importance on Mars

    NASA Technical Reports Server (NTRS)

    Baker, L. L.; Strawn, D. G.; McDaniel, P. A.; Nickerosn, R. N.; Bishop, J. L.; Ming, D. W.; Morris, Richard V.

    2011-01-01

    Martian rocks and sediments contain weathering products including evaporite salts and clay minerals that only form as a result of interaction between rocks and water [1-6]. These weathering products are key to studying the history of water on Mars because their type, abundance and location provide clues to past conditions on the surface of the planet, as well as to the possible location of present-day reservoirs of water. Weathering of terrestrial volcanic rocks similar to those on Mars produces nano-sized, variably hydrated aluminosilicate and iron oxide minerals [7-10] including allophane, imogolite, halloysite, hisingerite, and ferrihydrite. The nanoaluminosilicates can contain isomorphically substituted Fe, which affects their spectral and physical properties. Detection and quantification of such minerals in natural environments on earth is difficult due to their variable chemical composition and lack of long-range crystalline order [9, 11, 12]. Despite the difficulty in characterizing these materials, they are common on Earth, and data from orbital remote sensing and rover-based instruments suggest that they are also present on Mars [9, 10, 13-17]. Their accurate detection and quantification require a better understanding of how composition affects their spectral properties. We present here the results of XAFS spectroscopy; these results will be corroborated with planned Mossbauer and reflectance spectroscopy.

  16. Seed-Assisted Synthesis of MWW-Type Zeolite with Organic Structure-Directing Agent-Free Na-Aluminosilicate Gel System.

    PubMed

    Kamimura, Yoshihiro; Itabashi, Keiji; Kon, Yoshihiro; Endo, Akira; Okubo, Tatsuya

    2017-03-02

    The seed-assisted synthesis of zeolites without using organic structure-directing agents (OSDAs) has enabled alternative routes to the simple, environmentally friendly and low-cost production of industrially important zeolites. In this study, the successful seed-assisted synthesis of MCM-22 (MWW-type) zeolite with an OSDA-free gel is reported for the first time. MWW-type zeolites are obtained by the addition of as-synthesized MCM-22 seeds prepared with hexamethyleneimine (HMI) into OSDA-free Na-aluminosilicate gels. Based on the results of XRD, ICP-AES, NMR, N2 physisorption and NH3 -TPD, the product exhibited different features compared to those of the seeds. The H-form product can serve as a catalyst in Friedel-Crafts alkylation reaction of anisole with 1-phenylethanol, and its catalytic activity is comparable to the seeds. Furthermore, XRD, FE-SEM, TG-DTA, CHN, FT-IR and NMR analyses of products and intermediates provide insights into the role of seeds and occluded HMI, the crystallization process, and key factors for achieving seed-assisted synthesis of MWW-type zeolites with an OSDA-free gel system. The present results provide a new perspective for the economical and environmentally friendly production of MWW-type zeolites.

  17. Immobilization of Cs and Sr in aluminosilicate matrices derived from natural zeolites

    NASA Astrophysics Data System (ADS)

    Cappelletti, Piergiulio; Rapisardo, Gianmarco; de Gennaro, Bruno; Colella, Abner; Langella, Alessio; Graziano, Sossio Fabio; Bish, David Lee; de Gennaro, Maurizio

    2011-07-01

    Three Italian zeolitized volcanoclastic deposits with predominant phillipsite, chabazite or clinoptilolite were selected to investigate their attitude to form ceramized products of the Cs- and Sr-enriched forms and to evaluate the effectiveness of immobilization by means of leaching tests. The mineralogical evolution was carefully followed after thermal treatments at increasing temperatures (800 °C up to 1100 °C) which led to the crystallization of prevailing pollucite for Cs-exchanged phillipsite and chabazite and of a Sr-feldspar (about 35 wt.%) along with cristobalite and amorphous matter for all Sr-exchanged zeolites. Cs-enriched clinoptilolite at the same temperature was almost totally amorphous. Leaching tests confirm the substantial immobilization of the polluting cations in the ceramized materials with slight higher values only for the Cs-enriched clinoptilolite, mostly amorphous. Finally, calorimetric tests account for a hydrolysis process widely decreasing after thermal treatments at 1100 °C for phillipsite and chabazite, both Cs- and Sr-enriched, substantially similar for Sr-enriched clinoptilolite and definitely increased in the prevailing amorphous Cs-enriched clinoptilolite.

  18. The Chemistry, Crystallization, Physicochemical Properties and Behavior of Sodium Aluminosilicate Solid Phases: Final Report

    SciTech Connect

    Rosencrance, S.

    2003-03-12

    The synthesis of sodium aluminosilicate solids phases precipitated from NO{sub 2}/NO{sub 3}-free and NO{sub 2}/NO{sub 3}-rich liquors has been performed. Four sodium aluminosilicate precipitation products were formed. These are (1) X-ray/electron diffraction-indifferent amorphous phase; (2) crystalline zeolite A; (3)NO{sub 2}/NO{sub 3}-rich crystalline sodalite; and (4) NO{sub 2}/NO{sub 3}-rich crystalline cancrinite phase. Characterization of the physicochemical properties for these phases has been performed under conditions simulating Westinghouse Savannah River Company liquid waste processing.

  19. One-pot synthesis of hierarchical FeZSM-5 zeolites from natural aluminosilicates for selective catalytic reduction of NO by NH3

    PubMed Central

    Yue, Yuanyuan; Liu, Haiyan; Yuan, Pei; Yu, Chengzhong; Bao, Xiaojun

    2015-01-01

    Iron-modified ZSM-5 zeolites (FeZSM-5s) have been considered to be a promising catalyst system to reduce nitrogen oxide emissions, one of the most important global environmental issues, but their synthesis faces enormous economic and environmental challenges. Herein we report a cheap and green strategy to fabricate hierarchical FeZSM-5 zeolites from natural aluminosilicate minerals via a nanoscale depolymerization-reorganization method. Our strategy is featured by neither using any aluminum-, silicon-, or iron-containing inorganic chemical nor involving any mesoscale template and any post-synthetic modification. Compared with the conventional FeZSM-5 synthesized from inorganic chemicals with the similar Fe content, the resulting hierarchical FeZSM-5 with highly-dispersed iron species showed superior catalytic activity in the selective catalytic reduction of NO by NH3. PMID:25791958

  20. One-pot synthesis of hierarchical FeZSM-5 zeolites from natural aluminosilicates for selective catalytic reduction of NO by NH3

    NASA Astrophysics Data System (ADS)

    Yue, Yuanyuan; Liu, Haiyan; Yuan, Pei; Yu, Chengzhong; Bao, Xiaojun

    2015-03-01

    Iron-modified ZSM-5 zeolites (FeZSM-5s) have been considered to be a promising catalyst system to reduce nitrogen oxide emissions, one of the most important global environmental issues, but their synthesis faces enormous economic and environmental challenges. Herein we report a cheap and green strategy to fabricate hierarchical FeZSM-5 zeolites from natural aluminosilicate minerals via a nanoscale depolymerization-reorganization method. Our strategy is featured by neither using any aluminum-, silicon-, or iron-containing inorganic chemical nor involving any mesoscale template and any post-synthetic modification. Compared with the conventional FeZSM-5 synthesized from inorganic chemicals with the similar Fe content, the resulting hierarchical FeZSM-5 with highly-dispersed iron species showed superior catalytic activity in the selective catalytic reduction of NO by NH3.

  1. Growth of zeolite crystals in the microgravity environment of space

    NASA Technical Reports Server (NTRS)

    Sacco, A., Jr.; Sand, L. B.; Collette, D.; Dieselman, K.; Crowley, J.; Feitelberg, A.

    1986-01-01

    Zeolites are hydrated, crystalline aluminosilicates with alkali and alkaling earth metals substituted into cation vacancies. Typically zeolite crystals are 3 to 8 microns. Larger cyrstals are desirable. Large zeolite crystals were produced (100 to 200 microns); however, they have taken restrictively long times to grow. It was proposed if the rate of nucleation or in some other way the number of nuclei can be lowered, fewer, larger crystals will be formed. The microgravity environment of space may provide an ideal condition to achieve rapid growth of large zeolite crystals. The objective of the project is to establish if large zeolite crystals can be formed rapidly in space.

  2. Microsphere zeolite materials derived from coal fly ash cenospheres as precursors to mineral-like aluminosilicate hosts for 135,137Cs and 90Sr

    NASA Astrophysics Data System (ADS)

    Vereshchagina, Tatiana A.; Vereshchagin, Sergei N.; Shishkina, Nina N.; Vasilieva, Nataly G.; Solovyov, Leonid A.; Anshits, Alexander G.

    2013-06-01

    Hollow microsphere zeolite materials with a bilayered zeolite/glass crystalline shell bearing NaP1 zeolite were synthesized by the hydrothermal treatment of coal fly ash cenospheres (Si/Al = 2.7) in an alkaline medium. Cs+ and/or Sr2+ forms of zeolitized cenospheres with the different Cs+ and/or Sr2+ loading were prepared by the ion exchange from nitrate solutions. The resulted (Cs,Na)P1, (Sr,Na)P1 and (Cs,Sr,Na)P1 bearing microsphere zeolites were converted to glass ceramics by heating at 900-1000 °C. The differential scanning calorimetry and quantitative phase analysis were used to monitor the solid-phase transformation of the initial and ion exchanged zeolite materials. It was established that the final solidified forms of Cs+ and/or Sr2+ are glass-crystalline ceramic materials based on pollucite-nepheline, Sr-feldspar-nepheline and Sr-feldspar-pollucite composites including ˜60 wt.% of the major host phases (pollucite, Sr-feldspar) and 10-20 wt.% of glass. The 137Cs leaching rate of 4.1 × 10-7 g cm-2 day-1 was determined for the pollucite glass-ceramic according to Russian State Standard (GOST) No. 52126 P-2003 (7 day, 25 °C, distilled water).

  3. Iridium Complexes and Clusters in Dealuminated Zeolite HY: Distribution between Crystalline and Impurity Amorphous Regions

    SciTech Connect

    Martinez-Macias, Claudia; Xu, Pinghong; Hwang, Son-Jong; Lu, Jing; Chen, Cong-Yan; Browning, Nigel D.; Gates, Bruce C.

    2014-07-08

    Dealuminated zeolite HY was used to support Ir(CO)2 complexes formed from Ir(CO)2(C5H7O2). Infrared and X-ray absorption spectra and atomic-resolution electron microscopy images identify these complexes, and the images and 27Al NMR spectra identify impurity amorphous regions in the zeolite where the iridium is more susceptible to aggregation than in the crystalline regions. The results indicate a significant stability limitation of metal in amorphous impurity regions of zeolites.

  4. Influence of starting zeolite on synthesis of RUT type zeolite by interzeolite conversion method

    NASA Astrophysics Data System (ADS)

    Itakura, Masaya; Ota, Kai; Shibata, Shohei; Inoue, Takayuki; Ide, Yusuke; Sadakane, Masahiro; Sano, Tsuneji

    2011-01-01

    In this study, hydrothermal conversions of *BEA and FAU type zeolites using various structure-directing agents were carried out. Highly crystalline and pure RUT type zeolites were obtained from both zeolites in the presence of tetramethylammonium hydroxide. There were no major differences between the characteristics of the RUT type zeolites obtained from the two starting zeolites. However, the Si/Al ratio and the crystallization rate of the RUT type zeolites were strongly dependent on both the framework structure and the Si/Al ratio of the starting zeolite. That is, the crystallization rate of the RUT type zeolite from the *BEA type zeolite did not depend on the Si/Al ratio of the starting *BEA type zeolite, whereas the crystallization rate of the RUT type zeolite from the FAU type zeolite was dependent on the Si/Al ratio of the starting FAU type zeolite. This suggests that the chemical structure and the concentration of locally ordered aluminosilicate species produced by the decomposition/dissolution of the starting zeolite can be altered by changing the framework structure of the zeolite.

  5. Feasible conversion of solid waste bauxite tailings into highly crystalline 4A zeolite with valuable application

    SciTech Connect

    Ma, Dongyang; Wang, Zhendong; Guo, Min; Zhang, Mei; Liu, Jingbo

    2014-11-15

    Highlights: • Concept to convert waste to valuable product is carried out in this study. • An industrially feasible and cost-effective approach was developed and optimized. • Highly crystalline and well-defined zeolite was produced under moderate conditions. • The zeolite derived from the bauxite tailings displayed high ion exchange capacity. • Bauxite tailings have potential application in heavy metal ions adsorbent. - Abstract: Bauxite tailings are a major type of solid wastes generated in the flotation process. The waste by-products caused significant environmental impact. To lessen this hazardous effect from poisonous mine tailings, a feasible and cost-effective solution was conceived and implemented. Our approach focused on reutilization of the bauxite tailings by converting it to 4A zeolite for reuse in diverse applications. Three steps were involved in the bauxite conversion: wet-chemistry, alkali fusion, and crystallization to remove impurities and to prepare porous 4A zeolite. It was found that the cubic 4A zeolite was single phase, in high purity, with high crystallinity and well-defined structure. Importantly, the 4A zeolite displayed maximum calcium ion exchange capacity averaged at 296 mg CaCO{sub 3}/g, comparable to commercially-available zeolite (310 mg CaCO{sub 3}/g) exchange capacity. Base on the optimal synthesis condition, the reaction yield of zeolite 4A from bauxite tailings achieved to about 38.43%, hence, this study will provide a new paradigm for remediation of bauxite tailings, further mitigating the environmental and health care concerns, particularly in the mainland of PR China.

  6. Comparing the activity of aluminum in two B horizons developed from volcanic ash deposits in Japan, dominated by short-range ordered aluminosilicates and crystalline clay minerals, respectively

    NASA Astrophysics Data System (ADS)

    Yagasaki, Yasumi; Mulder, Jan; Okazaki, Masanori

    2006-01-01

    Mechanisms controlling the activity of free aluminum (Al) in Bw1 horizons of soils developed from volcanic ash deposits in Japan were investigated by means of acid-base titrations and kinetic studies. In a Bw1 horizon, with a high content of acid-oxalate extractable Al, soil solution reached equilibrium with short-range ordered aluminosilicates in the order of days. Relatively fast kinetics of the release and precipitation of Al and Si indicate a high reactivity of short-range ordered aluminosilicates in the soil. In the Bw1 horizon of an adjacent soil, with a high content of crystalline clay minerals like halloysite and interlayered vermiculite, solution remained well undersaturated with respect to short-range ordered aluminosilicates and aluminum hydroxide. Apparent equilibrium with respect to halloysite occurred after more than 30 days. This halloysite ( logKso0=3.74±0.02 (25 °C)) has a solubility that is less than that reported in the literature ( logKso0=4.36 (25°C)). Our findings suggest that different reactive aluminosilicates may control the activity of free Al in sub-surface horizons of volcanic ash soils with different mineralogy.

  7. Feasible conversion of solid waste bauxite tailings into highly crystalline 4A zeolite with valuable application.

    PubMed

    Ma, Dongyang; Wang, Zhendong; Guo, Min; Zhang, Mei; Liu, Jingbo

    2014-11-01

    Bauxite tailings are a major type of solid wastes generated in the flotation process. The waste by-products caused significant environmental impact. To lessen this hazardous effect from poisonous mine tailings, a feasible and cost-effective solution was conceived and implemented. Our approach focused on reutilization of the bauxite tailings by converting it to 4A zeolite for reuse in diverse applications. Three steps were involved in the bauxite conversion: wet-chemistry, alkali fusion, and crystallization to remove impurities and to prepare porous 4A zeolite. It was found that the cubic 4A zeolite was single phase, in high purity, with high crystallinity and well-defined structure. Importantly, the 4A zeolite displayed maximum calcium ion exchange capacity averaged at 296 mg CaCO3/g, comparable to commercially-available zeolite (310 mg CaCO3/g) exchange capacity. Base on the optimal synthesis condition, the reaction yield of zeolite 4A from bauxite tailings achieved to about 38.43%, hence, this study will provide a new paradigm for remediation of bauxite tailings, further mitigating the environmental and health care concerns, particularly in the mainland of PR China.

  8. π-π interaction of aromatic groups in amphiphilic molecules directing for single-crystalline mesostructured zeolite nanosheets.

    PubMed

    Xu, Dongdong; Ma, Yanhang; Jing, Zhifeng; Han, Lu; Singh, Bhupendra; Feng, Ji; Shen, Xuefeng; Cao, Fenglei; Oleynikov, Peter; Sun, Huai; Terasaki, Osamu; Che, Shunai

    2014-06-24

    One of the challenges in material science has been to prepare macro- or mesoporous zeolite. Although examples of their synthesis exist, there is a need for a facile yet versatile approach to such hierarchical structures. Here we report a concept for designing a single quaternary ammonium head amphiphilic template with strong ordered self-assembling ability through π-π stacking in hydrophobic side, which stabilizes the mesostructure to form single-crystalline mesostructured zeolite nanosheets. The concept is demonstrated for the formation of a new type of MFI (zeolite framework code by International Zeolite Association) nanosheets joined with a 90° rotational boundary, which results in a mesoporous zeolite with highly specific surface area even after calcination. Low binding energies for this self-assembling system are supported by a theoretical analysis. A geometrical matching between the arrangement of aromatic groups and the zeolitic framework is speculated for the formation of single-crystalline MFI nanosheets.

  9. SSZ-52, a zeolite with an 18-layer aluminosilicate framework structure related to that of the DeNOx catalyst Cu-SSZ-13.

    PubMed

    Xie, Dan; McCusker, Lynne B; Baerlocher, Christian; Zones, Stacey I; Wan, Wei; Zou, Xiaodong

    2013-07-17

    A new zeolite (SSZ-52, |(C14H28N)6Na6(H2O)18|[Al12Si96O216]), related to the DeNOx catalyst Cu-SSZ-13 (CHA framework type), has been synthesized using an unusual polycyclic quaternary ammonium cation as the structure-directing agent. By combining X-ray powder diffraction (XPD), high-resolution transmission electron microscopy (HRTEM) and molecular modeling techniques, its porous aluminosilicate framework structure (R3m, a = 13.6373(1) Å, c = 44.7311(4) Å), which can be viewed as an 18-layer stacking sequence of hexagonally arranged (Si,Al)6O6 rings (6-rings), has been elucidated. The structure has a three-dimensional 8-ring channel system and is a member of the ABC-6 family of zeolites (those that can be described in terms of 6-ring stacking sequences) like SSZ-13, but it has cavities that are twice as large. The code SFW has been assigned to this new framework type. The large cavities contain pairs of the bulky organic cations. HRTEM and XPD simulations show that stacking faults do occur, but only at the 5-10% level. SSZ-52 has considerable potential as a catalyst in the areas of gas conversion and sequestration.

  10. Results of Aluminosilicate Formation Testing

    SciTech Connect

    Wilmarth, W.R.

    2001-09-11

    The purpose of this work was to examine several experimental parameters of the formation of aluminosilicates under several tank chemistries, examine the conversion of crystalline phases, and determine inherent solubilities of certain crystal phases.

  11. Synthesis of Foam-Shaped Nanoporous Zeolite Material: A Simple Template-Based Method

    ERIC Educational Resources Information Center

    Saini, Vipin K.; Pires, Joao

    2012-01-01

    Nanoporous zeolite foam is an interesting crystalline material with an open-cell microcellular structure, similar to polyurethane foam (PUF). The aluminosilicate structure of this material has a large surface area, extended porosity, and mechanical strength. Owing to these properties, this material is suitable for industrial applications such as…

  12. Applications of natural zeolites on agriculture and food production.

    PubMed

    Eroglu, Nazife; Emekci, Mevlut; Athanassiou, Christos

    2017-03-14

    Zeolites are crystalline hydrated aluminosilicates with remarkable physical and chemical properties including losing and receiving water in a reverse way, adsorbing molecules that act as molecular sieves, and replacing their constituent cations without structural change. Commercial production of natural zeolites has accelerated during last fifty years. The Structure Commission of the International Zeolite Association recorded more than 200 zeolites which currently include more than 40 naturally occurring zeolites. Recent findings supported their role in stored-pest management as inert dust applications, pesticide and fertilizer carriers, soil amendments, animal feed additives, mycotoxin binders and food packaging materials. There are many advantages of inert dust application including low cost, non-neurotoxic action, low mammalian toxicity and safety for human consumption. Latest consumer trends and government protocols have shifted toward organic origin materials to replace synthetic chemical products. In the current review, we summarized most of the main uses of zeolites in food and agruculture, with specific paradigms that illustrate their important role.

  13. Crystalline zeolite composition (ECR-5) having a cancrinite-like structure and process for its preparation

    SciTech Connect

    Vaughan, D.E.

    1988-01-05

    This patent describes a crystalline zeolite, being isostructural to cancrinite, in which the twelve-ring channel has a sorption of greater than about 1% by weight hexane, the crystalline zeolite having a composition, in terms of mole ratios of oxides in the range: 1.0 to 1.3 Na/sub 2/:Al/sub 2/O/sub 3/:2.1 to 8.0 SiO/sub 2/. A process for preparing a crystalline zeolite having a composition, in terms of mole ratios of oxides, in the range: 1.0 to 1.3 Na/sub 2/O:Al/sub 2/O/sub 3/:2.1 to 8.0 SiO/sub 2/ and being isostructural to cancrinite, in which the twelve-ring channel thereof has a sorption of greater than about 1% by weight hexane, comprising the steps of: (a) preparing a reaction mixture comprising aqueous ammonia, a source of silica-alumina, and sodium hyroxide, the reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges: Na/sub 2/O:Al/sub 2/O/sub 3/:2 to 17; SiO/sub 2/:Al/sub 2/O/sub 3/:2 to 25; H/sub 2/O:Al/sub 2/:30 to 450; (H/sub 2/O + NH/sub 3/):Al/sub 2/O/sub 3/:50 to 600 wherein the ammonia is present in the reaction mixture in an amount of 15 to 30 percent, based on total moles of H/sub 2/O; and (b) maintaining the reaction mixture at a temperature between about 70/sup 0/ and 180/sup 0/C and for a time of about 1 to 10 days.

  14. Interface Induced Growth and Transformation of Polymer-Conjugated Proto-Crystalline Phases in Aluminosilicate Hybrids: A Multiple-Quantum (23)Na-(23)Na MAS NMR Correlation Spectroscopy Study.

    PubMed

    Brus, Jiri; Kobera, Libor; Urbanova, Martina; Doušová, Barbora; Lhotka, Miloslav; Koloušek, David; Kotek, Jiří; Čuba, Pavel; Czernek, Jiri; Dědeček, Jiří

    2016-03-22

    Nanostructured materials typically offer enhanced physicochemical properties because of their large interfacial area. In this contribution, we present a comprehensive structural characterization of aluminosilicate hybrids with polymer-conjugated nanosized zeolites specifically grown at the organic-inorganic interface. The inorganic amorphous Al-O-Si framework is formed by alkali-activated low-temperature transformation of metakaoline, whereas simultaneous copolymerization of organic comonomers creates a secondary epoxide network covalently bound to the aluminosilicate matrix. This secondary epoxide phase not only enhances the mechanical integrity of the resulting hybrids but also introduces additional binding sites accessible for compensating negative charge on the aluminosilicate framework. This way, the polymer network initiates growth and subsequent transformation of protocrystalline short-range ordered zeolite domains that are located at the organic-inorganic interface. By applying an experimental approach based on 2D (23)Na-(23)Na double-quantum (DQ) MAS NMR spectroscopy, we discovered multiple sodium binding sites in these protocrystalline domains, in which immobilized Na(+) ions form pairs or small clusters. It is further demonstrated that these sites, the local geometry of which allows for the pairing of sodium ions, are preferentially occupied by Pb(2+) ions during the ion exchange. The proposed synthesis protocol thus allows for the preparation of a novel type of geopolymer hybrids with polymer-conjugated zeolite phases suitable for capturing and storage of metal cations. The demonstrated (23)Na-(23)Na DQ MAS NMR combined with DFT calculations represents a suitable approach for understanding the role of Na(+) ions in aluminositicate solids and related inorganic-organic hybrids, particularly their specific arrangement and clustering at interfacial areas.

  15. [What a physician should know about zeolites].

    PubMed

    Boranić, M

    2000-01-01

    Zeolites are natural and synthetic hydrated crystalline aluminosilicates endowed with absorptive and ion exchange properties. They have found numerous and multifarous applications--in industry as catalysts and absorbents, in water sanitation for the removal of ammonia and heavy metals, in agriculture as fertilizers, and in animal husbandry as the absorbents of excreted material and as food additives. Medical applications have included the use in filtration systems for anesthesia or dialysis and as the contrast materials in NMR imaging. Recently, zeolite powders for external use have found application as deodorants, antimycotic agents and wound dressings. Peroral use of encapsulated zeolite powders enriched with vitamins, oligoelements or other ingredients has been claimed to exert beneficial medical effects. Ingestion of zeolites may be considered analogous to the clay eating (geophagia), considered in traditional medicine as a remedy for various illnesses. Being amphoteric, zeolites are partly soluble in acid or alkaline media, but within the physiological pH range the solubility is generally low. Minimal amounts of free aluminium or silicium from the ingested zeolites are resorbed from the gut. The bulk of ingested zeolite probably remains undissolved in the gut. In view of the ion exchange properties, zeolites may be expected to change the ionic content, pH and buffering capacity of the gastrointestinal secretions and to affect the transport through the intestinal epithelium. In addition, zeolites could affect the bacterial flora and the resorption of bacterial products, vitamins and oligoelements. The contact of zeolite particles with gastrointestinal mucosa may elicit the secretion of cytokines with local and systemic actions. Reactive silicium ions might react with biomolecules of the intestinal epithelium, and if resorbed, do so in other cells. Mutagenic and carcinogenic effects of zeolite particles have been described, resembling such effects of asbestos

  16. Nuclear Magnetic Resonance Studies of Aluminosilicate Gels Prepared in High-Alkaline and Salt-Concentrated Solutions

    SciTech Connect

    Wang, Li Q.; Mattigod, Shas V.; Parker, Kent E.; Hobbs, David T.; McCready, David E.

    2005-11-01

    Solid-state 29Si, 27Al, and 23Na MAS (magic angle spinning) NMR techniques in combination with x-ray powder diffraction (XRD) are used to characterize aluminosilicate gels as a function of composition, pH, and reaction times. These gels were prepared at 80 C using initial solutions with low Si/Al ratios, high alkaline and salt concentrations that are characteristic of nuclear tank wastes. XRD data show that cancrinite and sodalite are the main crystalline phases in the aluminosilicate gels produced. It is found that the pH and the salt content have significant effects on the nature of the aluminosilicate gels. Higher pH appears to increase the rate of crystallization, the degree of overall crystallinity and the percentage of cancrinite phases in aluminosilicate gels, whereas the high salt concentration promotes the formation of cancrinite and sodalite and prohibits the formation of other zeolites. Complementary to XRD, NMR is extremely useful for providing the information on the structure of amorphous intermediate gels with no long-range order.

  17. X-ray Excited Optical Fluorescence and Diffraction Imaging of Reactivity and Crystallinity in a Zeolite Crystal: Crystallography and Molecular Spectroscopy in One.

    PubMed

    Ristanović, Zoran; Hofmann, Jan P; Richard, Marie-Ingrid; Jiang, Tao; Chahine, Gilbert A; Schülli, Tobias U; Meirer, Florian; Weckhuysen, Bert M

    2016-06-20

    Structure-activity relationships in heterogeneous catalysis are challenging to be measured on a single-particle level. For the first time, one X-ray beam is used to determine the crystallographic structure and reactivity of a single zeolite crystal. The method generates μm-resolved X-ray diffraction (μ-XRD) and X-ray excited optical fluorescence (μ-XEOF) maps of the crystallinity and Brønsted reactivity of a zeolite crystal previously reacted with a styrene probe molecule. The local gradients in chemical reactivity (derived from μ-XEOF) were correlated with local crystallinity and framework Al content, determined by μ-XRD. Two distinctly different types of fluorescent species formed selectively, depending on the local zeolite crystallinity. The results illustrate the potential of this approach to resolve the crystallographic structure of a porous material and its reactivity in one experiment via X-ray induced fluorescence of organic molecules formed at the reactive centers.

  18. Zeolites US market to reach $1 billion by 2000

    SciTech Connect

    Morris, G.D.L.

    1997-02-05

    This article describes the growth of the U.S. market for zeolites, specifically sodium aluminosilicate. The largest application for zeolites is for petrochemical and petroleum catalysts; however, detergents are also a specific application addressed in the article.

  19. Sonochemical synthesis of zeolite NaP from clinoptilolite.

    PubMed

    Behin, Jamshid; Kazemian, Hossein; Rohani, Sohrab

    2016-01-01

    In the present work, natural clinoptilolite was converted to zeolite NaP using ultrasonic energy, in which the transformation time shortened remarkably. The effect of post-synthesis treatment using conventional hydrothermal was also investigated. The synthesized powders were characterized by XRD, TGA/DTA, SEM, and PSD analysis. The results showed that, increasing the sonication time (energy) has no significant effect on the product's morphology. The crystallinity of the synthesized samples increased slightly with increasing sonication time, but their yield remained relatively unchanged. Furthermore, post-synthesis hydrothermal treatment showed very little influence on properties of the final product. Because the ultrasonic irradiation creates acoustic cavitation cracks on the surface structure of clinoptilolite particulates and increases the concentration of soluble alumino-silicate species, which favors the prevailing super-saturation, crystallization and crystal growth of zeolite NaP happen faster. The particles of zeolite NaP synthesized by ultrasonic irradiation consist of small crystallites of uniform size.

  20. Synthesis strategies in the search for hierarchical zeolites.

    PubMed

    Serrano, D P; Escola, J M; Pizarro, P

    2013-05-07

    Great interest has arisen in the past years in the development of hierarchical zeolites, having at least two levels of porosities. Hierarchical zeolites show an enhanced accessibility, leading to improved catalytic activity in reactions suffering from steric and/or diffusional limitations. Moreover, the secondary porosity offers an ideal space for the deposition of additional active phases and for functionalization with organic moieties. However, the secondary surface represents a discontinuity of the crystalline framework, with a low connectivity and a high concentration of silanols. Consequently, hierarchical zeolites exhibit a less "zeolitic behaviour" than conventional ones in terms of acidity, hydrophobic/hydrophilic character, confinement effects, shape-selectivity and hydrothermal stability. Nevertheless, this secondary surface is far from being amorphous, which provides hierarchical zeolites with a set of novel features. A wide variety of innovative strategies have been developed for generating a secondary porosity in zeolites. In the present review, the different synthetic routes leading to hierarchical zeolites have been classified into five categories: removal of framework atoms, surfactant-assisted procedures, hard-templating, zeolitization of preformed solids and organosilane-based methods. Significant advances have been achieved recently in several of these alternatives. These include desilication, due to its versatility, dual templating with polyquaternary ammonium surfactants and framework reorganization by treatment with surfactant-containing basic solutions. In the last two cases, the materials so prepared show both mesoscopic ordering and zeolitic lattice planes. Likewise, interesting results have been obtained with the incorporation of different types of organosilanes into the zeolite crystallization gels, taking advantage of their high affinity for silicate and aluminosilicate species. Crystallization of organofunctionalized species favours the

  1. Evaluation of the Incorporation of Uranium into Sodium Aluminosilicate Phases

    SciTech Connect

    Oji, L.N.

    2003-03-26

    This report describes batch laboratory experiments performed to determine the relative amounts of uranium incorporated in aluminosilicate structures during synthesis. The findings summarized here are based on laboratory experiments, which involved the synthesis of sodium aluminosilicates (NAS) structures, amorphous, zeolites A and sodalite phases in the presence of depleted uranium and the analytical search for incorporated uranium in NAS internal structures after synthesis. These studies will support the basis for continued operation of evaporators at the Savannah River Site (SRS).

  2. Pure, single phase, high crystalline, chamfered-edge zeolite 4A synthesized from coal fly ash for use as a builder in detergents.

    PubMed

    Hui, K S; Chao, C Y H

    2006-09-01

    Single phase chamfered-edge zeolite 4A samples in pure form with a high crystallinity were synthesized by applying step-change of synthesis temperature during hydrothermal treatment of coal fly ash. The calcium binding capacity of these zeolite 4A samples (prepared from coal fly ash) and the commercial detergent grade zeolite 4A were tested for usage as a detergent builder. The results show that these zeolite 4A samples behaved similarly as the commercial one in removing calcium ions during the washing cycle. Moreover, from the leaching tests (evaluation of toxicological safety), the results show that these zeolite 4A samples leached the same elements (Sb, As, Se and Tl) as the commercial one with the concentrations in the same order of magnitude. This shows that the toxicological effect of the coal fly ash converted zeolite 4A was not worse than that of the commercial sample. Finally, economic and environmental aspects of converting coal fly ash to useful products were discussed.

  3. Removal of ammonia from poultry manure by aluminosilicates.

    PubMed

    Wlazło, Łukasz; Nowakowicz-Dębek, Bożena; Kapica, Jacek; Kwiecień, Małgorzata; Pawlak, Halina

    2016-12-01

    The aim of the study was to test the possibility of using aluminosilicates as natural sorbents of ammonia from poultry manure. The ammonia-absorbing properties of sodium bentonite and zeolite were confirmed in ex situ conditions. The most significant reduction in the level of ammonia with respect to the control was noted for 2% bentonite and 1% zeolite. The mean reduction for the entire period of the experiment ranged from 26.41% to 29.04%. The aluminosilicates tested can be used to neutralize ammonia released on poultry farms.

  4. X‐ray Excited Optical Fluorescence and Diffraction Imaging of Reactivity and Crystallinity in a Zeolite Crystal: Crystallography and Molecular Spectroscopy in One

    PubMed Central

    Ristanović, Zoran; Hofmann, Jan P.; Richard, Marie‐Ingrid; Jiang, Tao; Chahine, Gilbert A.; Schülli, Tobias U.; Meirer, Florian

    2016-01-01

    Abstract Structure–activity relationships in heterogeneous catalysis are challenging to be measured on a single‐particle level. For the first time, one X‐ray beam is used to determine the crystallographic structure and reactivity of a single zeolite crystal. The method generates μm‐resolved X‐ray diffraction (μ‐XRD) and X‐ray excited optical fluorescence (μ‐XEOF) maps of the crystallinity and Brønsted reactivity of a zeolite crystal previously reacted with a styrene probe molecule. The local gradients in chemical reactivity (derived from μ‐XEOF) were correlated with local crystallinity and framework Al content, determined by μ‐XRD. Two distinctly different types of fluorescent species formed selectively, depending on the local zeolite crystallinity. The results illustrate the potential of this approach to resolve the crystallographic structure of a porous material and its reactivity in one experiment via X‐ray induced fluorescence of organic molecules formed at the reactive centers. PMID:27145171

  5. X‐ray Excited Optical Fluorescence and Diffraction Imaging of Reactivity and Crystallinity in a Zeolite Crystal: Crystallography and Molecular Spectroscopy in One

    PubMed Central

    Ristanović, Zoran; Hofmann, Jan P.; Richard, Marie‐Ingrid; Jiang, Tao; Chahine, Gilbert A.; Schülli, Tobias U.; Meirer, Florian

    2016-01-01

    Abstract Structure–activity relationships in heterogeneous catalysis are challenging to be measured on a single‐particle level. For the first time, one X‐ray beam is used to determine the crystallographic structure and reactivity of a single zeolite crystal. The method generates μm‐resolved X‐ray diffraction (μ‐XRD) and X‐ray excited optical fluorescence (μ‐XEOF) maps of the crystallinity and Brønsted reactivity of a zeolite crystal previously reacted with a styrene probe molecule. The local gradients in chemical reactivity (derived from μ‐XEOF) were correlated with local crystallinity and framework Al content, determined by μ‐XRD. Two distinctly different types of fluorescent species formed selectively, depending on the local zeolite crystallinity. The results illustrate the potential of this approach to resolve the crystallographic structure of a porous material and its reactivity in one experiment via X‐ray induced fluorescence of organic molecules formed at the reactive centers. PMID:27478278

  6. Effect of ultrasound energy on the zeolitization of chemical extracts from fused coal fly ash.

    PubMed

    Bukhari, Syed Salman; Rohani, Sohrab; Kazemian, Hossein

    2016-01-01

    This paper investigates the effects of ultrasound (UTS) energy at different temperatures on the zeolitization of aluminosilicate constituents of coal fly ash. UTS energy irradiated directly into the reaction mixture utilizing a probe immersed into the reaction mixture, unlike previously reported works that have used UTS baths. Controlled synthesis was also conducted at constant stirring and at the same temperatures using conventional heating. The precursor reaction solution was obtained by first fusing the coal fly ash with sodium hydroxide at 550°C followed by dissolution in water and filtration. The synthesized samples were characterized by XRF, XRD, SEM and TGA. The crystallinity of crystals produced with UTS assisted conversion compared to conventional conversion at 85°C was twice as high. UTS energy also reduced the induction time from 60 min to 40 min and from 80 min to 60 min for reaction temperatures of 95°C and 85°C, respectively. Prolonging the UTS irradiation at 95°C resulted in the conversion of zeolite-A crystals to hydroxysodalite, which is a more stable zeolitic phase. It was found that at 85°C coupled with ultrasound energy produced the best crystalline structure with a pure single phase of zeolite-A. It has been shown that crystallization using UTS energy can produce zeolitic crystals at lower temperatures and within 1h, dramatically cutting the synthesis time of zeolite.

  7. Pressure dependence of ionic conductivity of hydrated and dehydrated zeolites A

    NASA Astrophysics Data System (ADS)

    Goryainov, S. V.; Secco, R. A.; Huang, Y.; Liu, H.

    2007-03-01

    Hydrated and dehydrated zeolites MA (where M=Li, Na and K) with LTA structure have been studied by impedance spectroscopy with scanning frequency from 1 Hz to 1 MHz at high pressure up to 4.5 GPa and high temperature up to 250 °C. Anomalous increase in electrical AC conductivity at about 1.5-2 GPa observed in hydrated zeolites is associated with changes in crystalline structure leading to the formation of high-diffusion state of cation and water stuffing of the channels. In dehydrated zeolites, electrical conductivity is controlled by diffusion of cations (Li +, Na + and K +), which is determined by cation sites and aluminosilicate ring windows. LiA and NaA zeolites show normal decrease of conductivity with pressure, whereas KA zeolite exhibits the anomalous dependence with considerable increase and then fast decrease of conductivity. The behaviour of KA zeolite is associated with nearly central location of cation site in 8-membered ring, different from that in LiA and NaA zeolites.

  8. Zeolite membranes from kaolin

    SciTech Connect

    Karle, B.G.; Brinker, C.J. |; Phillips, M.L.F.

    1996-07-01

    Zeolite films are sought as components of molecular sieve membranes. Different routes used to prepare zeolite composite membranes include growing zeolite layers from gels on porous supports, depositing oriented zeolites on supports, and dispersing zeolites in polymeric membranes. In most cases, it is very difficult to control and avoid the formation of cracks and/or pinholes. The approach to membrane synthesis is based on hydrothermally converting films of layered aluminosilicates into zeolite films. The authors have demonstrated this concept by preparing zeolite A membranes on alumina supports from kaolin films. The authors have optimized the process parameters not only for desired bulk properties, but also for preparing thin (ca. 5 {micro}m), continuous zeolite A films. Scanning electron microscopy shows highly intergrown zeolite A crystals over most of the surface area of the membrane, but gas permeation experiments indicate existence of mesoporous defects and/or intercrystalline gaps. It has been demonstrated that the thickness of the final zeolite A membrane can be controlled by limiting the amount of precursor kaolin present in the membrane.

  9. Hot isostatically-pressed aluminosilicate glass-ceramic with natural crystalline analogues for immobilizing the calcined high-level nuclear waste at the Idaho Chemical Processing Plant

    SciTech Connect

    Raman, S.

    1993-12-01

    The additives Si, Al, MgO, P{sub 2}O{sub 5} were mechanically blended with fluorinelsodium calcine in varying proportions. The batches were vacuum sealed in stainless steel canisters and hot isostatically pressed at 20,000 PSI and 1000 C for 4 hours. The resulting suite of glass-ceramic waste forms parallels the natural rocks in microstructural and compositional heterogeneity. Several crystalline phases ar analogous in composition and structure to naturally occurring minerals. Additional crystalline phases are zirconia and Ca-Mg borate. The glasses are enriched in silica and alumina. Approximately 7% calcine elements occur dissolved in this glass and the total glass content in the waste forms averages 20 wt%. The remainder of the calcine elements are partitioned into crystalline phases at 75 wt% calcine waste loading. The waste forms were tested for chemical durability in accordance with the MCC1-test procedure. The leach rates are a function of the relative proportions of additives and calcine, which in turn influence the composition and abundances of the glass and crystalline phases. The DOE leach rate criterion of less than 1 g/m{sup 2}-day is met by all the elements B, Cs and Na are increased by lowering the melt viscosity. This is related to increased crystallization or devitrification with increases in MgO addition. This exploratory work has shown that the increases in waste loading occur by preferred partitioning of the calcine components among crystalline and glass phases. The determination of optimum processing parameters in the form of additive concentration levels, homogeneous blending among the components, and pressure-temperature stabilities of phases must be continued to eliminate undesirable effects of chemical composition, microstructure and glass devitrification.

  10. Alkaline cations directing the transformation of FAU zeolites into five different framework types.

    PubMed

    Van Tendeloo, Leen; Gobechiya, Elena; Breynaert, Eric; Martens, Johan A; Kirschhock, Christine E A

    2013-12-28

    Exposure of faujasite zeolites to different alkali hydroxide solutions readily yields zeolites with ABW, CHA, MER and ANA topologies. In NaOH faujasite persisted. Aside from new opportunities for zeolite synthesis, this reveals that a suitable aluminosilicate connectivity in the source material significantly facilitates zeolite crystallization.

  11. Microprobes aluminosilicate ceramic membranes

    DOEpatents

    Anderson, Marc A.; Sheng, Guangyao

    1993-01-01

    Methods have been developed to make mixed alumina-silicate and aluminosilicate particulate microporous ceramic membranes. One method involves the making of separate alumina and silica sols which are then mixed. Another method involves the creation of a combined sol with aluminosilicate particles. The resulting combined alumina and silica membranes have high surface area, a very small pore size, and a very good temperature stability.

  12. Tailored crystalline microporous materials by post-synthesis modification.

    PubMed

    Valtchev, Valentin; Majano, Gerardo; Mintova, Svetlana; Pérez-Ramírez, Javier

    2013-01-07

    Crystalline microporous solids are an important class of inorganic materials with uses in different areas impacting our everyday lives, namely as catalysts, adsorbents, and ion exchangers. Advancements in synthesis have been invaluable in expanding the classical aluminosilicate zeolites to new unique framework types and compositions, motivating innovative developments. However, the inexhaustible post-synthetic options to tailor zeolite properties have been and will continue to be indispensable to realize emerging and to improve conventional applications. Starting from the routine drying and template removal processes that every zeolite must experience prior to use, a wide spectrum of treatments exists to alter individual or collective characteristics of these materials for optimal performance. This review documents the toolbox of post-synthetic strategies available to tune the properties of zeolitic materials for specific functions. The categorisation is based on the scale at which the alteration is aimed at, including the atomic structure (e.g. the introduction, dislodgment, or replacement of framework atoms), the micropore level (e.g. template removal and functionalisation by inorganic and organic species), and the crystal and particle levels (e.g. the introduction of auxiliary porosity). Through examples in the recent literature, it is shown that the combination of post-synthetic methods enables rational zeolite design, extending the characteristics of these materials way beyond those imposed by the synthesis conditions.

  13. Physical, Chemical and Structural Evolution of Zeolite-Containing Waste Forms Produced from Metakaolinite and Calcined Sodium Bearing Waste (HLW and/or LLW)

    SciTech Connect

    Grutzeck, Michael W.

    2005-06-27

    Zeolites are extremely versatile. They can adsorb liquids and gases and serve as cation exchange media. They occur in nature as well cemented deposits. The ancient Romans used blocks of zeolitized tuff as a building material. Using zeolites for the management of radioactive waste is not a new idea, but a process by which the zeolites can be made to act as a cementing agent is. Zeolitic materials are relatively easy to synthesize from a wide range of both natural and man-made substances. The process under study is derived from a well known method in which metakaolin (an impure thermally dehydroxylated kaolinite heated to {approx}700 C containing traces of quartz and mica) is mixed with sodium hydroxide (NaOH) and reacted in slurry form (for a day or two) at mildly elevated temperatures. The zeolites form as finely divided powders containing micrometer ({micro}m) sized crystals. However, if the process is changed slightly and only just enough concentrated sodium hydroxide solution is added to the metakaolinite to make a thick crumbly paste and then the paste is compacted and cured under mild hydrothermal conditions (60-200 C), the mixture will form a hard ceramic-like material containing distinct crystalline tectosilicate minerals (zeolites and feldspathoids) imbedded in an X-ray amorphous hydrated sodium aluminosilicate matrix. Due to its lack of porosity and vitreous appearance we have chosen to call this composite a ''hydroceramic''.

  14. Rapid synthesis of beta zeolites

    DOEpatents

    Fan, Wei; Chang, Chun -Chih; Dornath, Paul; Wang, Zhuopeng

    2015-08-18

    The invention provides methods for rapidly synthesizing heteroatom containing zeolites including Sn-Beta, Si-Beta, Ti-Beta, Zr-Beta and Fe-Beta. The methods for synthesizing heteroatom zeolites include using well-crystalline zeolite crystals as seeds and using a fluoride-free, caustic medium in a seeded dry-gel conversion method. The Beta zeolite catalysts made by the methods of the invention catalyze both isomerization and dehydration reactions.

  15. A Highly Ion-Selective Zeolite Flake Layer on Porous Membranes for Flow Battery Applications.

    PubMed

    Yuan, Zhizhang; Zhu, Xiangxue; Li, Mingrun; Lu, Wenjing; Li, Xianfeng; Zhang, Huamin

    2016-02-24

    Zeolites are crystalline microporous aluminosilicates with periodic arrangements of cages and well-defined channels, which make them very suitable for separating ions of different sizes, and thus also for use in battery applications. Herein, an ultra-thin ZSM-35 zeolite flake was introduced onto a poly(ether sulfone) based porous membrane. The pore size of the zeolite (ca. 0.5 nm) is intermediary between that of hydrated vanadium ions (>0.6 nm) and protons (<0.24 nm). The resultant membrane can thus be used to perfectly separate vanadium ions and protons, making this technology useful in vanadium flow batteries (VFB). A VFB with a zeolite-coated membrane exhibits a columbic efficiency of >99 % and an energy efficiency of >81 % at 200 mA cm(-2), which is by far the highest value ever reported. These convincing results indicate that zeolite-coated membranes are promising in battery applications.

  16. Spectroscopic studies of aluminosilicate formation in tank waste simulants

    SciTech Connect

    Su, Y.; Wang, L.; Bunker, B.C.; Windisch, C.F.

    1997-12-31

    Aluminosilicates are one of the major class of species controlling the volume of radioactive high-level waste that will be produced from future remediation at Hanford site. Here the authors present studies of the phases and structures of aluminosilicates as a function of sludge composition using X-ray powder diffraction, solid state {sup 27}Al and {sup 29}Si NMR, and Raman spectroscopy. The results show that the content of NaNO{sub 3} in solution has significant effects on the nature of the insoluble aluminosilicate phases produced. It was found that regardless of the initial Si:Al ratio, nitrate cancrinite was the main phase formed in the solution with pH of 13.5 and 5 M NaNO{sub 3}. However, at lower NaNO{sub 3} concentration with initial Si:Al ratios of 1.1, 2.2, and 11.0 in the solutions, a range of aluminosilicate zeolites was produced with Si:Al ratios of 1.1, 1.3, and 1.5, respectively. Lowering the solution pH appears to promote the formation of amorphous aluminosilicates. The results presented here are important for the prediction of the solubility and dissolution rate of Al in tank wastes.

  17. Zeolite A imidazolate frameworks

    NASA Astrophysics Data System (ADS)

    Hayashi, Hideki; Côté, Adrien P.; Furukawa, Hiroyasu; O'Keeffe, Michael; Yaghi, Omar M.

    2007-07-01

    Faujasite (FAU) and zeolite A (LTA) are technologically important porous zeolites (aluminosilicates) because of their extensive use in petroleum cracking and water softening. Introducing organic units and transition metals into the backbone of these types of zeolite allows us to expand their pore structures, enhance their functionality and access new applications. The invention of metal-organic frameworks and zeolitic imidazolate frameworks (ZIFs) has provided materials based on simple zeolite structures where only one type of cage is present. However, so far, no metal-organic analogues based on FAU or LTA topologies exist owing to the difficulty imposed by the presence of two types of large cage (super- and β-cages for FAU, α- and β-cages for LTA). Here, we have identified a strategy to produce an LTA imidazolate framework in which both the link geometry and link-link interactions play a decisive structure-directing role. We describe the synthesis and crystal structures of three porous ZIFs that are expanded analogues of zeolite A; their cage walls are functionalized, and their metal ions can be changed without changing the underlying LTA topology. Hydrogen, methane, carbon dioxide and argon gas adsorption isotherms are reported and the selectivity of this material for carbon dioxide over methane is demonstrated.

  18. Functionalized Amorphous Aluminosilicates

    NASA Astrophysics Data System (ADS)

    Mesgar, Milad

    Alkali treated aluminosilicate (geopolymer) was functionalized by surfactant to increase the hydrophobicity for making Pickering emulsion for the first part of this work. In the first part of this study, alkali treated metakaolin was functionalized with cetyltrimethylammonium bromide ((C16H33)N(CH 3)3Br, CTAB). The electrostatic interaction between this quaternary ammonium and the surface of the aluminosilicate which has negative charge has taken place. The particles then were used to prepare Pickering emulsion. The resulting stable dispersions, obtained very fast at very simple conditions with low ratio of aluminosilicate to liquid phase. In the second part, the interaction between geopolymer and glycerol was studied to see the covalent grafting of the geopolymer for making geopolymer composite. The composite material would be the basis material to be used as support catalyst, thin coating reagent and flame retardant material and so on, Variety of techniques, Thermogravimetric (TGA), Particle-induced X-ray emission (PIXE), FTIR, Solid state NMR, Powder X-ray diffraction (PXRD), BET surface area, Elemental analysis (CHN), TEM, SEM and Optical microscopy were used to characterize the functionalized geopolymer.

  19. Synthesis and characterization of aluminosilicate catalyst impregnated by nickel oxide

    NASA Astrophysics Data System (ADS)

    Maulida, Iffana Dani; Sriatun, Taslimah

    2015-09-01

    Aluminosilicate as a catalyst has been synthesized by pore-engineering using CetylTrimethylAmmonium-Bromide (CTAB) as templating agent. It can produce bigger aluminosilicate pore therefore it will be more suitable for bulky molecule. The aims of this research are to synthesize aluminosilicate supported by Nickel, using CTAB surfactant as templating agent for larger pore radius than natural zeolite and characterize the synthesis product, consist of total acid sites and surface area characteristic. This research has been done with following steps. First, making sodium silicate and sodium aluminate. Second, aluminosilicate was synthesized by direct methods, calcined at 550, 650 and 750°C variation temperature, characterized product by X-RD and FTIR spectrometer. Third, NiCl2 was impregnated to the aluminosilicate that has the best cristallinity and main TO4 functional groups product (550 sample). Variation of NiCl2:aluminosilicate (w/w) ratio were 25%:75%, 50%:50% and 75%:25%. Last but not least characterization of catalytic properties was performed. It comprised total acidity test (gravimetric method) and Surface Area Analyzer. The result shows that the product synthesized by direct method at 550oC calcination temperature has the best cristallinity and main functional groups of TO4. The highest total acid sites was 31.6 mmole/g (Imp-A sample). Surface Area Analyzer shows that Imp-B sample has the best pore distribution and highest total pore volume and specific surface area with value 32.424 cc/g and 46.8287 m2/g respectively. We can draw the conclusion that the most potential catalyst is Imp-A sample compared to Imp-B and Imp-C because it has the highest total acid sites. However the most effective catalyst used for product selectivity was Imp-B sample among all samples.

  20. Uranium and Aluminosilicate Surface Precipitation Tests

    SciTech Connect

    Hu, M.Z.

    2002-11-27

    The 2H evaporator at the Savannah River Site has been used to treat an aluminum-rich waste stream from canyon operations and a silicon-rich waste stream from the Defense Waste Processing Facility. The formation of aluminosilicate scale in the evaporator has caused significant operational problems. Because uranium has been found to accumulate in the aluminosilicate solids, the scale deposition has introduced criticality concerns as well. The objective of the tests described in this report is to determine possible causes of the uranium incorporation in the evaporator scale materials. The scope of this task is to perform laboratory experiments with simulant solutions to determine if (1) uranium can be deposited on the surfaces of various sodium aluminosilicate (NAS) forms and (2) aluminosilicates can form on the surfaces of uranium-containing solids. Batch experiments with simulant solutions of three types were conducted: (1) contact of uranium solutions/sols with NAS coatings on stainless steel surfaces, (2) contact of uranium solutions with NAS particles, and (3) contact of precipitated uranium-containing particles with solutions containing aluminum and silicon. The results show that uranium can be incorporated in NAS solids through encapsulation in bulk agglomerated NAS particles of different phases (amorphous, zeolite A, sodalite, and cancrinite) as well as through heterogeneous deposition on the surfaces of NAS coatings (amorphous and cancrinite) grown on stainless steel. The results also indicate that NAS particles can grow on the surfaces of precipitated uranium solids. Particularly notable for evaporator operations is the finding that uranium solids can form on existing NAS scale, including cancrinite solids. If NAS scale is present, and uranium is in sufficient concentration in solution to precipitate, a portion of the uranium can be expected to become associated with the scale. The data obtained to date on uranium-NAS affinity are qualitative. A necessary

  1. Properties and applications of zeolites.

    PubMed

    Rhodes, Christopher J

    2010-01-01

    Zeolites are aluminosilicate solids bearing a negatively charged honeycomb framework of micropores into which molecules may be adsorbed for environmental decontamination, and to catalyse chemical reactions. They are central to green-chemistry since the necessity for organic solvents is minimised. Proton-exchanged (H) zeolites are extensively employed in the petrochemical industry for cracking crude oil fractions into fuels and chemical feedstocks for other industrial processes. Due to their ability to perform cation-exchange, in which the cations that are originally present to counterbalance the framework negative charge may be exchanged out of the zeolite by cations present in aqueous solution, zeolites are useful as industrial water-softeners, in the removal of radioactive Cs+ and Sr2+ cations from liquid nuclear waste and in the removal of toxic heavy metal cations from groundwaters and run-off waters. Surfactant-modified zeolites (SMZ) find particular application in the co-removal of both toxic anions and organic pollutants. Toxic anions such as arsenite, arsenate, chromate, cyanide and radioactive iodide can also be removed by adsorption into zeolites that have been previously loaded with co-precipitating metal cations such as Ag+ and Pb2+ which form practically insoluble complexes that are contained within the zeolite matrix.

  2. Understanding the dissolution of zeolites.

    PubMed

    Hartman, Ryan L; Fogler, H Scott

    2007-05-08

    Scientific knowledge of how zeolites, a unique classification of microporous aluminosilicates, undergo dissolution in aqueous hydrochloric acid solutions is limited. Understanding the dissolution of zeolites is fundamental to a number of processes occurring in nature and throughout industry. To better understand the dissolution process, experiments were carried out establishing that the Si-to-Al ratio controls zeolite framework dissolution, by which the selective removal of aluminum constrains the removal of silicon. Stoichiometric dissolution is observed for Type 4A zeolite in HCl where the Si-to-Al ratio is equal to 1.0. Framework silicon dissolves completely during Type 4A dissolution and is followed by silicate precipitation. However, for the zeolite analcime which has a Si-to-Al ratio of 2.0 dissolves non-stoichiometrically as the selective removal of aluminum results in partially dissolved silicate particles followed by silicate precipitation. In Type Y zeolite, exhibiting a Si-to-Al ratio of 3.0, there is insufficient aluminum to weaken the structure and cause silicon to dissolve in HCl. Thus, little or no precipitation is observed, and amorphous undissolvable silicate particles remain intact. The initial dissolution rates of Type Y and 4A zeolites demonstrate that dissolution is constrained by the number of available reaction sites, and a selective removal rate parameter is applied to delineate the mechanism of particle dissolution by demonstrating the kinetic influence of the Si-to-Al ratio. Zeolite framework models are constructed and used to undergird the basic dissolution mechanism. The framework models, scanning electron micrographs of partially dissolved crystals, and experimentally measured dissolution rates all demonstrate that a zeolite's Si-to-Al framework ratio plays a universal role in the dissolution mechanism, independent of framework type. Consequently, the unique mechanism of zeolite dissolution has general implications on how petroleum

  3. Synthesis, structure, and carbon dioxide capture properties of zeolitic imidazolate frameworks.

    PubMed

    Phan, Anh; Doonan, Christian J; Uribe-Romo, Fernando J; Knobler, Carolyn B; O'Keeffe, Michael; Yaghi, Omar M

    2010-01-19

    Zeolites are one of humanity's most important synthetic products. These aluminosilicate-based materials represent a large segment of the global economy. Indeed, the value of zeolites used in petroleum refining as catalysts and in detergents as water softeners is estimated at $350 billion per year. A major current goal in zeolite chemistry is to create a structure in which metal ions and functionalizable organic units make up an integral part of the framework. Such a structure, by virtue of the flexibility with which metal ions and organic moieties can be varied, is viewed as a key to further improving zeolite properties and accessing new applications. Recently, it was recognized that the Si-O-Si preferred angle in zeolites (145 degrees ) is coincident with that of the bridging angle in the M-Im-M fragment (where M is Zn or Co and Im is imidazolate), and therefore it should be possible to make new zeolitic imidazolate frameworks (ZIFs) with topologies based on those of tetrahedral zeolites. This idea was successful and proved to be quite fruitful; within the last 5 years over 90 new ZIF structures have been reported. The recent application of high-throughput synthesis and characterization of ZIFs has expanded this structure space significantly: it is now possible to make ZIFs with topologies previously unknown in zeolites, in addition to mimicking known structures. In this Account, we describe the general preparation of crystalline ZIFs, discussing the methods that have been developed to create and analyze the variety of materials afforded. We include a comprehensive list of all known ZIFs, including structure, topology, and pore metrics. We also examine how complexity might be introduced into new structures, highlighting how link-link interactions might be exploited to effect particular cage sizes, create polarity variations between pores, or adjust framework robustness, for example. The chemical and thermal stability of ZIFs permit many applications, such as the

  4. Mineral resource of the month: natural and synthetic zeolites

    USGS Publications Warehouse

    Virta, Robert L.

    2008-01-01

    Volcanic rocks containing natural zeolites — hydrated aluminosilicate minerals that contain alkaline and alkaline-earth metals — have been mined worldwide for more than 1,000 years for use as cements and building stone. For centuries, people thought natural zeolites occurred only in small amounts inside cavities of volcanic rock. But in the 1950s and early 1960s, large zeolite deposits were discovered in volcanic tuffs in the western United States and in marine tuffs in Italy and Japan. And since then, similar deposits have been found around the world, from Hungary to Cuba to New Zealand. The discovery of these larger deposits made commercial mining of natural zeolite possible.

  5. Synthesis and testing of nanosized zeolite Y

    NASA Astrophysics Data System (ADS)

    Karami, Davood

    This work focuses on the synthesis and testing of nanosized zeolite Y. The synthesis formulations of faujasite-type structure of zeolite Y prepared in nanosized form are described. The synthetic zeolite Y is the most widely employed for the preparation of fluid catalytic cracking (FCC) catalysts. The synthesis of zeolite Y is very complicated process. The mean particle size of zeolite Y is 1800 nm. The major challenge of this work involved reducing this average particle size to less than 500 nm. The preliminary experiments were conducted to obtain the pure zeolite Y using the soluble silicates as a silica source. This was achieved by applying the experimental design approach to study the effects of many parameters. The ageing time turned out to be the most significant variable affecting product purity. Based on the preliminary results, a detailed investigation was carried out to determine the effects of silica-alumina precursor preparations on zeolite Y synthesis. Aluminosilicate precursors were prepared by gelling and precipitation of soluble silicate. The as-prepared precursors were used for the hydrothermal synthesis of zeolite Y. The procedure of the precipitation of soluble silicate yielded pure zeolite Y at the conventional synthesis conditions. The extent of purity of zeolite Y depends on the surface areas of aluminosilicate precursors. A novel approach to zeolite Y synthesis was employed for the preparation of the pure nanosized zeolite Y. This was achieved by applying the method of impregnation of precipitated silica. This novel method of impregnation for zeolite Y preparation allows eliminating the vigorous agitation step required for the preparation of a homogeneous silica solution, thereby simplifying the synthesis of zeolite Y in one single vessel. In case of the synthesis of nanosized zeolite Y, the effect of varying the organic templates on the formation of nanosized particles of zeolite Y was investigated, while all other reaction parameters were

  6. A new approach to evaluate natural zeolite ability to sorb lead (Pb) from aqueous solutions

    NASA Astrophysics Data System (ADS)

    Drosos, Evangelos I. P.; Karapanagioti, Hrissi K.

    2013-04-01

    Lead (Pb) is a hazardous pollutant commonly found in aquatic ecosystems. Among several methods available, the addition of sorbent amendments to soils or sediments is attractive, since its application is relatively simple, while it can also be cost effective when a low cost and re-usable sorbent is used; e.g. natural zeolites. Zeolites are crystalline aluminosilicates with a three-dimensional structure composed of a set of cavities occupied by large ions and water molecules. Zeolites can accommodate a wide variety of cations, such as Na+, K+, Ca2+, Mg2+, which are rather loosely held and can readily be exchanged for others in an aqueous solution. Natural zeolites are capable of removing cations, such as lead, from aqueous solutions by ion exchange. There is a wide variation in the cation exchange capacity (CEC) of natural zeolites because of the different nature of various zeolites cage structures, natural structural defects, adsorbed ions, and their associated gangue minerals. Naturally occurring zeolites are rarely pure and are contaminated to varying degrees by other minerals, such as clays and feldspars, metals, quartz, or other zeolites as well. These impurities affect the CEC even for samples originated from the same region but from a different source. CEC of the material increases with decreasing impurity content. Potentially exchangeable ions in such impurities do not necessarily participate in ion exchange mechanism, while, in some cases, impurities may additionally block the access to active sites. For zeoliferous rocks having the same percentage of a zeolitic phase, the CEC increases with decreasing Si/Al ratio, as the more Si ions are substituted by Al ions, the more negative the valence of the matrix becomes. Sodium seems to be the most effective exchangeable ion for lead. On the contrary, it is unlikely that the potassium content of the zeolite would be substituted. A pretreatment with high concentration solutions of Na, such as 2 M NaCl, can

  7. Synthesis of ‘unfeasible’ zeolites

    NASA Astrophysics Data System (ADS)

    Mazur, Michal; Wheatley, Paul S.; Navarro, Marta; Roth, Wieslaw J.; Položij, Miroslav; Mayoral, Alvaro; Eliášová, Pavla; Nachtigall, Petr; Čejka, Jiří; Morris, Russell E.

    2016-01-01

    Zeolites are porous aluminosilicate materials that have found applications in many different technologies. However, although simulations suggest that there are millions of possible zeolite topologies, only a little over 200 zeolite frameworks of all compositions are currently known, of which about 50 are pure silica materials. This is known as the zeolite conundrum—why have so few of all the possible structures been made? Several criteria have been formulated to explain why most zeolites are unfeasible synthesis targets. Here we demonstrate the synthesis of two such ‘unfeasible’ zeolites, IPC-9 and IPC-10, through the assembly-disassembly-organization-reassembly mechanism. These new high-silica zeolites have rare characteristics, such as windows that comprise odd-membered rings. Their synthesis opens up the possibility of preparing other zeolites that have not been accessible by traditional solvothermal synthetic methods. We envisage that these findings may lead to a step change in the number and types of zeolites available for future applications.

  8. The growth of zeolites A, X and mordenite in space

    NASA Technical Reports Server (NTRS)

    Sacco, Albert, Jr.; Bac, N.; Coker, E. N.; Dixon, A. G.; Warzywoda, J.; Thompson, R. W.

    1994-01-01

    Zeolites are a class of crystalline aluminosilicate materials that form the backbone of the chemical process industry worldwide. They are used primarily as adsorbents and catalysts and support to a significant extent the positive balance of trade realized by the chemical industry in the United States (around $19 billion in 1991). The magnitude of their efforts can be appreciated when one realizes that since their introduction as 'cracking catalysts' in the early 1960's, they have saved the equivalent of 60 percent of the total oil production from Alaska's North Slope. Thus the performance of zeolite catalysts can have a profound effect on the U.S. economy. It is estimated that a 1 percent increase in yield of the gasoline fraction per barrel of oil would represent a savings of 22 million barrels of crude oil per year, representing a reduction of $400 million in the United States' balance of payments. Thus any activity that results in improvement in zeolite catalyst performance is of significant scientific and industrial interest. In addition, due to their 'stability,' uniformity, and, within limits, their 'engineerable' structures, zeolites are being tested as potential adsorbents to purify gases and liquids at the parts-per-billion levels needed in today's electronic, biomedical, and biotechnology industries and for the environment. Other exotic applications, such as host materials for quantum-confined semiconductor atomic arrays, are also being investigated. Because of the importance of this class of material, extensive efforts have been made to characterize their structures and to understand their nucleation and growth mechanisms, so as to be able to custom-make zeolites for a desired application. To date, both the nucleation mechanics and chemistry (such as what are the 'key' nutrients) are, as yet, still unknown for many, if not all, systems. The problem is compounded because there is usually a 'gel' phase present that is assumed to control the degree of

  9. Crystalline Membranes

    NASA Technical Reports Server (NTRS)

    Tsapatsis, Michael (Inventor); Lai, Zhiping (Inventor)

    2008-01-01

    In certain aspects, the invention features methods for forming crystalline membranes (e.g., a membrane of a framework material, such as a zeolite) by inducing secondary growth in a layer of oriented seed crystals. The rate of growth of the seed crystals in the plane of the substrate is controlled to be comparable to the rate of growth out of the plane. As a result, a crystalline membrane can form a substantially continuous layer including grains of uniform crystallographic orientation that extend through the depth of the layer.

  10. Characterization of Uranium Solids Precipitated with Aluminosilicates

    SciTech Connect

    DUFF, MC

    2004-01-09

    At the Savannah River Site (SRS), the High-Level Waste (HLW) Tank Farms store and process high-level liquid radioactive wastes from the Canyons and recycle water from the Defense Waste Processing Facility. The waste is concentrated using evaporators to minimize the volume of space required for HLW storage. Recently, the 2H Evaporator was shutdown due to the crystallization of sodium aluminosilicate (NAS) solids (such as cancrinite and sodalite) that contained close to 10 weight percent of elementally-enriched uranium (U). Prior to extensive cleaning,the evaporator deposits resided on the evaporator walls and other exposed internal surfaces within the evaporator pot. Our goal is to support the basis for the continued safe operation of SRS evaporators and to gain more information that could be used to help mitigate U accumulation during evaporator operation. To learn more about the interaction between U(VI) and NAS in HLW salt solutions, we performed several fundamental studies to examine the mechanisms of U accumulation with NAS in highly caustic solutions. This larger group of studies focused on the following processes: co-precipitation/structural incorporation, sorption, and precipitation (with or without NAS), which will be reviewed in this presentation. We will present and discuss local atomic structural characterization data about U that has been co-precipitated with NAS solids (such as amorphous zeolite precursor material and sodalite) using X-ray absorption fine-structure (XAFS) spectroscopic techniques.

  11. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  12. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium aluminosilicate. 182.2727 Section 182.2727...) SUBSTANCES GENERALLY RECOGNIZED AS SAFE Anticaking Agents § 182.2727 Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance. This substance is generally recognized...

  13. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sodium aluminosilicate. 182.2727 Section 182.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  14. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  15. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium aluminosilicate. 182.2727 Section 182.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  16. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  17. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  18. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium aluminosilicate. 182.2727 Section 182.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  19. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  20. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Sodium aluminosilicate. 182.2727 Section 182.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  1. Amorphous and nanostructured silica and aluminosilicate spray-dried microspheres

    NASA Astrophysics Data System (ADS)

    Todea, M.; Turcu, R. V. F.; Frentiu, B.; Tamasan, M.; Mocuta, H.; Ponta, O.; Simon, S.

    2011-08-01

    Amorphous silica and aluminosilicate microspheres with diameters in the 0.1-20 μm range were produced by spray drying method. SEM, TEM and AFM images showed the spherical shape of the obtained particles. Based on thermal analysis data, several heat treatments have been applied on the as-prepared samples in order to check the amorphous state stability of the microspheres and to develop nanosized crystalline phases. As-prepared microspheres remain amorphous up to 1400 °C. By calcination at 1400 °C, cristobalite type nanocrystals are developed on silica sample, while in aluminosilicate sample first are developed mullite type nanocrystals and only after prolonged treatment are developed also cristobalite type nanocrystals. 29Si and 27Al MAS NMR results show that the local order around aluminum and silicon atoms strongly depend on the thermal history of the microspheres.

  2. Reclaiming silver from silver zeolite

    SciTech Connect

    Reimann, G.A.

    1991-10-01

    Silver zeolite is used to capture radioiodines from air cleaning systems in some nuclear facilities at the Idaho National Engineering Laboratory. It may become radioactively contaminated and/or poisoned by hydrocarbon vapors, which diminishes its capacity for iodine. Silver zeolite contains up to 38 wt% silver. A pyrometallurgical process was developed to reclaim the silver before disposing of the unserviceable zeolite as a radioactive waste. A flux was formulated to convert the refractory aluminosilicate zeolite structure into a low-melting fluid slag, with Na{sub 2}O added as NAOH instead of Na{sub 2}CO{sub 3} to avoid severe foaming due to CO{sub 2} evolution. A propane-fired furnace was built to smelt 45 kg charges at 1300C in a carbon-bonded silicon carbide crucible. A total of 218 kg (7000 tr oz) of silver was reclaimed from 1050 kg of unserviceable zeolite. Silver recoveries of 97% were achieved, and the radioisotopes were fixed as stable silicates in a vitreous slag that was disposed of as a low level waste. Recovered silver was refined using oxygen and cast into 100 tr oz bars assaying 99.8+% silver and showing no radioactive contamination.

  3. Reclaiming silver from silver zeolite

    SciTech Connect

    Reimann, G.A.

    1991-10-01

    Silver zeolite is used to capture radioiodines from air cleaning systems in some nuclear facilities at the Idaho National Engineering Laboratory. It may become radioactively contaminated and/or poisoned by hydrocarbon vapors, which diminishes its capacity for iodine. Silver zeolite contains up to 38 wt% silver. A pyrometallurgical process was developed to reclaim the silver before disposing of the unserviceable zeolite as a radioactive waste. A flux was formulated to convert the refractory aluminosilicate zeolite structure into a low-melting fluid slag, with Na[sub 2]O added as NAOH instead of Na[sub 2]CO[sub 3] to avoid severe foaming due to CO[sub 2] evolution. A propane-fired furnace was built to smelt 45 kg charges at 1300C in a carbon-bonded silicon carbide crucible. A total of 218 kg (7000 tr oz) of silver was reclaimed from 1050 kg of unserviceable zeolite. Silver recoveries of 97% were achieved, and the radioisotopes were fixed as stable silicates in a vitreous slag that was disposed of as a low level waste. Recovered silver was refined using oxygen and cast into 100 tr oz bars assaying 99.8+% silver and showing no radioactive contamination.

  4. Binding and catalytic reduction of NO by transition metal aluminosilicates

    SciTech Connect

    Klier, K.; Herman, R.G.; Hou, Shaolie.

    1991-09-01

    The objective of this research is to provide the scientific understanding of processes that actively and selectively reduce NO in dilute exhaust streams, as well as in concentrated streams, to N{sub 2}. Experimental studies of NO chemistry in transition metal-containing aluminosilicate catalysts are being carried out with the aim of determining the chemical rules for NO reduction on non-precious metals. The catalyst supports chosen for this investigation are A and Y zeolites, mordenite, and monoliths based on cordierite. The supported transition metal cations that were examined are principally the first row redox metals, e.g. Cr(2), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Cu(I). The reactions of interest are the reductions of NO by H{sub 2}, CO, and CH{sub 4}, as well as the disproportionation of NO. Rare earth cations that possess redox properties were placed in the more shielded sites, e.g. Site I in Y zeolite, prior to or simultaneously with the exchange procedure with the transition metal cations. Theoretical calculations of the electronic structure of the transition metal cations in zeolitic sites were carried out by ab initio methods. The aim of this part of the research is to find the best match between the metal-based antibonding orbitals and the antibonding orbitals of the NO molecule such that the N-O bond is weakened and is readily broken. 9 refs., 4 figs., 3 tabs.

  5. An IR Study of Benzoyl Chloride Adsorbed on KA, NaA, and CaA Zeolites

    NASA Astrophysics Data System (ADS)

    Bardakçı, B.; Bahçeli, Semiha

    2005-09-01

    Infrared spectroscopy has been used to investigate the adsorption of liquid benzoyl chloride on A-type zeolites. The data show that at room temperature the Fermi resonance phenomenon occurs in the adsorption on KA, NaA and CaA zeolites which are little acidic aluminosilicates.

  6. Crystallization Kinetics of Calcium-magnesium Aluminosilicate (CMAS) Glass

    NASA Technical Reports Server (NTRS)

    Wiesner, Valerie L.; Bansal, Narottam P.

    2015-01-01

    The crystallization kinetics of a calcium-magnesium aluminosilicate (CMAS) glass with composition relevant for aerospace applications, like air-breathing engines, were evaluated using differential thermal analysis (DTA) in powder and bulk forms. Activation energy and frequency factor values for crystallization of the glass were evaluated. X-ray diffraction (XRD) was used to investigate the onset of crystallization and the phases that developed after heat treating bulk glass at temperatures ranging from 690 to 960 deg for various times. Samples annealed at temperatures below 900 deg remained amorphous, while specimens heat treated at and above 900 deg exhibited crystallinity originating at the surface. The crystalline phases were identified as wollastonite (CaSiO3) and aluminum diopside (Ca(Mg,Al) (Si,Al)2O6). Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were employed to examine the microstructure and chemical compositions of crystalline phases formed after heat treatment.

  7. Zeolitic Boron Imidazolate Frameworks**

    PubMed Central

    Zhang, Jian; Wu, Tao; Zhou, Cong; Chen, Shumei; Feng, Pingyun; Bu, Xianhui

    2009-01-01

    From porous AlPO4 to porous BIFs Reported here are a family of crystalline materials based on boron imidazolate frameworks (BIFs). It is demonstrated that the synthetic method, which is based on the crosslinking of various pre-synthesized boron imidazolates by monovalent cations (Li+ and Cu+), is capable of generating a large variety of open frameworks ranging from the 4-connected zeolitic sodalite type to the 3-connected chiral (10,3)-a type. PMID:19241428

  8. Conventional hydrothermal synthesis of Na-A zeolite from cupola slag and aluminum sludge.

    PubMed

    Anuwattana, Rewadee; Khummongkol, Pojanie

    2009-07-15

    Na-A type zeolites were prepared from two industrial wastes: the solid by-product of cupola slag and aluminum sludge from an aluminum plating plant. Two preparation methods using the same starting material compositions were carried out. In the first method, alkaline fusion was introduced, followed by the hydrothermal treatment to obtain sodium aluminosilicate which was then crystallized in NaOH solution under the condition of 90+/-3 degrees C for 1-9h with different H(2)O/SiO2 ratios. The result shows that higher H(2)O/SiO2 ratio increases the rate of crystallization. The largest amount of crystallinity for Na-A was found at 3h. In the second method, alkaline hydrothermal treatment without fusion was carried out in the same condition as the first method. No Na-A zeolite was obtained by this method. The changes of the dissolved amounts of Si(4+) and Al(3+) in 3M NaOH were investigated during the hydrothermal reaction.

  9. Towards a sustainable manufacture of hierarchical zeolites.

    PubMed

    Verboekend, Danny; Pérez-Ramírez, Javier

    2014-03-01

    Hierarchical zeolites have been established as a superior type of aluminosilicate catalysts compared to their conventional (purely microporous) counterparts. An impressive array of bottom-up and top-down approaches has been developed during the last decade to design and subsequently exploit these exciting materials catalytically. However, the sustainability of the developed synthetic methods has rarely been addressed. This paper highlights important criteria to ensure the ecological and economic viability of the manufacture of hierarchical zeolites. Moreover, by using base leaching as a promising case study, we verify a variety of approaches to increase reactor productivity, recycle waste streams, prevent the combustion of organic compounds, and minimize separation efforts. By reducing their synthetic footprint, hierarchical zeolites are positioned as an integral part of sustainable chemistry.

  10. Aluminosilicate Precipitation Impact on Uranium

    SciTech Connect

    WILMARTH, WILLIAM

    2006-03-10

    Experiments have been conducted to examine the fate of uranium during the formation of sodium aluminosilicate (NAS) when wastes containing high aluminate concentrations are mixed with wastes of high silicate concentration. Testing was conducted at varying degrees of uranium saturation. Testing examined typical tank conditions, e.g., stagnant, slightly elevated temperature (50 C). The results showed that under sub-saturated conditions uranium is not removed from solution to any large extent in both simulant testing and actual tank waste testing. This aspect was not thoroughly understood prior to this work and was necessary to avoid criticality issues when actual tank wastes were aggregated. There are data supporting a small removal due to sorption of uranium on sites in the NAS. Above the solubility limit the data are clear that a reduction in uranium concentration occurs concomitant with the formation of aluminosilicate. This uranium precipitation is fairly rapid and ceases when uranium reaches its solubility limit. At the solubility limit, it appears that uranium is not affected, but further testing might be warranted.

  11. Synthesis of novel perfluoroalkylglucosides on zeolite and non-zeolite catalysts.

    PubMed

    Nowicki, Janusz; Mokrzycki, Łukasz; Sulikowski, Bogdan

    2015-04-08

    Perfluoroalkylglucosides comprise a very important class of fluorine-containing surfactants. These compounds can be synthesized by using the Fisher reaction, starting directly from glucose and the required perfluoroalcohols. We wish to report on the use of zeolite catalysts of different structure and composition for the synthesis of perfluoroalkylglucosides when using glucose and 1-octafluoropentanol as substrates. Zeolites of different pore architecture have been chosen (ZSM-5, ZSM-12, MCM-22 and Beta). Zeolites were characterized by XRD, nitrogen sorption, scanning electron microscopy (SEM) and solid-state 27Al MAS NMR spectroscopy. The activity of the zeolite catalysts in the glycosidation reaction was studied in a batch reactor at 100 °C below atmospheric pressure. The performance of zeolites was compared to other catalysts, an ion-exchange resin (Purolite) and a montmorillonite-type layered aluminosilicate. The catalytic performance of zeolite Beta was the highest among the zeolites studied and the results were comparable to those obtained over Purolite and montmorillonite type catalysts.

  12. Mesoporosity--a new dimension for zeolites.

    PubMed

    Möller, Karin; Bein, Thomas

    2013-05-07

    Frameworks of precisely defined pores with diameters matching the size of small molecules endow crystalline zeolites with valuable size- and shape-selectivity. Being important selective adsorbers and separators, zeolites are also indispensable as solid acids in size-selective catalysis. However, despite being extremely beneficial, micropores impose restrictions on the mass transport of reactants, especially when bulky molecules are involved. The prospect to boost the catalytic power of zeolites and to extend their applications into new areas has prompted numerous efforts to synthesize mesoporous zeolitic materials that combine diffusional pathways on two different size scales. Our tutorial review will introduce the reader to this exciting recent development in zeolite science. We will give a general overview of the diverse strategies on how to implement a secondary pore system in zeolites. We will distinguish top-down from bottom-up and template-assisted from 'template-free' procedures. Advantages and limitations of the different methods will also be addressed.

  13. Removal of ammonia nitrogen from distilled old landfill leachate by adsorption on raw and modified aluminosilicate.

    PubMed

    Couto, Rafael Schirmer de Paula; Oliveira, Aline Faria; Guarino, Alcides Wagner Serpa; Perez, Daniel Vidal; Marques, Mônica Regina da Costa

    2017-04-01

    This study aimed to evaluate the ammonia-nitrogen removal by aluminosilicates, using both standard solutions as pretreated landfill leachate. Three types of commercial clays and one commercial zeolite were initially tested using standard solution; however, only one clay with the best removability and the zeolite were tested with pretreated leachate. The chosen clay sorption capacity with the standard solution reached 83%, while with the pretreated leachate solution has reached 95% and zeolites have reached, respectively, a removal of 73% and 81%. For this two adsorbents' studies of equilibrium and kinetic of the sorption were also performed. The Langmuir model was more adequate to describe the ion exchange equilibrium and the sorption mechanism fit the pseudo-second-order kinetic model. Moreover, the pretreatment used on leachate proved to be essential not only for ammonium detection in solution, but also to facilitate its sorption in aluminosilicates. This alternative of ammonia-nitrogen removal also generates a product derived from treatment that can be used as agricultural feedstock in the form of fertilizer.

  14. Surface and interface investigation of aluminosilicate biomaterial by the “in vivo” experiments

    NASA Astrophysics Data System (ADS)

    Oudadesse, H.; Derrien, A. C.; Martin, S.; Chaair, H.; Cathelineau, G.

    2008-11-01

    Porous mixtures of aluminosilicate/calcium phosphate have been studied for biomaterials applications. Aluminosilicates formed with an inorganic polymeric constitution present amorphous zeolites because of their 3D network structure and present the ability to link to bone matrix. Amorphous geopolymers of the potassium-poly(sialate)-nanopolymer type were synthesised at low temperature and studied for their use as potential biomaterials. They were mixed with 13% weight of calcium phosphate like biphasic hydroxyapatite and β-tricalcium phosphate. In this study, " in vivo" experiments were monitored to evaluate the biocompatibility, the surface and the interface behaviour of these composites when used as bone implants. Moreover, it has been demonstrated using histological and physicochemical studies that the developed materials exhibited a remarkable bone bonding when implanted in a rabbit's thighbone for a period of 1 month. The easy synthesis conditions (low temperature) of this composite and the fast intimate links with bone constitute an improvement of synthetic bone graft biomaterial.

  15. A new approach to the determination of atomic-architecture of amorphous zeolite precursors by high-energy X-ray diffraction technique.

    PubMed

    Wakihara, Toru; Kohara, Shinji; Sankar, Gopinathan; Saito, Seijiro; Sanchez-Sanchez, Manuel; Overweg, Arian R; Fan, Wei; Ogura, Masaru; Okubo, Tatsuya

    2006-01-14

    The structure of amorphous precursor species formed under hydrothermal conditions, prior to the onset of crystallization of microporous aluminosilicate zeolites, is determined employing high-energy X-ray diffraction (HEXRD). The investigation, combined with the use of reverse Monte Carlo modelling suggests that even numbered rings, especially 4R (R: ring) and 6R, which are the dominant aluminosilicate rings in zeolite A, have already been produced in the precursor. The model implies that the formation of double 4Rs occurs at the final step of the crystallization of zeolite A.

  16. PHYSICAL, CHEMICAL AND STRUCTURAL EVOLUTIION OF ZEOLITE-CONTAINING WASTE FORMS PRODUCED FROM METAKAOLINITE AND CALCINED SODUIM BEARING WASTE (HLW AND/OR LLW)

    SciTech Connect

    Grutzeck, Michael W.

    2004-06-10

    Zeolites are extremely versatile. They can adsorb liquids and gases and serve as cation exchange media. They occur in nature as well cemented deposits. The Romans used blocks of zeolitized tuff as a building material. Using zeolites for the management of radioactive waste is not new, but a process by which the zeolites can be made to act as a cementing agent is. Zeolitic materials are relatively easy to synthesize from a wide range of both natural and man-made precursors. The process under study is derived from a well known method in which metakaolin (thermally dehydroxylated kaolin a mixture of kaolinite and smaller amounts of quartz and mica that has been heated to {approx}700 C) is mixed with sodium hydroxide (NaOH) and water and reacted in slurry form (for a day or two) at mildly elevated temperatures. The zeolites form as finely divided powders containing micrometer ({micro}m) sized crystals. However, if the process is changed slightly and just enough concentrated sodium hydroxide solution is added to the metakaolinite to make a thick paste and then the paste is cured under mild hydrothermal conditions (60-200 C), the mixture forms a concrete-like ceramic material made up of distinct crystalline tectosilicate minerals (zeolites and feldspathoids) imbedded in an X-ray amorphous hydrated sodium aluminosilicate matrix. Due to its vitreous character we have chosen to call this composite a ''hydroceramic''. Similar to zeolite powders, a hydroceramic is able to sequester cations in both lattice positions and within the channels and voids present in its tectosilicate framework structure. It can also accommodate a wide range of salt molecules (e.g., sodium nitrate) within these same openings thus rendering them insoluble. Due to its fine crystallite size and cementing character, the matrix develops significant physical strength. The obvious similarities between a hydroceramic waste form and a waste form based on solidified Portland cement grout are only superficial

  17. Regenerative Cu/La zeolite supported desulfurizing sorbents

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E. (Inventor); Sharma, Pramod K. (Inventor)

    1991-01-01

    Efficient, regenerable sorbents for removal of H2S from fluid hydrocarbons such as diesel fuel at moderate condition comprise a porous, high surface area aluminosilicate support, suitably a synthetic zeolite, and most preferably a zeolite having a free lattice opening of at least 6 Angstroms containing from 0.1 to 0.5 moles of copper ions, lanthanum ions or their mixtures. The sorbent removes sulfur from the hydrocarbon fuel in high efficiency and can be repetitively regenerated without loss of activity.

  18. Synthesis, Structure, and Carbon Dioxide Capture Properties of Zeolitic Imidazolate Frameworks

    SciTech Connect

    Phan, Anh; Doonan, Christian J.; Uribe-Romo, Fernando J.; Knobler, Carolyn B.; O’Keeffe, Michael; Yaghi, Omar M.

    2010-01-19

    Zeolites are one of humanity’s most important synthetic products. These aluminosilicate-based materials represent a large segment of the global economy. Indeed, the value of zeolites used in petroleum refining as catalysts and in detergents as water softeners is estimated at $350 billion per year. A major current goal in zeolite chemistry is to create a structure in which metal ions and functionalizable organic units make up an integral part of the framework. Such a structure, by virtue of the flexibility with which metal ions and organic moieties can be varied, is viewed as a key to further improving zeolite properties and accessing new applications. Recently, it was recognized that the Si-O-Si preferred angle in zeolites (145°) is coincident with that of the bridging angle in the M-Im-M fragment (where M is Zn or Co and Im is imidazolate), and therefore it should be possible to make new zeolitic imidazolate frameworks (ZIFs) with topologies based on those of tetrahedral zeolites. This idea was successful and proved to be quite fruitful; within the last 5 years over 90 new ZIF structures have been reported. The recent application of high-throughput synthesis and characterization of ZIFs has expanded this structure space significantly: it is now possible to make ZIFs with topologies previously unknown in zeolites, in addition to mimicking known structures. In this Account, we describe the general preparation of crystalline ZIFs, discussing the methods that have been developed to create and analyze the variety of materials afforded. We include a comprehensive list of all known ZIFs, including structure, topology, and pore metrics. We also examine how complexity might be introduced into new structures, highlighting how link-link interactions might be exploited to effect particular cage sizes, create polarity variations between pores, or adjust framework robustness, for example. The chemical and thermal stability of ZIFs permit many applications, such as the

  19. Preparation and characterization of zeolitic membrane

    SciTech Connect

    Shuanshi Fan; Chunhua Li; Jinqu Wang

    1994-12-31

    Zeolites with less than 10 {angstrom} pores are desirable membrane materials, due to their crystallinity, resistance to high temperature, and chemical inertness. Although several works have been done on them, zeolitic membranes have not been developed so perfect at present. In this paper, the authors reported the preparation and some properties of an asymmetric zeolitic membrane synthesized by hydrothermal process on the intermediate layer which was made on a porous ceramic support, meanwhile the results of separation of ethanol-water mixture on pervaporation were discussed.

  20. Dissolution and Separation of Aluminum and Aluminosilicates

    SciTech Connect

    McFarlane, Joanna; Benker, Dennis; DePaoli, David W.; Felker, Leslie Kevin; Mattus, Catherine H.

    2015-12-19

    The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as a function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.

  1. Dissolution and Separation of Aluminum and Aluminosilicates

    DOE PAGES

    McFarlane, Joanna; Benker, Dennis; DePaoli, David W.; ...

    2015-12-19

    The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as amore » function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.« less

  2. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium calcium aluminosilicate, hydrated. 182.2729... § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  3. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium calcium aluminosilicate, hydrated. 182.2729... (CONTINUED) SUBSTANCES GENERALLY RECOGNIZED AS SAFE Anticaking Agents § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium...

  4. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729... Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  5. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium calcium aluminosilicate, hydrated. 182.2729... § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  6. Imprinting the surface of mesoporous aluminosilicates using organic structure-directing agents

    NASA Astrophysics Data System (ADS)

    Sawant, Kaveri R.

    Combining the positive structural features of mesoporous materials and microporous zeolite aluminosilicates can lead to the synthesis and application of new materials useful for catalytic processes involving large organic reactant molecules. We used organic structure-directing agents (SDAs), typically used for the synthesis of zeolites, to imprint the surface of existing mesoporous materials to create novel materials with enhanced structural properties towards this aim: materials with large well-ordered pores allowing access to large reactants with strong accessible acid sites on the surface of the pores leading to stable and active catalysts. We developed new protocols for incorporating tetrapropyl ammonium and N,N,N-trimethyl-1-adamantylammonium, SDAs used for the synthesis of the zeolites ZSM-5 (MFI) and MCM-22 (MWW) respectively, into the walls of the siliceous mesoporous material SBA-15 by using a combination of an organic solvent (glycerol) and water, to form novel porous materials. We studied the evolution of the modified pore structure of the materials by a battery of characterization techniques. Results indicate that the new materials have well-ordered pores with significantly larger mesopore diameters and structurally modified thinner, denser pore walls. We carried out similar treatments and characterization on the aluminum containing form of SBA-15, Al-SBA-15, with high and low amounts of aluminum. Pair distribution function analysis was used to analyze the structural differences in the materials and catalytic test reactions such as cumene and n-hexane cracking to detect the presence of strong acid sites like the ones in ZSM-5. Results similar to the treatments on the all-silica materials, although promising, led to novel meso-micro aluminosilicate materials with limited increase in or no catalytic activity with reference to the test reactions employed. This led to the conclusion that the aluminum in the materials was merely a spectator and did not

  7. Molecular simulations and experimental studies of zeolites

    NASA Astrophysics Data System (ADS)

    Moloy, Eric C.

    Zeolites are microporous aluminosilicate tetrahedral framework materials that have symmetric cages and channels with open-diameters between 0.2 and 2.0 nm. Zeolites are used extensively in the petrochemical industries for both their microporosity and their catalytic properties. The role of water is paramount to the formation, structure, and stability of these materials. Zeolites frequently have extra-framework cations, and as a result, are important ion-exchange materials. Zeolites also play important roles as molecular sieves and catalysts. For all that is known about zeolites, much remains a mystery. How, for example, can the well established metastability of these structures be explained? What is the role of water with respect to the formation, stabilization, and dynamical properties? This dissertation addresses these questions mainly from a modeling perspective, but also with some experimental work as well. The first discussion addresses a special class of zeolites: pure-silica zeolites. Experimental enthalpy of formation data are combined with molecular modeling to address zeolitic metastability. Molecular modeling is used to calculate internal surface areas, and a linear relationship between formation enthalpy and internal surface areas is clearly established, producing an internal surface energy of approximately 93 mJ/m2. Nitrate bearing sodalite and cancrinite have formed under the caustic chemical conditions of some nuclear waste processing centers in the United States. These phases have fouled expensive process equipment, and are the primary constituents of the resilient heels in the bottom of storage tanks. Molecular modeling, including molecular mechanics, molecular dynamics, and density functional theory, is used to simulate these materials with respect to structure and dynamical properties. Some new, very interesting results are extracted from the simulation of anhydrous Na6[Si6Al 6O24] sodalite---most importantly, the identification of two distinct

  8. Noble gas adsorption in two-dimensional zeolites: a combined experimental and density functional theory study

    NASA Astrophysics Data System (ADS)

    Wang, Mengen; Zhong, Jianqiang; Boscoboinik, Jorge Anibal; Lu, Deyu

    Zeolites are important industrial catalysts with porous three-dimensional structures. The catalytically active sites are located inside the pores, thus rendering them inaccessible for surface science measurements. We synthesized a two-dimensional (2D) zeolite model system, consisting of an (alumino)silicate bilayer weakly bound to a Ru (0001) surface. The 2D zeolite is suitable for surface science studies; it allows a detailed characterization of the atomic structure of the active site and interrogation of the model system during the catalytic reaction. As an initial step, we use Ar adsorption to obtain a better understanding of the atomic structure of the 2D zeolite. In addition, atomic level studies of rare gas adsorption and separation by zeolite are important for its potential application in nuclear waste sequestration. Experimental studies found that Ar atoms can be trapped inside the 2D-zeolite, raising an interesting question on whether Ar atoms are trapped inside the hexagonal prism nano-cages or at the interface between the (alumino)silicate bilayer and Ru(0001), or both. DFT calculations using van der Waals density functionals were carried out to determine the preferred Ar adsorption sites and the corresponding adsorption energies. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704.

  9. Rapid synthesis of an aluminum-rich MSE-type zeolite by the hydrothermal conversion of an FAU-type zeolite.

    PubMed

    Inagaki, Satoshi; Tsuboi, Yasuyuki; Nishita, Yuji; Syahylah, Tuan; Wakihara, Toru; Kubota, Yoshihiro

    2013-06-10

    An aluminum-rich MSE-type zeolite (Si/Al is as small as 7) has been successfully synthesized in a remarkably short crystallization period of only 3 days by the hydrothermal conversion of an FAU-type zeolite, presumably by the assembly of four-membered-ring (4-R) aluminosilicate oligomers supplied by the double 6-R (D6R) components of the FAU framework with the aid of the structure-directing agents and seed crystals. The dealuminated version of the aluminum-rich MSE-type zeolite showed a high level of coke durability in addition to a significant yield of propylene, which indicates that this novel zeolitic material is suitable for industrial applications as a highly selective and long-lived catalyst.

  10. Crystallization of Yttrium and Samarium Aluminosilicate Glasses

    NASA Astrophysics Data System (ADS)

    Lago, Diana C.; Prado, Miguel O.

    Aluminosilicate glasses containing samarium and yttrium (SmAS and YAS glasses) exhibit high glass transition temperatures, corrosion resistance, and glass stability on heating which make them useful for technological applications. Yttrium aluminosilicate glass microspheres are currently being used for internal selective radiotherapy of liver cancer. During the preparation process, crystallization needs to be totally or partially avoided depending on the final application. Thus knowing the crystallization kinetics can help to prevent or avoid it, by designing a proper thermal pathway. In this work we studied the crystallization kinetics of YAS and SmAS glasses. It was found that both, YAS and SmAS glasses crystallize from the surface. SmAS glass presented lower densities of nucleation sites. The results also showed that the crystal growth apparent enthalpy is larger for SmAS glasses.

  11. Adsorption of chromium ions from aqueous solution by using activated carbo-aluminosilicate material from oil shale.

    PubMed

    Shawabkeh, Reyad Awwad

    2006-07-15

    A novel activated carbo-aluminosilicate material was prepared from oil shale by chemical activation. The chemicals used in the activation process were 95 wt% sulfuric and 5 wt% nitric acids. The produced material combines the sorption properties and the mechanical strength of both activated carbon and zeolite. An X-ray diffraction analysis shows the formation of zeolite Y, Na-X, and A-types, sodalite, sodium silicate, mullite, and cancrinite. FT-IR spectrum shows the presence of carboxylic, phenolic, and lactonic groups on the surface of this material. The zero point of charge estimated at different mass to solution ratio ranged from 7.9 to 8.3. Chromium removal by this material showed sorption capacity of 92 mg/g.

  12. Selenium clusters in zeolites -- theory.

    NASA Astrophysics Data System (ADS)

    Demkov, Alex; Sankey, Otto

    1997-03-01

    We investigate theoretically atomic geometries, energetics and electronic properties of Se clusters in cages and channels of the zeolites Linde A and cancrinite, and compare them with the properties of the bulk Se phases. Such regular 3D arrays of nanosize clusters supported by a host crystalline matrix are known as supralattices (A.A. Demkov, and O.F. Sankey, Chem. Mater. 8), 1793 (1996). Host zeolite frameworks are transparent, and the presence of Se gives rise to electronic cluster-like states in the energy gap region of the host material. We find that the encapsulation causes structural changes in the cluster geometry which alter its electronic structure, we call this a ``pressure'' effect. In addition, the quantum confinement further changes these states upon the encapsulation. We discuss the relative importance of these two effects, and compare our calculations with the recent experimental work ( Y. Nozue, et al.), J. Phys.: Condens. Matter. 2, 5209 (1990).

  13. Ammonium removal from high-strength aqueous solutions by Australian zeolite.

    PubMed

    Wijesinghe, D Thushari N; Dassanayake, Kithsiri B; Sommer, Sven G; Jayasinghe, Guttila Y; J Scales, Peter; Chen, Deli

    2016-07-02

    Removal of ammonium nitrogen (NH4(+)-N) particularly from sources which are highly rich in nitrogen is important for addressing environmental pollution. Zeolites, aluminosilicate minerals, are commonly used as commercial adsorbents and ion-exchange medium in number of commercial applications due to its high adsorption capacity of ammonium (NH4(+)). However, detailed investigations on NH4(+) adsorption and ion exchange capacities of Australian natural zeolites are rare, particularly under higher NH4(+) concentrations in the medium. Therefore, this study was conducted to determine NH4(+) adsorption characteristics of Australian natural zeolites at high NH4(+) concentrations with and without other chemical compounds in an aqueous solution. Results showed that initial NH4(+) concentration, temperature, reaction time, and pH of the solution had significant effects on NH4(+) adsorption capacity of zeolite. Increased retention time and temperature generally had a positive impact on adsorption. Freundlich model fitted well with adsorption process of Australian natural zeolites; however, Langmuir model had best fitted for the adsorption process of sodium (Na(+)) treated zeolites. NaCl treatment increased the NH4(+) adsorption capacity of Australian zeolites by 25% at 1000 mg-N, NH4(+) solution. The maximum adsorption capacity of both natural Australian zeolites and Na(+) treated zeolites were estimated as 9.48 and 11.83 mg-N/g, respectively, which is lower than many zeolites from other sources. Compared to the NH4(+) only medium, presence of other competitive ions and acetic acid in the medium (resembling composition in digested swine manure slurries) reduced NH4(+) removal of natural and Na(+) treated zeolites by 44% and 57%, respectively. This suggests detailed investigations are required to determine practically achievable NH4(+) -N removal potential of zeolites for applications in complex mediums such as animal manure slurries.

  14. The effect of TiO2/aluminosilicate nanocomposite additives on the mechanical and thermal properties of polyacrylic coatings

    NASA Astrophysics Data System (ADS)

    Nosrati, Rahimeh; Olad, Ali

    2015-12-01

    The commercial grade polyacrylic latex was modified in order to prepare a mechanical and thermal improved coating. TiO2/Ag-exchanged-aluminosilicate nanocomposites with montmorillonite, zeolite-A and clinoptilolite aluminosilicates were prepared and used as additive in the matrix of polyacrylic latex to achieve a coating with proper mechanical and thermal properties. X-ray diffraction patterns and FESEM were used to characterize the composition, structure, and morphology of the nanocomposite additives. Polyacrylic coatings modified by TiO2/Ag-exchanged-aluminosilicate nanocomposite additives showed higher adhesion strength and hardness compared to unmodified commercial grade polyacrylic coatings. Differential Scanning Calorimetry (DSC) analysis showed lower glass transition temperature for modified polyacrylic coatings than that of unmodified polyacrylic coatings. The tensile tests were also carried out for unmodified and modified polyacrylic coatings. According to the results, the modified polyacrylic based coating with TiO2/Ag-exchanged-clinoptilolite nanocomposite additive was the best coating considering most of useful properties.

  15. High-Aluminum-Affinity Silica Is a Nanoparticle That Seeds Secondary Aluminosilicate Formation

    PubMed Central

    Jugdaohsingh, Ravin; Brown, Andy; Dietzel, Martin; Powell, Jonathan J.

    2013-01-01

    Despite the importance and abundance of aluminosilicates throughout our natural surroundings, their formation at neutral pH is, surprisingly, a matter of considerable debate. From our experiments in dilute aluminum and silica containing solutions (pH ~ 7) we previously identified a silica polymer with an extraordinarily high affinity for aluminium ions (high-aluminum-affinity silica polymer, HSP). Here, further characterization shows that HSP is a colloid of approximately 2.4 nm in diameter with a mean specific surface area of about 1,000 m2 g-1 and it competes effectively with transferrin for Al(III) binding. Aluminum binding to HSP strongly inhibited its decomposition whilst the reaction rate constant for the formation of the β-silicomolybdic acid complex indicated a diameter between 3.6 and 4.1 nm for these aluminum-containing nanoparticles. Similarly, high resolution microscopic analysis of the air dried aluminum-containing silica colloid solution revealed 3.9 ± 1.3 nm sized crystalline Al-rich silica nanoparticles (ASP) with an estimated Al:Si ratio of between 2 and 3 which is close to the range of secondary aluminosilicates such as imogolite. Thus the high-aluminum-affinity silica polymer is a nanoparticle that seeds early aluminosilicate formation through highly competitive binding of Al(III) ions. In niche environments, especially in vivo, this may serve as an alternative mechanism to polyhydroxy Al(III) species binding monomeric silica to form early phase, non-toxic aluminosilicates. PMID:24349573

  16. Synthetic Zeolites as Controlled-Release Delivery Systems for Anti-Inflammatory Drugs.

    PubMed

    Khodaverdi, Elham; Soleimani, Hossein Ali; Mohammadpour, Fatemeh; Hadizadeh, Farzin

    2016-06-01

    Scientists have always been trying to use artificial zeolites to make modified-release drug delivery systems in the gastrointestinal tract. An ideal carrier should have the capability to release the drug in the intestine, which is the main area of absorption. Zeolites are mineral aluminosilicate compounds with regular structure and huge porosity, which are available in natural and artificial forms. In this study, soaking, filtration and solvent evaporation methods were used to load the drugs after activation of the zeolites. Weight measurement, spectroscopy FTIR, thermogravimetry and scanning electronic microscope were used to determine drug loading on the systems. Finally, consideration of drug release was made in a simulated gastric fluid and a simulated intestinal fluid for all matrixes (zeolites containing drugs) and drugs without zeolites. Diclofenac sodium (D) and piroxicam (P) were used as the drug models, and zeolites X and Y as the carriers. Drug loading percentage showed that over 90% of drugs were loaded on zeolites. Dissolution tests in stomach pH environment showed that the control samples (drug without zeolite) released considerable amount of drugs (about 90%) within first 15 min when it was about 10-20% for the matrixes. These results are favorable as NSAIDs irritate the stomach wall and it is ideal not to release much drugs in the stomach. Furthermore, release rate of drugs from matrixes has shown slower rate in comparison with control samples in intestine pH environment.

  17. Structural and redox effects in iron-doped magnesium aluminosilicates

    NASA Astrophysics Data System (ADS)

    Ferreira, N. M.; Kovalevsky, A. V.; Valente, M. A.; Waerenborgh, J. C.; Frade, J. R.; Costa, F. M.

    2017-01-01

    Magnesium aluminosilicates (MAS) represent a great importance for many electrical and catalytic applications. Recently, MAS-based glasses were considered as prospective for use as an electrolyte in steel making by molten oxide electrolysis process, an alternative electrometallurgical technique which offers prospects for environmental and economic advantages over traditional steelmaking. In the present work, low-iron content MAS glasses were processed by an unconventional method: the laser floating zone (LFZ), to simulate the strongly-nonequilibrium high-temperature conditions which may arise during pyroelectrolysis process. The work focuses on the effect of pulling rate on crystallization kinetics, taking into account structural, electrical and magnetic properties of the as-grown material. The results revealed that faster pulling rates promote formation of isolated iron cations in the glass forming network. The crystallization process is strongly affected by lower pulling rates. LFZ method shows good prospects for studying the crystallization mechanisms in silicate-based glasses with additions of redox-active cations, by providing flexibility in tuning their oxidation state and crystalline/amorphous conditions.

  18. Modeling of Macroscopic/Microscopic Transport and Growth Phenomena in Zeolite Crystal Solutions Under Microgravity Conditions

    NASA Technical Reports Server (NTRS)

    Gatsonis, Nikos A.; Alexandrou, Andreas; Shi, Hui; Ongewe, Bernard; Sacco, Albert, Jr.

    1999-01-01

    Crystals grown from liquid solutions have important industrial applications. Zeolites, for instance, a class of crystalline aluminosilicate materials, form the backbone of the chemical process industry worldwide, as they are used as adsorbents and catalysts. Many of the phenomena associated with crystal growth processes are not well understood due to complex microscopic and macroscopic interactions. Microgravity could help elucidate these phenomena and allow the control of defect locations, concentration, as well as size of crystals. Microgravity in an orbiting spacecraft could help isolate the possible effects of natural convection (which affects defect formation) and minimize sedimentation. In addition, crystals will stay essentially suspended in the nutrient pool under a diffusion-limited growth condition. This is expected to promote larger crystals by allowing a longer residence time in a high-concentration nutrient field. Among other factors, the crystal size distribution depends on the nucleation rate and crystallization. These two are also related to the "gel" polymerization/depolymerization rate. Macroscopic bulk mass and flow transport and especially gravity, force the crystals down to the bottom of the reactor, thus forming a sedimentation layer. In this layer, the growth rate of the crystals slows down as crystals compete for a limited amount of nutrients. The macroscopic transport phenomena under certain conditions can, however, enhance the nutrient supply and therefore, accelerate crystal growth. Several zeolite experiments have been performed in space with mixed results. The results from our laboratory have indicated an enhancement in size of 30 to 70 percent compared to the best ground based controls, and a reduction of lattice defects in many of the space grown crystals. Such experiments are difficult to interpret, and cannot be easily used to derive empirical or other laws since many physical parameters are simultaneously involved in the process

  19. The growth of carbon nanotubes on montmorillonite and zeolite (clinoptilolite)

    NASA Astrophysics Data System (ADS)

    Kadlečíková, M.; Breza, J.; Jesenák, K.; Pastorková, K.; Luptáková, V.; Kolmačka, M.; Vojačková, A.; Michalka, M.; Vávra, I.; Križanová, Z.

    2008-06-01

    Synthesis of carbon nanotubes described in the present work is based on activation of methane in a hot filament CVD reactor and subsequent creation of nanostructures on a catalyst pre-treated polished surface of silicon. An essential step of the synthesis is the use of natural minerals as catalysts. We have studied the catalyst parameters, the way of its application and the amount of Fe 3+ cations on the surface of aluminosilicates on the quality of the grown nanotube layers. The growth of carbon nanotubes catalyzed by montmorillonite and zeolite (clinoptilolite) was confirmed by scanning electron microscopy and Raman spectroscopy.

  20. Synthesis and characterization of nitrogen substituted zeolites

    NASA Astrophysics Data System (ADS)

    Dogan, Fulya

    The interest in basic solid materials, particularly for basic zeolites has considerably increased in the last two decades because of their potential use in catalysis and separation. Basic zeolites have most often been obtained by ion-exchange or impregnation with alkali metal cations or grafting of organic bases onto zeolite pore walls. Such materials often suffer from instability and/or pore blockage, because none of these approaches places basic sites directly into the zeolite framework. Recently zeolitic materials have been made with some of the bridging oxygen atoms in Si--O--Si and/or Si--O--Al linkages replaced by NH groups, i.e. by substitution of framework oxygen by nitrogen. As a result, the basic strength of the framework increases due to the lower electronegativity of nitrogen with respect to oxygen. In this study, solid base catalysts are obtained by nitrogen substitution of the faujasite type of zeolites under ammonia flow at high temperatures. The efficiency of the reaction is tested by using zeolites with different aluminum contents and extraframework cations and varying the reaction conditions such as ammonia flow rate, reaction temperature and duration. The characterization studies show that high levels of nitrogen substitution can be achieved while maintaining porosity, particularly for NaY and low-aluminum HY zeolites, without a significant loss in the crystallinity. 27Al and 29 Si MAS NMR experiments performed on the nitrogen substituted zeolites show dealumination of the framework and preferential substitution for Si--OH--Al sites at the early stages of the reaction (temperatures at 750--800 °C). No preference is seen for reactions performed at higher temperatures and longer reaction times (e.g., 850 °C and 48 h). X-ray PDF analysis performed on the modified zeolites show that the Si-N distance in the 1st shell is longer than Si-O bond distance and Si-Si/Al bond distance of the Si-O/N-Si/Al linkage decreases, as an indication of a decrease in

  1. Zeolite-like liquid crystals

    PubMed Central

    Poppe, Silvio; Lehmann, Anne; Scholte, Alexander; Prehm, Marko; Zeng, Xiangbing; Ungar, Goran; Tschierske, Carsten

    2015-01-01

    Zeolites represent inorganic solid-state materials with porous structures of fascinating complexity. Recently, significant progress was made by reticular synthesis of related organic solid-state materials, such as metal-organic or covalent organic frameworks. Herein we go a step further and report the first example of a fluid honeycomb mimicking a zeolitic framework. In this unique self-assembled liquid crystalline structure, transverse-lying π-conjugated rod-like molecules form pentagonal channels, encircling larger octagonal channels, a structural motif also found in some zeolites. Additional bundles of coaxial molecules penetrate the centres of the larger channels, unreachable by chains attached to the honeycomb framework. This creates a unique fluid hybrid structure combining positive and negative anisotropies, providing the potential for tuning the directionality of anisotropic optical, electrical and magnetic properties. This work also demonstrates a new approach to complex soft-matter self-assembly, by using frustration between space filling and the entropic penalty of chain extension. PMID:26486751

  2. Zeolite-like liquid crystals

    NASA Astrophysics Data System (ADS)

    Poppe, Silvio; Lehmann, Anne; Scholte, Alexander; Prehm, Marko; Zeng, Xiangbing; Ungar, Goran; Tschierske, Carsten

    2015-10-01

    Zeolites represent inorganic solid-state materials with porous structures of fascinating complexity. Recently, significant progress was made by reticular synthesis of related organic solid-state materials, such as metal-organic or covalent organic frameworks. Herein we go a step further and report the first example of a fluid honeycomb mimicking a zeolitic framework. In this unique self-assembled liquid crystalline structure, transverse-lying π-conjugated rod-like molecules form pentagonal channels, encircling larger octagonal channels, a structural motif also found in some zeolites. Additional bundles of coaxial molecules penetrate the centres of the larger channels, unreachable by chains attached to the honeycomb framework. This creates a unique fluid hybrid structure combining positive and negative anisotropies, providing the potential for tuning the directionality of anisotropic optical, electrical and magnetic properties. This work also demonstrates a new approach to complex soft-matter self-assembly, by using frustration between space filling and the entropic penalty of chain extension.

  3. Synthesis, characterization, and mercury adsorption properties of hybrid mesoporous aluminosilicate sieve prepared with fly ash

    PubMed Central

    Liu, Minmin; Hou, Li-an; Xi, Beidou; Zhao, Ying; Xia, Xunfeng

    2013-01-01

    A novel hybrid mesoporous aluminosilicate sieve (HMAS) was prepared with fly ash and impregnated with zeolite A precursors. This improved the mercury adsorption of HMAS compared to original MCM-41. The HMAS was characterized by X-ray diffraction (XRD), nitrogen adsorption–desorption, Fourier transform infrared (FTIR) analysis, transmission electron microscopy (TEM) images and 29Si and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra. These showed that the HMAS structure was still retained after impregnated with zeolite A. But the surface area and pore diameter of HMAS decreased due to pore blockage. Adsorption of mercury from aqueous solution was studied on untreated MCM-41and HMAS. The mercury adsorption rate of HMAS was higher than that of origin MCM-41. The adsorption of mercury was investigated on HMAS regarding the pH of mercury solution, initial mercury concentration, and the reaction temperature. The experimental data fit well to Langmuir and Freundlich isotherm models. The Dublin–Radushkevich isotherm and the characterization show that the mercury adsorption on HMAS involved the ion-exchange mechanisms. In addition, the thermodynamic parameters suggest that the adsorption process was endothermic in nature. The adsorption of mercury on HMAS followed the first order kinetics. PMID:23687400

  4. Synthesis, characterization, and mercury adsorption properties of hybrid mesoporous aluminosilicate sieve prepared with fly ash

    NASA Astrophysics Data System (ADS)

    Liu, Minmin; Hou, Li-an; Xi, Beidou; Zhao, Ying; Xia, Xunfeng

    2013-05-01

    A novel hybrid mesoporous aluminosilicate sieve (HMAS) was prepared with fly ash and impregnated with zeolite A precursors. This improved the mercury adsorption of HMAS compared to original MCM-41. The HMAS was characterized by X-ray diffraction (XRD), nitrogen adsorption-desorption, Fourier transform infrared (FTIR) analysis, transmission electron microscopy (TEM) images and 29Si and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra. These showed that the HMAS structure was still retained after impregnated with zeolite A. But the surface area and pore diameter of HMAS decreased due to pore blockage. Adsorption of mercury from aqueous solution was studied on untreated MCM-41and HMAS. The mercury adsorption rate of HMAS was higher than that of origin MCM-41. The adsorption of mercury was investigated on HMAS regarding the pH of mercury solution, initial mercury concentration, and the reaction temperature. The experimental data fit well to Langmuir and Freundlich isotherm models. The Dublin-Radushkevich isotherm and the characterization show that the mercury adsorption on HMAS involved the ion-exchange mechanisms. In addition, the thermodynamic parameters suggest that the adsorption process was endothermic in nature. The adsorption of mercury on HMAS followed the first order kinetics.

  5. Synthesis, characterization, and mercury adsorption properties of hybrid mesoporous aluminosilicate sieve prepared with fly ash.

    PubMed

    Liu, Minmin; Hou, Li-An; Xi, Beidou; Zhao, Ying; Xia, Xunfeng

    2013-05-15

    A novel hybrid mesoporous aluminosilicate sieve (HMAS) was prepared with fly ash and impregnated with zeolite A precursors. This improved the mercury adsorption of HMAS compared to original MCM-41. The HMAS was characterized by X-ray diffraction (XRD), nitrogen adsorption-desorption, Fourier transform infrared (FTIR) analysis, transmission electron microscopy (TEM) images and (29)Si and (27)Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra. These showed that the HMAS structure was still retained after impregnated with zeolite A. But the surface area and pore diameter of HMAS decreased due to pore blockage. Adsorption of mercury from aqueous solution was studied on untreated MCM-41and HMAS. The mercury adsorption rate of HMAS was higher than that of origin MCM-41. The adsorption of mercury was investigated on HMAS regarding the pH of mercury solution, initial mercury concentration, and the reaction temperature. The experimental data fit well to Langmuir and Freundlich isotherm models. The Dublin-Radushkevich isotherm and the characterization show that the mercury adsorption on HMAS involved the ion-exchange mechanisms. In addition, the thermodynamic parameters suggest that the adsorption process was endothermic in nature. The adsorption of mercury on HMAS followed the first order kinetics.

  6. ZEOLITES: EFFECTIVE WATER PURIFIERS

    EPA Science Inventory

    Zeolites are known for their adsorption, ion exchange and catalytic properties. Various natural zeolites are used as odor and moisture adsorbents and water softeners. Due to their acidic nature, synthetic zeolites are commonly employed as solid acid catalysts in petrochemical ind...

  7. Inelastic X-ray Scattering Studies of Zeolite Collapse

    SciTech Connect

    Greaves, G. Neville; Kargl, Florian; Ward, David; Holliman, Peter; Meneau, Florian

    2009-01-29

    In situ inelastic x-ray scattering (IXS) experiments have been used to probe heterogeneity and deformability in zeolte Y as this thermally collapses to a high density amorphous (HDA) aluminosilicate phase. The Landau-Placzek ratio R{sub LP} falls slowly as amorphisation advances, increasing in the later stages of collapse clearly showing how homogeneity improves non-linearly--behaviour linked closely with the decline in molar volume V{sub Molar}. The Brillouin frequency {omega}{sub Q} also decreases with amorphisation in a similar fashion, signifying a non-uniform decrease in the speed of sound v{sub l}. All of these changes with zeolite amorphisation infer formation of an intermediate low density amorphous (LDA) phase. This low entropy or 'perfect glass' has mechanical properties which are closer to the zeolite rather to the HDA glass--notably a very small value of Poisson's Ratio signifying unusually low resistance to deformation.

  8. Double rotation NMR studies of zeolites and aluminophosphate molecular sieves

    SciTech Connect

    Jelinek, Raz

    1993-07-01

    Goal is to study the organization and structures of guest atoms and molecules and their reactions on internal surfaces within pores of zeolites and aluminophosphate molecular sieves. 27Al and 23Na double rotation NMR (DOR) is used since it removes the anisotropic broadening in NMR spectra of quadrupolar nuclei, thus increasing resolution. This work concentrates on probing aluminum framework atoms in aluminophosphate molecular sieves and sodium extra framework cations in porous aluminosilicates. In aluminophosphates, ordering and electronic environments of the framework 27Al nuclei are modified upon adsorption of water molecules within the channels; a relation is sought between the sieve channel topology and the organization of adsorbed water, as well as the interaction between the Al nuclei and the water molecules. Extra framework Na+ cations are directly involved in adsorption processes and reactions in zeolite cavities.

  9. Zeolite catalysis: technology

    SciTech Connect

    Heinemann, H.

    1980-07-01

    Zeolites have been used as catalysts in industry since the early nineteen sixties. The great majority of commercial applications employ one of three zeolite types: zeolite Y; Mordenite; ZSM-5. By far the largest use of zeolites is in catalytic cracking, and to a lesser extent in hydrocracking. This paper reviews the rapid development of zeolite catalysis and its application in industries such as: the production of gasoline by catalytic cracking of petroleum; isomerization of C/sub 5/ and C/sub 6/ paraffin hydrocarbons; alkylation of aromatics with olefins; xylene isomerization; and conversion of methanol to gasoline.

  10. Aluminosilicates as controlled molecular environments for selective photochemical and catalytic reactions

    SciTech Connect

    Carrado, K.A.

    1986-01-01

    This dissertation concerns research that involves photochemical, catalytic and spectroscopic studies of clays, pillared clays and zeolites. Incorporation of uranyl ions into hectorite, montmorillonite, bentonite and vermiculite clays was monitored by XRD and luminescence methods. Excitation and emission characteristics were studied in order to understand the behavior of uranyl ions in clays after various thermal treatments. Luminescence lifetime measurements elucidated the number of uranyl sites. Uranyl-exchanged clays were found to absorb light at lower energies (445-455nm) than analogous uranyl-exchanged zeolites (425nm). Each uranyl-exchanged clay was tested as a catalyst for the photoassisted oxidation of isopropyl alcohol. Energy transfer (ET) between uranyl and Eu(III) ions in different zeolite framework systems was examined. The efficiency of ET (eta/sub t/) was found to be affected by the type of framework present. Pillared bentonites were examined in the hydrocracking of decane. A catalytically and spectroscopically active dopant ion, Cr(III), was introduced into the clays in both pillared and unpillared forms depending upon synthetic conditions. EPR and DRS were employed to monitor the environment of Cr(III) for determination of its location - whether in the micropore structure or associated with alumina pillars. Catalytic behavior based upon this variability of location was examined. Incorporation of Cr(III) ions into an alumina pillar was found to increase the stability and activity with respect to an alumina PILC catalyst. The results of these studies suggest that selective, efficient catalysts can be designed around inorganic ions in aluminosilicate supports.

  11. IR spectroscopy studies of zeolites in geopolymeric materials derived from kaolinite

    NASA Astrophysics Data System (ADS)

    Król, M.; Minkiewicz, J.; Mozgawa, W.

    2016-12-01

    This study investigated the effect of alkali activation process conditions on the IR spectra, on which amount and types of zeolites in the resultant geopolymers influence significantly. Kaolinite was used as starting materials. The kaolinitic clay was first calcined to transform into the amorphous aluminosilicate phases (metakaolinite) and then activated with sodium silicate (as water glass) and sodium hydroxide. The effects of reaction systems composition (expressed as SiO2/Al2O3 and Al2O3/Na2O molar ratios) as well as synthesis temperature on the phase composition of obtained products have been determined. In particular, the structures of materials were examined using FT-IR spectroscopy in the middle infrared range. The results were compared to the XRD measurements, as well as SEM observations. Alkali-activation treatment of the metakaolin yielded bulk materials with different amounts and types of zeolite, which reveal the IR spectra of received materials. With proper selection of the initial conditions (temperature and composition), it is possible to obtain a solid material containing zeolite phase such as zeolite X, zeolite A or sodalite. The presence of zeolite phase was confirmed by the measurement of spectra in the middle infrared. In particular in pseudolattice range of the spectra, i.e. 800-400 cm-1, there are bands associated with the ring vibrations, which are characteristic for secondary building units (SBU) occurred in zeolite structure. IR spectroscopy is also useful in the studies of resulting amorphous phase structure.

  12. Densification of salt-occluded zeolite a powders to a leach-resistant monolith

    SciTech Connect

    Lewis, M.A.; Fischer, D.F.; Murhpy, C.D.

    1993-10-01

    Pyrochemical processing of spent fuel from the Integral Fast Reactor (IFR) yields a salt waste of LiCl-KCl that contains approximately 6 wt% fission products, primarily as CsCl and SrCl{sub 2}. Past work has shown that zeolite A will preferentially sorb cesium and strontium and will encapsulate the salt waste in a leach-resistant, radiation-resistant aluminosilicate matrix. However, a method is sill needed to convert the salt-occluded zeolite powders into a form suitable for geologic disposal. We are thus investigating a method that forms bonded zeolite by hot pressing a mixture of glass frit and salt-occluded zeolite powders at 990 K (717{degree}C) and 28 MPa. The leach resistance of the bonded zeolite was measured in static leach tests run for 28 days in 363 K (90{degree}C) deionized water. Normalized release rates of all elements in the bonded zeolite were low, <1 g/m{sup 2} d. Thus, the bonded zeolite may be a suitable waste form for IFR salt waste.

  13. Silanization-Based Zeolite Crystallization: Participation Degree and Pathway.

    PubMed

    Yan, Yueer; Azhati, Arepati; Guo, Xiao; Zhang, Yahong; Tang, Yi

    2015-08-17

    A clear and deep understanding of zeolite crystallization with the addition of organosilane is desirable for the reasonable design and preparation of hierarchical zeolites. Herein, the effects of different organosilanes on zeolite crystallization were systematically studied. It was found that organosilane plays the role of an inhibitor in the silanization-based zeolite preparation, and this inhibition effect was determined by its participation degree. An organosilane with a high participation degree can result in the prolongation of nucleation and growth periods of zeolite as well as the variation of product properties. More importantly, a dynamic participation pathway of organosilane is proposed, that is, the growth of zeolite is accompanied by the continuous removal of organosilane, leading to an increase of product crystallinity as well as the decrease of mesoporosity. This study gives a new insight into the role that organosilane plays in zeolite crystallization, which will help to direct the rational selection of organosilane and design of crystallization condition for the optimal synthesis of hierarchical zeolites.

  14. Technetium (VII) Co-precipitation with Framework Aluminosilicates

    SciTech Connect

    Harsh, James B.; Dickson, Johnbull Otah; Pierce, Eric M.; Bargar, John

    2015-07-13

    Technetium-99 (99Tc), a long-lived radionuclide, is one of the most widespread contaminants within the Hanford subsurface. At some depths, it is only extractable with strong acids, suggesting incorporation into a solid phase. We hypothesized that Tc may have coprecipitated with feldspathoid aluminosilicates under waste tanks that had leaked caustic solutions into the vadose zone. Our objectives were to determine if Tc could be incorporated into the feldspathoids cancrinite and sodalite and under what conditions coprecipitation could occur. Our hypothesis was that sodalite was more likely to incorporate and retain Tc. Our approach was to use known methods of feldspathoid formation in solutions resembling those in Hanford waste tanks contacting sediments in terms of major ion (Na, NO3, OH, Al(OH)4, and Si(OH)4 concentrations. In some cases, Al and Si were supplied from zeolite. We used perrhenate (ReO4) as a surrogate for pertechnetate (TcO4) to avoid the radioactivity. The major findings of this study were 1) ReO4 could be incorporated into either sodalite or cancrinite but the concentration in the solid was < 1% of the competing ion Cl, NO3, or NO2. 2) The small amount of ReO4 incorporated was not exchangeable with NO3 or NO2. 3) In sodalite, NO3 was highly preferred over ReO4 but significant Re-sodalite was formed when the mole fraction in solution (Re/Re+N) exceeded 0.8. 4) A nonlinear relation between the unit cell parameter and amount of Re incorporated suggested that a separate Re-sodalite phase was formed rather than a solid solution. 5) We determined that sodalite preference for sodalite in the presence of different anions increased with the ionic size of the competing anion: Cl < CO3 < NO3 < SO4 < MnO4 < WO4 and significant incorporation did not occur unless the difference in anion radii was less than 12%. 6) Re(VII) was not significantly reduced to Re(IV) under the conditions of this experiment and Re appeared to be a good surrogate for Tc under oxidizing

  15. Characterization of Uranium Solids Precipitated with Aluminosilicates

    SciTech Connect

    DUFF, MC

    2004-04-29

    At the Savannah River Site (SRS), the High-Level Waste (HLW) Tank Farms store and process high-level liquid radioactive wastes from the Canyons and recycle water from the Defense Waste Processing Facility. The waste is concentrated using evaporators to minimize the volume of space required for HLW storage. Recently, the 2H Evaporator was shutdown due to the crystallization of sodium aluminosilicate (NAS) solids (such as cancrinite and sodalite) that contained close to 10 weight percent of elementally-enriched uranium (U). Prior to extensive cleaning,the evaporator deposits resided on the evaporator walls and other exposed internal surfaces within the evaporator pot. Our goal is to support the basis for the continued safe operation of SRS evaporators and to gain more information that could be used to help mitigate U accumulation during evaporator operation.

  16. Statistical Approach to the Transformation of Fly Ash into Zeolites

    NASA Astrophysics Data System (ADS)

    Derkowski, Arkadiusz; Michalik, Marek

    2007-01-01

    The experimental conversion of F-class fly ash into zeolites is described. The ash, composed mainly of aluminosilicate glass, mullite and quartz, was collected in the Cracow power plant (southern Poland). The experiments involved the heating of fly ash samples in PTFE vessels. Time, temperature and solution composition were the reaction parameters considered in the experiments and in the subsequent modeling. A series of reactions with 0.5, 3 and 5M NaOH solutions (and some with additional 3M NaCl) were carried out at 70°, 100° and 150°C for 12-48 hours under autogenic pressure (not measured) and at a constant ash-to-solution ratio of 33.3 g/l. The following zeolite phases were synthesized: sodalite (SOD structure), hydroxysodalite (SOD), CAN type phases, Na-X (FAU), and NaP1 (GIS). Statistically calculated relationships based on the mineral- and chemical compositions of the reaction products support the conclusion that the type of zeolite phase that crystallizes depends on the concentration of OH- and Cl- in solution and on the temperature of the reaction. The duration of reaction, if on the order of tens of hours, is of less significance. The nature of the zeolite phase that crystalises is controlled by the intensity and selectivity of the substrate dissolution. That dissolution can favour, in sequence, one or other of the components in the substrate, resulting in Si/Al variation in the reaction solutions. Mullite dissolution (decreasing solution Si/Al) characterizes the most advanced reaction stages. The sequence of crystallization of the zeolite phases mirrors the sequential dissolution of substrate components, and the composition of the crystallizing zeolite crystals reflects the changes in the solution Si/Al.

  17. Inorganic-organic composite nanoengineered films using self-assembled monolayers for directed zeolite film growth

    SciTech Connect

    Dye, R.C.; Hermes, R.E.; Martinez, M.G.; Peachey, N.M.

    1997-10-01

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Zeolites, or molecular sieves, are aluminosilicate cage structures that are typically grown from a heterogeneous mixture of organic template molecules, inorganic salts of alumina and silica, and water. These zeolites are used in industry for catalytic cracking of hydrocarbons (gasoline manufacture from oil), and contaminant removal from chemical production processes. Within one year, we developed a viable method for the deposition of a quaternary ammonium salt amphiphile onto silicon wafer substrates. Using a biomimetic growth process, we were also able to demonstrate the first thin-film formation of a zeolite structure from such an organic template. Additionally, we synthesized the precursor to another amphiphile which was to be for further studies.

  18. On the potential of positron lifetime spectroscopy for the study of early stages of zeolites formation from their amorphous precursors

    NASA Astrophysics Data System (ADS)

    Bosnar, S.; Kosanović, C.; Subotić, B.; Bosnar, D.; Kajcsos, Zs.; Liszkay, L.; Lohonyai, L.; Molnár, B.; Lázár, K.

    2007-02-01

    The applicability of positron lifetime (LT) spectroscopy to the study of progress of formation of Secondary Building Units (SBU) in gels yielding in FAU and LTA type zeolites was investigated. Samples were prepared from aluminosilicate gels with various degrees of local structural order. LT measurements were performed at room temperature in air and in vacuum. Coexistence of annihilation modi with long lifetime components was shown; a correlation with precursors of nucleation and type of exchanged ions was also indicated.

  19. Solid state NMR of porous materials : zeolites and related materials.

    PubMed

    Koller, Hubert; Weiss, Mark

    2012-01-01

    Solid state NMR spectroscopy applied to the science of crystalline micro- and mesoporous silica materials over the past 10 years is reviewed. A survey is provided of framework structure and connectivity analyses from chemical shift effects of various elements in zeolites including heteroatom substitutions, framework defects and pentacoordinated silicon for zeolites containing fluoride ions. New developments in the field of NMR crystallography are included. Spatial host-guest ordering and confinement effects of zeolite-sorbate complexes are outlined, with special emphasis on NMR applications utilizing the heteronuclear dipolar interaction. The characterization of zeolite acid sites and in situ NMR on catalytic conversions is also included. Finally, the motion of extra-framework cations is investigated in two tutorial cases of sodium hopping in sodalite and cancrinite.

  20. Investigation of aluminosilicate refractory for solid oxide fuel cell applications

    NASA Astrophysics Data System (ADS)

    Gentile, Paul Steven

    Stationary solid oxide fuel cells (SOFCs) have been demonstrated to provide clean and reliable electricity through electro-chemical conversion of various fuel sources (CH4 and other light hydrocarbons). To become a competitive conversion technology the costs of SOFCs must be reduced to less than $400/kW. Aluminosilicate represents a potential low cost alternative to high purity alumina for SOFC refractory applications. The objectives of this investigation are to: (1) study changes of aluminosilicate chemistry and morphology under SOFC conditions, (2) identify volatile silicon species released by aluminosilicates, (3) identify the mechanisms of aluminosilicate vapor deposition on SOFC materials, and (4) determine the effects of aluminosilicate vapors on SOFC electrochemical performance. It is shown thermodynamically and empirically that low cost aluminosilicate refractory remains chemically and thermally unstable under SOFC operating conditions between 800°C and 1000°C. Energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) of the aluminosilicate bulk and surface identified increased concentrations of silicon at the surface after exposure to SOFC gases at 1000°C for 100 hours. The presence of water vapor accelerated surface diffusion of silicon, creating a more uniform distribution. Thermodynamic equilibrium modeling showed aluminosilicate remains stable in dry air, but the introduction of water vapor indicative of actual SOFC gas streams creates low temperature (<1000°C) silicon instability due to the release of Si(OH)4 and SiO(OH) 2. Thermal gravimetric analysis and transpiration studies identified a discrete drop in the rate of silicon volatility before reaching steady state conditions after 100-200 hours. Electron microscopy observed the preferential deposition of vapors released from aluminosilicate on yttria stabilized zirconia (YSZ) over nickel. The adsorbent consisted of alumina rich clusters enclosed in an amorphous siliceous

  1. Effect of temperature and aluminium on calcium (alumino)silicate hydrate chemistry under equilibrium conditions

    SciTech Connect

    Myers, Rupert J.; L'Hôpital, Emilie; Provis, John L.; Lothenbach, Barbara

    2015-02-15

    There exists limited information regarding the effect of temperature on the structure and solubility of calcium aluminosilicate hydrate (C–A–S–H). Here, calcium (alumino)silicate hydrate (C–(A–)S–H) is synthesised at Ca/Si = 1, Al/Si ≤ 0.15 and equilibrated at 7–80 °C. These systems increase in phase-purity, long-range order, and degree of polymerisation of C–(A–)S–H chains at higher temperatures; the most highly polymerised, crystalline and cross-linked C–(A–)S–H product is formed at Al/Si = 0.1 and 80 °C. Solubility products for C–(A–)S–H were calculated via determination of the solid-phase compositions and measurements of the concentrations of dissolved species in contact with the solid products, and show that the solubilities of C–(A–)S–H change slightly, within the experimental uncertainty, as a function of Al/Si ratio and temperature between 7 °C and 80 °C. These results are important in the development of thermodynamic models for C–(A–)S–H to enable accurate thermodynamic modelling of cement-based materials.

  2. Direct hydrothermal synthesis of hierarchically porous siliceous zeolite by using alkoxysilylated nonionic surfactant.

    PubMed

    Mukti, Rino R; Hirahara, Hirotomo; Sugawara, Ayae; Shimojima, Atsushi; Okubo, Tatsuya

    2010-02-16

    A hierarchically porous siliceous MFI zeolite (silicalite-1) with narrow mesoporosity has been hydrothermally synthesized by using trialkoxysilylated alkyl poly(oxyethylene ether) as mesopore-directing agent. A mesostructured silica-surfactant composite was formed at the early stage of the reaction, and zeolite crystallization proceeded during subsequent hydrothermal treatment. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations of the crystallized products showed that micro- and mesopores were hierarchically assembled in unique particle morphology with rugged surfaces. Solid-state (29)Si and (13)C NMR revealed that the covalent bonds between the zeolite framework and mesopore-directing agent were present in the products before calcination. The use of nonsilylated alkyl poly(oxyethylene ether) or a silylated alkytrimethyl-ammonium-type cationic surfactant for the synthesis of silicalite-1 resulted in a mixture of mesoporous silica and zeolite as the final product, which suggests that the covalent interaction and nonelectrostatic charge matching interaction favor the formation of hierarchically mesoporous siliceous zeolite. This alkoxysilylated nonionic surfactant can also be extended to synthesize aluminosilicate MFI zeolite (ZSM-5).

  3. Catalytic Fast Pyrolysis of Lignin over High-Surface-Area Mesoporous Aluminosilicates: Effect of Porosity and Acidity.

    PubMed

    Custodis, Victoria B F; Karakoulia, Stamatia A; Triantafyllidis, Kostas S; van Bokhoven, Jeroen A

    2016-05-23

    Catalytic fast pyrolysis (CFP) of lignin with amorphous mesoporous aluminosilicates catalysts yields a high fraction of aromatics and a relatively low amount of char/coke. The relationship between the acidity and porosity of Al-MCM-41, Al-SBA-15, and Al-MSU-J with product selectivity during lignin CFP is determined. The acid sites (mild Brønsted and stronger Lewis) are able to catalyze pyrolysis intermediates towards fewer oxygenated phenols and aromatic hydrocarbons. A generalized correlation of the product selectivity and yield with the aluminum content and acidity of the mesoporous aluminosilicates is hard to establish. Zeolitic strong acid sites are not required to achieve high conversion and selectivity to aromatic hydrocarbon because nanosized MCM-41 produces a high liquid yield and selectivity. The two most essential parameters are diffusion, which is influenced by pore and grain size, and the active site, which may be mildly acidic, but is dominated by Lewis acid sites. Nanosized grains and mild acidity are essential ingredients for a good lignin CFP catalyst.

  4. Dietary aluminosilicate supplement enhances immune activity in mice and reinforces clearance of porcine circovirus type 2 in experimentally infected pigs.

    PubMed

    Jung, Bock-Gie; Toan, Nguyen Tat; Cho, Sun-Ju; Ko, Jae-hyung; Jung, Yeon-Kwon; Lee, Bong-Joo

    2010-07-14

    Aluminosilicate is the major component of clay minerals such as zeolite, bentonite and clinoptilolite. The minerals possess a number of beneficial activities, especially in regulating the immune system. The aims of the present study were to evaluate immune enhancing effects of dietary aluminosilicate supplement (DAS) in mice, and to demonstrate clearance effects of DAS against porcine circovirus type 2 (PCV2) in experimentally infected pigs as an initial step towards the development of an antibiotic substitute for use in pigs. Relative messenger RNA expression levels of interferon-gamma, interleukin-4 and tumor necrosis factor-alpha, phagocytic activities of polymorphonuclear leucocytes, serum antibody production level and spleen B cell ratio were significantly increased in the DAS groups of mice compared with the control group (each feeding group had three replications with 5 mice each). The results indicated that general immune activity including cellular and humoral immunity could be enhanced by DAS in mice. In experimentally PCV2-infected pigs, the load of viral genome in nasal swab, serum and lung of the DAS group of pigs was significantly decreased compared with the control group at 28 days post-infection (each group three pigs). Corresponding histopathological analyses demonstrated that pigs in the DAS group displayed mild and less severe abnormal changes compared with the control group, indicating that DAS reinforces clearance of PCV2 in experimentally infected pigs. This may relate to general immune enhancing effects of DAS in mice. Therefore DAS will help the health of animal, especially in swine.

  5. Fly ash from a Mexican mineral coal. II. Source of W zeolite and its effectiveness in arsenic (V) adsorption.

    PubMed

    Medina, Adriana; Gamero, Prócoro; Almanza, José Manuel; Vargas, Alfredo; Montoya, Ascención; Vargas, Gregorio; Izquierdo, María

    2010-09-15

    Coal-fired plants in Coahuila (Mexico) produce highly reactive fly ash (MFA), which is used in a one-step process as a raw material in producing zeolite. We explored two routes in the synthesis of zeolite: (a) direct MFA zeolitization, which resulted in the formation of W zeolite with KOH and analcime with NaOH and (b) a MFA fusion route, which resulted in the formation of zeolite W or chabazite with KOH and zeolite X or P with NaOH. No residual crystalline phases were present. When LiOH was employed, ABW zeolite with quartz and mullite were obtained. For both zeolitization routes, the nature of the alkali (KOH, NaOH, LiOH), the alkali/MFA ratio (0.23-1.46), and the crystallization temperature and time (90-175 degrees C; 8-24 h) were evaluated. Additionally, the effect of temperature and time on MFA fusion was studied. W zeolite was obtained by both zeolitization methods. The direct route is preferred because it is a straightforward method using soft reaction conditions that results in a high yield of low cost zeolites with large crystal agglomerates. It was demonstrated that aluminum modified W zeolite has the ability to remove 99% of the arsenic (V) from an aqueous solution of Na(2)HAsO(4).7H(2)O originally containing 740 ppb.

  6. Stability and thermal transformation studies of Zn2+- and Fe2+- loaded zeolite Y prepared from Egyptian kaolin

    NASA Astrophysics Data System (ADS)

    EL-Mekkawi, Doaa M.; Ibrahim, Fatma A.; Selim, Mohamed M.

    2015-10-01

    The stability and thermal transformation of Zn2+ and Fe2+- zeolites based kaolin were studied with respect to their loading experimental conditions. Zeolite Y prepared from Egyptian kaolin was used in our investigations. Zeolite shows different degrees of framework stability according to the type of cation and the loading experimental conditions. The obtained data indicate the predominance of adsorption and ion exchange mechanisms during Fe2+ and Zn2+ loading, respectively. The loading experimental conditions also greatly affect the solid-solid interactions of transition metal-zeolites at elevated temperatures. ZnAl2O4 and silica phases were formed upon thermal treatment of Zn-Y zeolites. The ratio of ZnAl2O4 to silica phases increases as the amount of loaded Zn2+ increases in the corresponding unheated zeolites. However, nepheline phase was obtained upon heating Fe-Y zeolites loaded at low initial Fe2+ concentrations. Upon increasing of loaded Fe2+, iron oxide beside other amorphous phases from silica, alumina and/or aluminosilicates were obtained.

  7. Aluminosilicate glass thin films elaborated by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Carlier, Thibault; Saitzek, Sébastien; Méar, François O.; Blach, Jean-François; Ferri, Anthony; Huvé, Marielle; Montagne, Lionel

    2017-03-01

    In the present work, we report the elaboration of aluminosilicate glass thin films by Pulsed Laser Deposition at various temperatures deposition. The amorphous nature of glass thin films was highlighted by Grazing Incidence X-Ray Diffraction and no nanocristallites were observed in the glassy matrix. Chemical analysis, obtained with X-ray Photoelectron Spectroscopy and Time of Flight Secondary Ion Mass Spectroscopy, showed a good transfer and homogeneous elementary distribution with of chemical species from the target to the film a. Structural studies performed by Infrared Spectroscopy showed that the substrate temperature plays an important role on the bonding configuration of the layers. A slight shift of Si-O modes to larger wavenumber was observed with the synthesis temperature, assigned to a more strained sub-oxide network. Finally, optical properties of thins film measured by Spectroscopic Ellipsometry are similar to those of the bulk aluminosilicate glass, which indicate a good deposition of aluminosilicate bulk glass.

  8. Microstructural and phase evolution in metakaolin geopolymers with different activators and added aluminosilicate fillers

    NASA Astrophysics Data System (ADS)

    Sarkar, Madhuchhanda; Dana, Kausik; Das, Sukhen

    2015-10-01

    This work aims to investigate the microstructural and phase evolution of alkali activated metakaolin products with different activators and added aluminosilicate filler phases. The added filler phases have different reactivity to the alkali activated metakaolin system. Microstructural evolution in the alkali activated products has been investigated by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Field Emission Scanning Electron Microscope (FESEM). Variation in strength development in alkali activated metakaolin products was followed by compressive strength measurement test. Microstructural study shows that in case of metakaolin with NaOH activator crystalline sodalite formed in all the product samples irrespective of the added filler phases. The microstructure of these NaOH activated products investigated by FESEM showed crystalline and inhomogeneous morphology. Mixed activator containing both NaOH and sodium silicate in a fixed mass ratio formed predominantly amorphous phase. Microstructure of these samples showed more homogeneity than that of NaOH activated metakaolin products. The study further shows that addition of α-Al2O3 powder, non reactive phase to the alkali activated metakaolin system when used in larger amount increased crystalline phase in the matrix. α-Al2O3 powder addition increased the compressive strength of the product samples for both the activator compositions. Added phase of colloidal silica, reactive to the alkali activated metakaolin system when used in larger amount was found to increase amorphous nature of the matrix. Addition of colloidal silica influenced the compressive strength property differently with different activator compositions.

  9. Applications of high resolution NMR to geochemistry: crystalline, glass, and molten silicates

    SciTech Connect

    Schneider, E.

    1985-11-01

    The nuclear spin interactions and the associated quantum mechanical dynamics which are present in solid state NMR are introduced. A brief overview of aluminosilicate structure is presented and crystalline structure is then reviewed, with emphasis on the contributions made by /sup 29/Si NMR spectroscopy. The local structure of glass aluminosilicates as observed by NMR, is presented with analysis of the information content of /sup 29/Si spectra. A high-temperature (to 1300/sup 0/C) NMR spectroscopic investigation of the local environment and dynamics of molecular motion in molten aluminosilicates is described. A comparison is made of silicate liquid, glass, and crystalline local structure. The atomic and molecular motions present in a melt are investigated through relaxation time (T/sub 1/ and T/sub 2/) measurements as a function of composition and temperature for /sup 23/Na and /sup 29/Si.

  10. Structure and Properties of Rare Earth Aluminosilicate Glasses.

    NASA Astrophysics Data System (ADS)

    Kohli, Jeffrey Todd

    1991-02-01

    Rare earth aluminosilicate (REAS) glasses have been formed using conventional melting techniques. The glass-forming regions of six different ternary systems have been defined with praseodymium, neodymium, samarium, terbium, erbium, or ytterbium oxides, with alumina and silica. The glass-forming regions systematically decreased in size as the atomic number of the particular rare earth in the ternary systems increased. Glasses, of the molar composition 2R_2O_3 -2Al_2O_3 -6SiO_2, were formed with twelve of the fourteen true rare earth oxides in order to investigate further effects related to the identity of the rare earth ion in the glasses. Several properties of the rare earth aluminosilicate glasses were measured. These properties include: thermal expansion, glass transformation temperature, dilatometric softening point, density, molar volume, index of refraction, Vicker's hardness, magnetic susceptibility and the Faraday rotatory response. The structures of rare earth aluminosilicate glasses were investigated using infrared and Raman spectroscopies as well as magic angle spinning nuclear magnetic resonance (MAS-NMR). MAS-NMR provided information regarding the local environments of silicon and aluminum ions in yttrium aluminosilicate (YAS) glasses. Since the size and valence of the yttrium ion are similar to the true rare earth ions, and the properties of the REAS and YAS glasses are similar, it is believed that the structures of yttrium aluminosilicate glasses are similar to those of the true rare earth aluminosilicate glasses. Several rare earth aluminogermanate glasses, having the molar formula 2R_2O _3-2Al_2O _3-6GeO_2, were also formed using conventional melting techniques. The properties of these glasses were compared and contrasted with those of the REAS glasses. Finally, a chapter on the study of magnetic susceptibility in common insulator glasses was added to the thesis. Several techniques used to measure magnetic susceptibility are reviewed in this chapter

  11. Zeolites for reforming catalysts

    SciTech Connect

    Kao, J.L.; Nadler, M.; Potter, M.J.; Martir, R.V.

    1991-01-22

    This patent describes a reforming catalyst exhibiting enhanced selectivity, activity, and activity maintenance. It comprises: zeolite crystals having a pH within the range of 9.4 to 10.0, wherein the pH is determined by measuring pH of supernatent liquid from a mixture of one part of the zeolite crystals with ten parts of dionized water by weight, and comprising exchangeable cations and at least one catalytically active metal selected from the group consisting of Group VII of the Periodic Table of Elements, tin and germanium. This patten also describes a process for treating zeolite to have a pH within a range effective in imparting enhanced activity, selectivity and activity maintenance to catalysts loaded onto the zeolite. The process comprising washing zeolite with an aqueous liquid in a manner so as to result with zeolite having a pH within the pH range of 9.4 to 10.0. The PH of supernatent liquid from a mixture of one part of the zeolite crystals with ten parts of dionized water by weight.

  12. Recycling of aluminosilicate waste: Impact onto geopolymer formation

    NASA Astrophysics Data System (ADS)

    Essaidi, N.; Gharzouni, A.; Vidal, L.; Gouny, F.; Joussein, E.; Rossignol, S.

    2015-07-01

    Geopolymers are innovative ecomaterials resulting from the activation of an aluminosilicate source by an alkaline solution. Their properties depend on the used raw materials. This paper focuses on the possibility to obtain geopolymer materials with aluminosilicate laboratory waste. The effect of these additions on the geopolymer properties was studied by FTIR spectroscopy and mechanical test. It was evidenced a slowdown of the polycondensation reaction as well as the compressive strength due to the addition of laboratory waste which decreases the Si/K ratio of mixture.

  13. Diagram of Zeolite Crystals

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The Center for Advanced Microgravity Materials Processing (CAMMP) in Cambridge, MA, a NASA-sponsored Commercial Space Center, is working to improve zeolite materials for storing hydrogen fuel. CAMMP is also applying zeolites to detergents, optical cables, gas and vapor detection for environmental monitoring and control, and chemical production techniques that significantly reduce by-products that are hazardous to the environment. Depicted here is one of the many here complex geometric shapes which make them highly absorbent. Zeolite experiments have also been conducted aboard the International Space Station

  14. Zeolites: Exploring Molecular Channels

    SciTech Connect

    Arslan, Ilke; Derewinski, Mirek

    2015-05-22

    Synthetic zeolites contain microscopic channels, sort of like a sponge. They have many uses, such as helping laundry detergent lather, absorbing liquid in kitty litter, and as catalysts to produce fuel. Of the hundreds of types of zeolites, only about 15 are used for catalysis. PNNL catalysis scientists Ilke Arslan and Mirek Derewinksi are studying these zeolites to understand what make them special. By exploring the mystery of these microscopic channels, their fundamental findings will help design better catalysts for applications such as biofuel production.

  15. Zeolites: Exploring Molecular Channels

    ScienceCinema

    Arslan, Ilke; Derewinski, Mirek

    2016-07-12

    Synthetic zeolites contain microscopic channels, sort of like a sponge. They have many uses, such as helping laundry detergent lather, absorbing liquid in kitty litter, and as catalysts to produce fuel. Of the hundreds of types of zeolites, only about 15 are used for catalysis. PNNL catalysis scientists Ilke Arslan and Mirek Derewinksi are studying these zeolites to understand what make them special. By exploring the mystery of these microscopic channels, their fundamental findings will help design better catalysts for applications such as biofuel production.

  16. The roles of entropy and enthalpy in stabilizing ion-pairs at transition states in zeolite acid catalysis.

    PubMed

    Gounder, Rajamani; Iglesia, Enrique

    2012-02-21

    Acidic zeolites are indispensable catalysts in the petrochemical industry because they select reactants and their chemical pathways based on size and shape. Voids of molecular dimensions confine reactive intermediates and transition states that mediate chemical reactions, stabilizing them by van der Waals interactions. This behavior is reminiscent of the solvation effects prevalent within enzyme pockets and has analogous consequences for catalytic specificity. Voids provide the "right fit" for certain transition states, reflected in their lower free energies, thus extending the catalytic diversity of zeolites well beyond simple size discrimination. This catalytic diversity is even more remarkable because acid strength is essentially unaffected by confinement among known crystalline aluminosilicates. In this Account, we discuss factors that determine the "right fit" for a specific chemical reaction, exploring predictive criteria that extend the prevailing discourse based on size and shape. We link the structures of reactants, transition states, and confining voids to chemical reactivity and selectivity. Confinement mediates enthalpy-entropy compromises that determine the Gibbs free energies of transition states and relevant reactants; these activation free energies determine turnover rates via transition state theory. At low temperatures (400-500 K), dimethyl ether carbonylation occurs with high specificity within small eight-membered ring (8-MR) voids in FER and MOR zeolite structures, but at undetectable rates within larger voids (MFI, BEA, FAU, and SiO(2)-Al(2)O(3)). More effective van der Waals stabilization within 8-MR voids leads to lower ion-pair enthalpies but also lower entropies; taken together, carbonylation activation free energies are lower within 8-MR voids. The "right fit" is a "tight fit" at low temperatures, a consequence of how temperature appears in the defining equation for Gibbs free energy. In contrast, entropy effects dominate in high

  17. Hierarchical zeolites from class F coal fly ash

    NASA Astrophysics Data System (ADS)

    Chitta, Pallavi

    Fly ash, a coal combustion byproduct is classified as types class C and class F. Class C fly ash is traditionally recycled for concrete applications and Class F fly ash often disposed in landfills. Class F poses an environmental hazard due to disposal and leaching of heavy metals into ground water and is important to be recycled in order to mitigate the environmental challenges. A major recycling option is to reuse the fly ash as a low-cost raw material for the production of crystalline zeolites, which serve as catalysts, detergents and adsorbents in the chemical industry. Most of the prior literature of fly ash conversion to zeolites does not focus on creating high zeolite surface area zeolites specifically with hierarchical pore structure, which are very important properties in developing a heterogeneous catalyst for catalysis applications. This research work aids in the development of an economical process for the synthesis of high surface area hierarchical zeolites from class F coal fly ash. In this work, synthesis of zeolites from fly ash using classic hydrothermal treatment approach and fusion pretreatment approach were examined. The fusion pretreatment method led to higher extent of dissolution of silica from quartz and mullite phases, which in turn led to higher surface area and pore size of the zeolite. A qualitative kinetic model developed here attributes the difference in silica content to Si/Al ratio of the beginning fraction of fly ash. At near ambient crystallization temperatures and longer crystallization times, the zeolite formed is a hierarchical faujasite with high surface area of at least 360 m2/g. This work enables the large scale recycling of class F coal fly ash to produce zeolites and mitigate environmental concerns. Design of experiments was used to predict surface area and pore sizes of zeolites - thus obviating the need for intense experimentation. The hierarchical zeolite catalyst supports tested for CO2 conversion, yielded hydrocarbons

  18. Binding and catalytic reduction of NO by transition metal aluminosilicates

    SciTech Connect

    Klier, K.; Herman, R.G.; Hou, S.

    1992-06-01

    Na, Co{sup 2+}, Ce{sup 3+}, and Co{sup 2+}Ce{sup 3+} exchanged A type zeolite have been tested for NO and N{sub 2}O adsorption and decomposition at room temperature. Dynamic temperature programmed desorption (TPD) studies were also carried out with these four zeolites, as well as with CeO{sub 2} and CoA zeolite mixed with CeO{sub 2}. It was demonstrated that NO was especially decomposed into N{sub 2}, with some N{sub 2}, with some N{sub 2}O, over the doubly ion exchanged CoCeA zeolite that contained 1.77 Co and 2 Ce per unit cell. Some segregation of CeO{sub 2} occurred during these experiments, and a lower content of Ce in the CoCeA zeolite might be utilizable.

  19. IMPROVED CATALYSTS FOR HEAVY OIL UPGRADING BASED ON ZEOLITE Y NANOPARTICLES ENCAPSULATED IN STABLE NANOPOROUS HOSTS

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2004-06-30

    The focus of this project is to improve the catalytic performance of zeolite Y for heavy petroleum hydrocracking by synthesizing nanoparticles of the zeolite ({approx}20-30 nm) inside nanoporous silicate or aluminosilicate hosts of similar pore diameters. The encapsulated zeolite nanoparticles are expected to possess pores of reduced diffusional path lengths, hence hydrocarbon substrates will diffuse in, are converted and the products quickly diffused out. This is expected to prevent over-reaction, hence minimizing pore blockage and active sites deactivation. In this phase of the project, research activities were focused on refining procedures to: (a) improve the synthesis of ordered, high surface area nanoporous silica, such as SBA-15, with expanded pore size using trimethylbenzene as additive to the parent SBA-15 synthesis mixture; and (b) reduce the particle size of zeolite Y such that they can be effectively incorporated into the nanoporous silicas. The synthesis of high surface ordered nanoporous silica containing enlarged pores of diameter of 25 nm (larger than the standard size of 8.4 nm) using trimethylbenzene as a pore size expander was accomplished. The synthesis of zeolite Y nanoparticles with median pore size of approximately 50 nm (smaller than the 80 nm typically obtained with TMAOH) using combined TMABr/TMAOH as organic additives was also accomplished.

  20. IMPROVED CATALYSTS FOR HEAVY OIL UPGRADING BASED ON ZEOLITE Y NANOPARTICLES ENCAPSULATED IN STABLE NANOPOROUS HOSTS

    SciTech Connect

    Conrad Ingram

    2003-09-03

    The focus of this project is to improve the catalytic performance of zeolite Y for petroleum hydrocracking by synthesizing nanoparticles of the zeolite ({approx}20-25 nm) inside nanoporous silicate or aluminosilicate hosts. The encapsulated zeolite nanoparticles are expected to possess reduced diffusional path lengths, hence hydrocarbon substrates will diffuse in, are converted and the products quickly diffused out. This is expected to prevent over-reaction and the blocking of the zeolite pores and active sites will be minimized. In this phase of the project, procedures for the synthesis of ordered nanoporous silica, such as SBA-15, using block copolymers and nonionic surfactant were successful reproduced. Expansion of the pores sizes of the nanoporous silica using trimethylbenzene is suggested based on shift in the major X-Ray Diffraction peak in the products to lower 2 angles compared with the parent SBA-15 material. The synthesis of ordered nanoporous materials with aluminum incorporated in the predominantly silicate framework was attempted but is not yet successful, and the procedures needs will be repeated and modified as necessary. Nanoparticles of zeolite Y of particle sizes in the range 40 nm to 120 nm were synthesized in the presence of TMAOH as the particle size controlling additive.

  1. Europium (II)-doped microporous zeolite derivatives with enhanced photoluminescence by isolating active luminescence centers.

    PubMed

    Yang, Xuyong; Tiam, Tan Swee; Yu, Xibin; Demir, Hilmi Volkan; Sun, Xiao Wei

    2011-11-01

    Solid-state reaction is the most common method for preparing luminescent materials. However, the luminescent dopants in the hosts tend to aggregate in the high-temperature annealing process, which causes adverse effect in photoluminescence. Herein, we report a novel europium (II)-doped zeolite derivative prepared by a combined ion-exchange and solid-state reaction method, in which the europium (II) ions are isolated to a large extent by the micropores of the zeolite. Excited by a broad ultraviolet band from 250 to 420 nm, a strong blue emission peaking at 450 nm was observed for these Eu-embedded zeolites annealed at 800 °C in a reducing atmosphere. The zeolite host with pores of molecular dimension was found to be an excellent host to isolate and stabilize the Eu(2+) ions. The as-obtained europium (II)-doped zeolite derivative showed an approximately 9 fold enhancement in blue emission compared to that of the general europium (II)-doped aluminosilicates obtained by conventional solid-state reaction, indicating that, by isolating active luminescence centers, it is promising to achieve highly luminescent materials. Also, the strong blue emission with broad UV excitation band suggests a potential candidate of phosphor for ultraviolet excited light-emitting diode.

  2. ZEOLITE CHARACTERIZATION TESTING

    SciTech Connect

    Jacobs, W; Herbert Nigg, H

    2007-09-13

    The Savannah River Site isolates tritium from its process streams for eventual recycling. This is done by catalyzing the formation of tritiated water (from process streams) and then sorbing that water on a 3A zeolite (molsieve) bed. The tritium is recovered by regenerating the saturated bed into a Mg-based water cracking unit. The process described has been in use for about 15 years. Recently chloride stress corrosion cracking (SCC) was noted in the system piping. This has resulted in the need to replace the corroded piping and associated molecular sieve beds. The source of chlorine has been debated and one possible source is the zeolite itself. Since new materials are being purchased for recently fabricated beds, a more comprehensive analysis protocol for characterizing zeolite has been developed. Tests on archived samples indicate the potential for mobile chloride species to be generated in the zeolite beds.

  3. Composite zeolite membranes

    DOEpatents

    Nenoff, Tina M.; Thoma, Steven G.; Ashley, Carol S.; Reed, Scott T.

    2002-01-01

    A new class of composite zeolite membranes and synthesis techniques therefor has been invented. These membranes are essentially defect-free, and exhibit large levels of transmembrane flux and of chemical and isotopic selectivity.

  4. Flexibility of zeolite frameworks

    NASA Astrophysics Data System (ADS)

    Kapko, Vitaliy; Treacy, Michael; Thorpe, Michael

    2009-03-01

    Zeolites are an important class of industrial catalysts because of their large internal surfaces and molecular-sieving properties. Recent geometric simulations (1) show that almost all of the known zeolites can exist without distortion of their tetrahedra within some range of densities, which we call the flexibility window. Within this window, the framework accommodates density changes by rotations about the shared tetrahedral corners. We argue that the presence of a flexibility window can be used as a topological criterion to select potential candidates for synthesis from millions of hypothetical structures. We also investigate the exceptions to the rule, as well as the shape of the flexibility window and the symmetric properties of zeolites inside it. (1) A. Sartbaeva, S.A. Wells, M.M.J. Treacy and M.F. Thorpe The flexibility window in zeolites, Nature Materials 5, 962-965 (2006); I. Rivin, commentary 931-932.

  5. Heterostructured layered aluminosilicate-itraconazole nanohybrid for drug delivery system.

    PubMed

    Yang, Jae-Hun; Jung, Hyun; Kim, Su Yeon; Yo, Chul Hyun; Choy, Jin-Ho

    2013-11-01

    A nanohybrid, consisting of layered aluminosilicate as a host material and itraconazole as a guest molecule, was successfully synthesized through the interfacial intercalation reaction across the boundary between water and water-immiscible liquid at the various pH. According to the powder X-ray diffraction pattern, the basal spacing of the intraconazole-layered aluminosilicate nanohybrid increased from 14.7 to 22.7 A depending on the pH of the aqueous suspension. The total amounts of itraconazole in the hybrids were determined to be 2.3-25.4 wt% by HPLC analysis. The in vivo pharmacokinetics study was performed in rats in order to compare the absorptions of itraconazole for the itraconazole-layered aluminosilicate nanohybrid and a commercial product, Sporanox. The pharmacokinetic data for the nanohybrid and Sporanox showed that the mean area under the plasma concentration-time curve (AUC, 2477 +/- 898 ng x hr/mL and 2630 +/- 953 ng x hr/mL, respectively) and maximum concentration (Cmax, 225.4 +/- 77.4 ng x hr/mL and 223.6 +/- 51.9 ng x hr/mL, respectively), were within the bioequivalence (BE) range. Therefore, we concluded that this drug-layered aluminosilicate nanohybrid system has a great potential for its application in formulation of poorly soluble drugs.

  6. A particulate isotopic standard of plutonium in an aluminosilicate matrix

    SciTech Connect

    Stoffels, J.J.; Cannon, W.C.; Robertson, D.M. )

    1991-01-01

    Plutonium isotopic microstandard particles have been produced for mass spectrometer calibration. The particles may also be useful as an elemental standard for calibration of electron and ion microprobe instruments. The standard consists of spherical, micrometer-size aluminosilicate particles loaded with plutonium of known isotopic distribution. The morphology, elemental composition, and plutonium isotopic composition of the particles have been characterized.

  7. Sodium Aluminosilicate Formation in Tank 43H Simulants

    SciTech Connect

    Wilmarth, W.R.; Walker, D.D.; Fink, S.D.

    1997-11-01

    This work studied the formation of a sodium aluminosilicate, Na{sub 8}Al{sub 6}Si{sub 6}O{sub 24}(NO{sub 3}){sub 2?4}H{sub 2}O, at 40{degree} 110{degree} C in simulated waste solutions with varied amounts of silicon and aluminum. The data agree well with literature solubility data for sodalite, the analogous chloride salt. The following conclusions result from this work: (1) The study shows, by calculation and experiments, that evaporation of the September 1997 Tank 43H inventory will only form minor quantities of the aluminosilicate. (2) The data indicate that the rate of formation of the nitrate enclathrated sodalite solid at these temperatures falls within the residence time ({lt}; 4 h) of liquid in the evaporator. (3) The silicon in entrained Frit 200 transferred to the evaporator with the Tank 43H salt solution will quantitatively convert to the sodium aluminosilicate. One kilogram of Frit 200 produces 2.1 kg of the sodium aluminosilicate.

  8. Hydraulic conductivity of compacted zeolites.

    PubMed

    Oren, A Hakan; Ozdamar, Tuğçe

    2013-06-01

    Hydraulic conductivities of compacted zeolites were investigated as a function of compaction water content and zeolite particle size. Initially, the compaction characteristics of zeolites were determined. The compaction test results showed that maximum dry unit weight (γ(dmax)) of fine zeolite was greater than that of granular zeolites. The γ(dmax) of compacted zeolites was between 1.01 and 1.17 Mg m(-3) and optimum water content (w(opt)) was between 38% and 53%. Regardless of zeolite particle size, compacted zeolites had low γ(dmax) and high w(opt) when compared with compacted natural soils. Then, hydraulic conductivity tests were run on compacted zeolites. The hydraulic conductivity values were within the range of 2.0 × 10(-3) cm s(-1) to 1.1 × 10(-7) cm s(-1). Hydraulic conductivity of all compacted zeolites decreased almost 50 times as the water content increased. It is noteworthy that hydraulic conductivity of compacted zeolite was strongly dependent on the zeolite particle size. The hydraulic conductivity decreased almost three orders of magnitude up to 39% fine content; then, it remained almost unchanged beyond 39%. Only one report was found in the literature on the hydraulic conductivity of compacted zeolite, which is in agreement with the findings of this study.

  9. Structural analysis of hierarchically organized zeolites

    PubMed Central

    Mitchell, Sharon; Pinar, Ana B.; Kenvin, Jeffrey; Crivelli, Paolo; Kärger, Jörg; Pérez-Ramírez, Javier

    2015-01-01

    Advances in materials synthesis bring about many opportunities for technological applications, but are often accompanied by unprecedented complexity. This is clearly illustrated by the case of hierarchically organized zeolite catalysts, a class of crystalline microporous solids that has been revolutionized by the engineering of multilevel pore architectures, which combine unique chemical functionality with efficient molecular transport. Three key attributes, the crystal, the pore and the active site structure, can be expected to dominate the design process. This review examines the adequacy of the palette of techniques applied to characterize these distinguishing features and their catalytic impact. PMID:26482337

  10. Synthesis of zeolite Li-ABW from fly ash by fusion method.

    PubMed

    Yao, Z T; Xia, M S; Ye, Y; Zhang, L

    2009-10-30

    The zeolite Li-ABW was synthesized by fusion method using fly ash as raw material. It comprised alkaline fusion followed by hydrothermal treatment in LiOH x H2O medium. Crystallinity of zeolite as high as 97.8% was attained under the following conditions: LiOH x H2O concentration, 3M; hydrothermal temperature, 180 degrees C; the corresponding aging time, 12 h. The content of Li-ABW increased at the expense of lithium aluminum silicate or quartz with an increase of LiOH x H2O concentration. With increasing hydrothermal temperature and aging time, the soluble species re-crystallized and crystalline phase transformation between different zeolites was observed. Scanning electron microscopy (SEM) observation revealed that the obtained zeolite Li-ABW was a rod-like crystal. The pore size distribution curve indicated the presence of mesopores.

  11. Preparation of functionalized zeolitic frameworks

    DOEpatents

    Yaghi, Omar M; Furukawa, Hiroyasu; Wang, Bo

    2013-07-09

    The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

  12. Preparation of functionalized zeolitic frameworks

    DOEpatents

    Yaghi, Omar M; Hayashi, Hideki; Banerjee, Rahul; Park, Kyo Sung; Wang, Bo; Cote, Adrien P

    2012-11-20

    The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

  13. Preparation of functionalized zeolitic frameworks

    SciTech Connect

    Yaghi, Omar M.; Hayashi, Hideki; Banerjee, Rahul; Park, Kyo Sung; Wang, Bo; Cote, Adrien P.

    2014-08-19

    The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

  14. The influence of using Jordanian natural zeolite on the adsorption, physical, and mechanical properties of geopolymers products.

    PubMed

    Yousef, Rushdi Ibrahim; El-Eswed, Bassam; Alshaaer, Mazen; Khalili, Fawwaz; Khoury, Hani

    2009-06-15

    Geopolymers consist of an amorphous, three-dimensional structure resulting from the polymerization of aluminosilicate monomers that result from dissolution of kaolin in an alkaline solution at temperatures around 80 degrees C. One potential use of geopolymers is as Portland cement replacement. It will be of great importance to provide a geopolymer with suitable mechanical properties for the purpose of water storage and high adsorption capacity towards pollutants. The aim of this work is to investigate the effect of using Jordanian zeolitic tuff as filler on the mechanical performance and on the adsorption capacity of the geopolymers products. Jordanian zeolitic tuff is inexpensive and is known to have high adsorption capacity. The results confirmed that this natural zeolitic tuff can be used as a filler of stable geopolymers with high mechanical properties and high adsorption capacity towards methylene blue and Cu(II) ions. The XRD measurements showed that the phillipsite peaks (major mineral constituent of Jordanian zeolite) were disappeared upon geopolymerization. The zeolite-based geopolymers revealed high compressive strength compared to reference geopolymers that employ sand as filler. Adsorption experiments showed that among different geopolymers prepared, the zeolite-based geopolymers have the highest adsorption capacity towards methylene blue and copper(II) ions.

  15. Determining the aluminium occupancy on the active T-sites in zeolites using X-ray standing waves

    NASA Astrophysics Data System (ADS)

    van Bokhoven, Jeroen A.; Lee, Tien-Lin; Drakopoulos, Michael; Lamberti, Carlo; Thieß, Sebastian; Zegenhagen, Jörg

    2008-07-01

    Zeolites are microporous crystalline materials that find wide application in industry, for example, as catalysts and gas separators, and in our daily life, for example, as adsorbents or as ion exchangers in laundry detergents. The tetrahedrally coordinated silicon and aluminium atoms in the zeolite unit cell occupy the so-called crystallographic T-sites. Besides their pore size, the occupation of specific T-sites by the aluminium atoms determines the performance of the zeolites. Despite its importance, the distribution of aluminium over the crystallographic T-sites remains one of the most challenging, unresolved issues in zeolite science. Here, we report how to determine unambiguously and directly the distribution of aluminium in zeolites by means of the X-ray standing wave technique using brilliant, focused X-rays from a third-generation synchrotron source. We report in detail the analysis of the aluminium distribution in scolecite, which demonstrates how the aluminium occupancy in zeolites can systematically be determined.

  16. IMPROVED CATALYSTS FOR HEAVY OIL UPGRADING BASED ON ZEOLITE Y NANOPARTICLES ENCAPSULATED STABLE NANOPOROUS HOST

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2005-03-21

    The objectives of this project are to synthesis nanocrystals of highly acidic zeolite Y, encapsulate them within the channels of mesoporous (nanoporous) silicates or nanoporous organosilicates and evaluate the ''zeolite Y/Nanoporous host'' composites as catalysts for the upgrading of heavy petroleum feedstocks. Our results to date are summarized as follows. The synthesis of high surface ordered nanoporous silica of expanded pore diameter of 25 nm (larger than the standard size of 8.4 nm) using trimethylbenzene as a pore size expander was accomplished. The synthesis of zeolite Y nanoparticles with median pore size of approximately 50 nm (smaller than the 80 nm typically obtained with TMAOH) using combined TMABr/TMAOH as organic additives was also accomplished. The successful synthesis of zeoliteY/Nanoporous host composite materials by sequential combination of zeolite precursors and nanoporous material precursor mixtures was implied based on results from various characterization techniques such as X-Ray diffraction, infrared spectra, thermal analysis, porosimetry data. The resulting materials showed pore sizes up to 11 nm, and infrared band at 570 cm{sup -1} suggesting the presence of both phases. Work in the immediate future will be focused on the following three areas: (1) Further characterization of all-silica and aluminosilicate mesoporous materials with expanded pore sizes up to 30 nm will continue; (2) Research efforts to reduce the average particle size of zeolite nanoparticles down to 35-30 nm will continue; (3) Further synthesis of polymer-SBA15 nanocomposites will be conducted by changing the amount and chemistry of the zeolitic precursors added; and (4) Investigation on the catalytic properties of the materials using probe catalytic reactions (such as cumene cracking), followed by catalytic testing for heavy oil conversion.

  17. Changes in the Vibrational Spectra of Zeolites Due to Sorption of Heavy Metal Cations

    NASA Astrophysics Data System (ADS)

    Król, M.; Mozgawa, W.; Barczyk, K.; Bajda, T.; Kozanecki, M.

    2013-11-01

    This work presents the results of spectroscopic (MIR and Raman) studies of zeolite structures after immobilization of heavy metal cations from aqueous solutions. The sorption of Ag+, Cu2+, Cd2+, Pb2+, Zn2+, and Cr3+ ions has been conducted on zeolites belonging to different structural groups, i.e., sodium forms of natural chabazite, mordenite, ferrierite, and clinoptilolite, as well as on synthetic zeolite Y. Systematic changes in intensities and positions of the bands corresponding to the characteristic ring vibrations have been observed in the measured spectra. The most visible changes are observed in the FT-IR spectra of the samples in the range of 850-450 cm-1, and in the Raman spectra in the range of 600-250 cm-1. Depending on the zeolite structure, the bands, which can be regarded as a kind of indicator of ion exchange, were indentifi ed. For example, in the case of IR spectra, these bands are at 766, 703, 648, 578, and 506 cm-1 for zeolite Y, at 733 and 560 cm-1 for mordenite, at 675 cm-1 for clinoptilolite, etc. The degree of changes depends on both the type of cation and its concentration in the initial solution. This is connected with the way of binding of metal ions to the zeolite aluminosilicate framework, i.e., a proportion of the ion exchange and chemisorption in the process. Cations mainly undergoing ion exchange, such as Cd2+ or Pb2+, have the greatest impact on the character of the spectra. On the other hand, Cr3+ ions practically do not modify the spectra of zeolites. Results of IR and Raman spectroscopic studies have been compared with those obtained by atomic absorption spectroscopy (AAS), from which the proportion of ion exchange to chemisorption in the process and the effective cation exchange capacity of the individual samples have been estimated.

  18. Phosphorus promotion and poisoning in zeolite-based materials: synthesis, characterisation and catalysis

    PubMed Central

    van der Bij, Hendrik E.

    2015-01-01

    Phosphorus and microporous aluminosilicates, better known as zeolites, have a unique but poorly understood relationship. For example, phosphatation of the industrially important zeolite H-ZSM-5 is a well-known, relatively inexpensive and seemingly straightforward post-synthetic modification applied by the chemical industry not only to alter its hydrothermal stability and acidity, but also to increase its selectivity towards light olefins in hydrocarbon catalysis. On the other hand, phosphorus poisoning of zeolite-based catalysts, which are used for removing nitrogen oxides from exhaust fuels, poses a problem for their use in diesel engine catalysts. Despite the wide impact of phosphorus–zeolite chemistry, the exact physicochemical processes that take place require a more profound understanding. This review article provides the reader with a comprehensive and state-of-the-art overview of the academic literature, from the first reports in the late 1970s until the most recent studies. In the first part an in-depth analysis is undertaken, which will reveal universal physicochemical and structural effects of phosphorus–zeolite chemistry on the framework structure, accessibility, and strength of acid sites. The second part discusses the hydrothermal stability of zeolites and clarifies the promotional role that phosphorus plays. The third part of the review paper links the structural and physicochemical effects of phosphorus on zeolite materials with their catalytic performance in a variety of catalytic processes, including alkylation of aromatics, catalytic cracking, methanol-to-hydrocarbon processing, dehydration of bioalcohol, and ammonia selective catalytic reduction (SCR) of NOx. Based on these insights, we discuss potential applications and important directions for further research. PMID:26051875

  19. Phosphorus promotion and poisoning in zeolite-based materials: synthesis, characterisation and catalysis.

    PubMed

    van der Bij, Hendrik E; Weckhuysen, Bert M

    2015-10-21

    Phosphorus and microporous aluminosilicates, better known as zeolites, have a unique but poorly understood relationship. For example, phosphatation of the industrially important zeolite H-ZSM-5 is a well-known, relatively inexpensive and seemingly straightforward post-synthetic modification applied by the chemical industry not only to alter its hydrothermal stability and acidity, but also to increase its selectivity towards light olefins in hydrocarbon catalysis. On the other hand, phosphorus poisoning of zeolite-based catalysts, which are used for removing nitrogen oxides from exhaust fuels, poses a problem for their use in diesel engine catalysts. Despite the wide impact of phosphorus-zeolite chemistry, the exact physicochemical processes that take place require a more profound understanding. This review article provides the reader with a comprehensive and state-of-the-art overview of the academic literature, from the first reports in the late 1970s until the most recent studies. In the first part an in-depth analysis is undertaken, which will reveal universal physicochemical and structural effects of phosphorus-zeolite chemistry on the framework structure, accessibility, and strength of acid sites. The second part discusses the hydrothermal stability of zeolites and clarifies the promotional role that phosphorus plays. The third part of the review paper links the structural and physicochemical effects of phosphorus on zeolite materials with their catalytic performance in a variety of catalytic processes, including alkylation of aromatics, catalytic cracking, methanol-to-hydrocarbon processing, dehydration of bioalcohol, and ammonia selective catalytic reduction (SCR) of NOx. Based on these insights, we discuss potential applications and important directions for further research.

  20. Effect of synthetic conditions on the adsorption properties of the resulting offretite-type zeolite

    NASA Astrophysics Data System (ADS)

    Gorshunova, K. K.; Travkina, O. S.; Kapustin, G. I.; Kustov, L. M.; Pavlov, M. L.; Kutepov, B. I.

    2015-05-01

    The effect of the nature of the silicon-containing component of the reaction mixture and that of the crystallization conditions on characteristics of the resulting offretite-type zeolite powder, including its degree of crystallinity, particle-size distribution, and adsorption properties with respect to toluene, cyclohexane, n-hexane, and water molecules, are considered. The thermal desorption of toluene from cationic forms of the offretite-type zeolite is reported. The K-forms of this zeolite can retain adsorbed toluene up to 300-400°C.

  1. Sustained release of doxorubicin from zeolite magnetite nanocomposites prepared by mechanical activation

    NASA Astrophysics Data System (ADS)

    Arruebo, Manuel; Fernández-Pacheco, Rodrigo; Irusta, Silvia; Arbiol, Jordi; Ibarra, M. Ricardo; Santamaría, Jesús

    2006-08-01

    Nanocomposites consisting of magnetite and FAU zeolite with a high surface area and adsorption capacity have been prepared by mechanical activation using high-energy milling at room temperature. FTIR results, as well as HRTEM, EFTEM, and XPS measurements, show that the resulting magnetic nanoparticles are covered by a thin aluminosilicate coating. A saturation magnetization as high as 16 emu g-1 and 94.2 Oe of coercivity were observed for the obtained composites. The main advantages of this synthesis procedure are (i) simplicity of the preparation procedure, (ii) prevention of agglomeration of the magnetite nanoparticles to a large extent, and (iii) absence of free magnetite outside the zeolitic matrix. In addition, in vitro experiments revealed that the nanoparticles prepared were able to store and release substantial amounts of doxorubicin. In view of these advantages, these magnetic nanoparticles can be considered as potential candidates for drug-delivery applications.

  2. The physicochemical properties of micro/mesoporous materials prepared by the recrystallization of zeolite BEA

    NASA Astrophysics Data System (ADS)

    Ordomskii, V. V.; Monakhova, Yu. V.; Knyazeva, E. E.; Nesterenko, N. S.; Ivanova, I. I.

    2009-06-01

    Micro-mesoporous materials with various ratios between micro- and mesopores were prepared by the recrystallization of zeolite BEA in an alkaline medium in the presence of cetyltrimethylammonium bromide. The materials were characterized by X-ray diffraction, low-temperature nitrogen adsorption, and IR spectroscopy. Recrystallization under mild conditions did not cause substantial changes in the number of acid centers but increased the accessibility of acid centers to large-sized molecules because of the creation of mesopores. An increase in the degree of recrystallization caused first partial and then complete zeolite transformation into MSM-41 mesoporous aluminosilicate, which was accompanied by a decrease in the number of acid centers. The IR spectra were used to determine the diffusion coefficients of cumene in the initial and recrystallized samples. Recrystallization increased the diffusion coefficient by 3-4 times.

  3. Synthesis and characterization of zeolites prepared from industrial fly ash.

    PubMed

    Franus, Wojciech; Wdowin, Magdalena; Franus, Małgorzata

    2014-09-01

    In this paper, we present the possibility of using fly ash to produce synthetic zeolites. The synthesis class F fly ash from the Stalowa Wola SA heat and power plant was subjected to 24 h hydrothermal reaction with sodium hydroxide. Depending on the reaction conditions, three types of synthetic zeolites were formed: Na-X (20 g fly ash, 0.5 dm(3) of 3 mol · dm(-3) NaOH, 75 °C), Na-P1 (20 g fly ash, 0.5 dm(3) of 3 mol · dm(-3) NaOH, 95 °C), and sodalite (20 g fly ash, 0.8 dm(3) of 5 mol · dm(-3) NaOH + 0.4 dm(3) of 3 mol · dm(-3) NaCl, 95 °C). As synthesized materials were characterized to obtain mineral composition (X-ray diffractometry, Scanning electron microscopy-energy dispersive spectrometry), adsorption properties (Brunauer-Emmett-Teller surface area, N2 isotherm adsorption/desorption), and ion exchange capacity. The most effective reaction for zeolite preparation was when sodalite was formed and the quantitative content of zeolite from X-ray diffractometry was 90 wt%, compared with 70 wt% for the Na-X and 75 wt% for the Na-P1. Residues from each synthesis reaction were the following: mullite, quartz, and the remains of amorphous aluminosilicate glass. The best zeolitic material as characterized by highest specific surface area was Na-X at almost 166 m(2) · g(-1), while for the Na-P1 and sodalite it was 71 and 33 m(2) · g(-1), respectively. The ion exchange capacity decreased in the following order: Na-X at 1.8 meq · g(-1), Na-P1 at 0.72 meq · g(-1), and sodalite at 0.56 meq · g(-1). The resulting zeolites are competitive for commercially available materials and are used as ion exchangers in industrial wastewater and soil decontamination.

  4. Synthesis, deposition and characterization of magnesium hydroxide nanostructures on zeolite 4A

    SciTech Connect

    Koh, Pei-Yoong; Yan, Jing; Ward, Jason; Koros, William J.; Teja, Amyn S.; Xu, Bo

    2011-03-15

    Research highlights: {yields} Reports a simple precipitation-growth method to produce nanostructures of Mg(OH){sub 2} on the surface of zeolite 4A. {yields} Able to control the growth of the nanostructures by manipulating the experimental procedure. {yields} Able to deposit Mg(OH){sub 2} onto specific sites namely bridging hydroxyl protons (SiOHAl) on the surface of zeolite 4A. -- Abstract: The precipitation and self-assembly of magnesium hydroxide Mg(OH){sub 2} nanopetals on dispersed zeolite 4A particles was investigated. Mg(OH){sub 2}/zeolite nanocomposites were produced from magnesium chloride solutions and characterized via X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Fourier transform infrared analysis (FTIR), and solid state NMR. It was determined that Mg(OH){sub 2} interacted with bridging hydroxyl protons (SiOHAl) on the zeolite surface, but not with silanol or aluminol groups. NMR analysis showed that 13% of the tetrahedral Al sites on the zeolite were converted to octahedral Al. The zeolite structure and crystallinity remained intact after treatment, and no dealumination reactions were detected. This suggests that the deposition-precipitation process at ambient conditions is a facile method for controlling Mg(OH){sub 2} nanostructures on zeolites.

  5. Adsorption of aqueous Zn(II) species on synthetic zeolites

    NASA Astrophysics Data System (ADS)

    Badillo-Almaraz, Véronica; Trocellier, Patrick; Dávila-Rangel, Ignacio

    2003-09-01

    To supply a good quality drinkable water tends to become a strategic task in both developed and under development countries in the world due to the number of potential contamination sources. One of the major problems is derived from the presence of heavy toxic metals like zinc or lead resulting from industrial activities. Zeolites are known as very efficient mineral substrates for fixing aqueous ionic species through their wide range of channels present in the crystalline structure and due to their strong surface reactivity. MicroPIXE coupled with microRBS (3.05 MeV 4He + ions) have been used to quantify the incorporation of zinc within two commercial zeolites containing alkali elements (zeolite X and clinoptilolite) in the concentration range of: 0.0002-0.05 M at neutral pH. At the beginning of the interaction between zeolite and Zn(II) solution, the adsorption process exhibits a direct proportionality between the content of zinc fixed on the mineral substrate and the aqueous concentration up to 0.01 M. Beyond this point a saturation effect seems to occur, indicating the strong decrease of available adsorption sites. Sodium or potassium ions are probably exchanged with Zn(II) ions during this process. The compared behaviour of the two zeolites is then discussed in terms of kinetic effects based on ionic radius values. A co-adsorption test carried on with a 50-50% Zn(II) 0.001 M-Pb(II) 0.001 M solution shows that lead does not occupy the same sites as zinc because the content of zinc fixed on the zeolite sample exactly corresponds to the result obtained with a pure 0.001 M Zn(II) solution. All these data clearly showed that zeolite surface reactivity is greatly influenced by the mineral cage-like structure and particularly the presence of pockets, spaces and channels.

  6. XPS study of protein adsorption onto nanocrystalline aluminosilicate microparticles

    NASA Astrophysics Data System (ADS)

    Vanea, E.; Simon, V.

    2011-01-01

    X-ray photoelectron spectroscopy (XPS) was used to study the interaction of two different sized proteins, bovine serum albumin (BSA) and fibrinogen, with an aluminosilicate system containing yttrium and iron that is a potential biomaterial. Serum albumin and fibrinogen are two major plasma proteins and the most relevant proteins adsorbed on the surface of biomaterials in blood contact. The aluminosilicate samples were incubated for several exposure times, up to 24 h, in simulated body fluid enriched with BSA, and in buffered fibrinogen solution. Time dependence of proteins adsorption onto surface of the investigated samples is reflected by the evolution of the new N 1s photoelectron peak and by the modification of C 1s core-level spectra recorded from the samples immersed in protein solution.

  7. A high acid mesoporous USY zeolite prepared by alumination

    NASA Astrophysics Data System (ADS)

    Ma, Jinghong; Kang, Yuhong; Ma, Ning; Hao, Wenming; Wang, Yan; Li, Ruifeng

    2013-01-01

    A high-acidity HUSY zeolite with mesoporous structure was prepared by alumination with a dilute aqueous NaAlO2 solution and characterized by XRD, N2 adsorption, IR framework vibration and 29Si MAS NMR methods. The results indicated the extra-framework aluminum was reinserted into the tetrahedral framework through isomorphic substitution of framework Si (0Al) sites by Al ions, whereas the crystal and micropore structure were unaltered. FTIR spectra of hydroxyl vibrations and pyridine adsorbed on realuminated zeolites showed that the number of Brønsted acid sites and strong Lewis acid sites increased whereas weak Lewis acid sites decreased twice. The mesoporous structure composed of inter-and intra-crystalline pores in the aluminated HUSY increased the external surface area of the zeolite, improving accessibility of molecules to the active sites and enhancing its catalytic ability. The realuminated HUSY zeolite supported with Ru catalyst exhibited a higher catalytic activity for benzene hydrogenation than the parent HUSY zeolite; the reaction rate in comparison to the mesozeolite increased by 5.5 times.

  8. The structural behavior of ferric and ferrous iron in aluminosilicate glass near meta-aluminosilicate joins

    NASA Astrophysics Data System (ADS)

    Mysen, Bjorn O.

    2006-05-01

    Iron-57 resonant absorption Mössbauer spectroscopy was used to describe the redox relations and structural roles of Fe 3+ and Fe 2+ in meta-aluminosilicate glasses. Melts were formed at 1500 °C in equilibrium with air and quenched to glass in liquid H 2O with quenching rates exceeding 200 °C/s. The aluminosilicate compositions were NaAlSi 2O 6, Ca 0.5AlSi 2O 6, and Mg 0.5AlSi 2O 6. Iron oxide was added in the form of Fe 2O 3, NaFeO 2, CaFe 2O 4, and MgFe 2O 4 with total iron oxide content in the range ˜0.9 to ˜5.6 mol% as Fe 2O 3. The Mössbauer spectra, which were deconvoluted by assuming Gaussian distributions of the hyperfine field, are consistent with one absorption doublet of Fe 2+ and one of Fe 3+. From the area ratios of the Fe 2+ and Fe 3+ absorption doublets, with corrections for differences in recoil-fractions of Fe 3+ and Fe 2+, the Fe 3+/ΣFe is positively correlated with increasing total iron content and with decreasing ionization potential of the alkali and alkaline earth cation. There is a distribution of hyperfine parameters from the Mössbauer spectra of these glasses. The maximum in the isomer shift distribution function of Fe 3+, δFe 3+, ranges from about 0.25 to 0.49 mm/s (at 298 K relative to Fe metal) with the quadrupole splitting maximum, ΔFe 3+, ranging from ˜1.2 to ˜1.6 mm/s. Both δFe 3+ and δFe 2+ are negatively correlated with total iron oxide content and Fe 3+/ΣFe. The dominant oxygen coordination number Fe 3+ changes from 4 to 6 with decreasing Fe 3+/ΣFe. The distortion of the Fe 3+-O polyhedra of the quenched melts (glasses) decreases as the Fe 3+/ΣFe increases. These polyhedra do, however, coexist with lesser proportions of polyhedra with different oxygen coordination numbers. The δFe 2+ and ΔFe 2+ distribution maxima at 298 K range from ˜0.95 to 1.15 mm/s and 1.9 to 2.0 mm/s, respectively, and decrease with increasing Fe 3+/ΣFe. We suggest that these hyperfine parameter values for the most part are more consistent

  9. Zeolites and Catalysis

    DTIC Science & Technology

    1999-12-15

    financial together as shown in the top line of Fig. 1, the market size (not in terms of tonnage) with an cubo-octahedron, also referred to as a sodalite ...various zeolite structures derive. If This review will cover the basic principles of sodalite units are connected via their hexagonal faces zeolite... Sodalite Unit 0.57 nm x’.1nm ZS - 0 .56 nm --- x 0.53 nm Si0 4 /2 - or -~ ~ IZSM-50.5n A10 dra - Silicalite-1 x 0.51 nm Tetrahedra X Pentasil Unit 0.45 nmx

  10. Hard x-ray nanotomography of amorphous aluminosilicate cements.

    SciTech Connect

    Provis, J. L.; Rose, V.; Winarski, R. P.; van Deventer, J. S. J.

    2011-08-01

    Nanotomographic reconstruction of a sample of low-CO{sub 2} 'geopolymer' cement provides the first three-dimensional view of the pore structure of the aluminosilicate geopolymer gel, as well as evidence for direct binding of geopolymer gel onto unreacted fly ash precursor particles. This is central to understanding and optimizing the durability of concretes made using this new class of binder, and demonstrates the value of nanotomography in providing a three-dimensional view of nanoporous inorganic materials.

  11. Development of Li+ alumino-silicate ion source

    SciTech Connect

    Roy, P.K.; Seidl, P.A.; Waldron, W.; Greenway, W.; Lidia, S.; Anders, A.; Kwan, J.

    2009-04-21

    To uniformly heat targets to electron-volt temperatures for the study of warm dense matter, one strategy is to deposit most of the ion energy at the peak of energy loss (dE/dx) with a low (E< 5 MeV) kinetic energy beam and a thin target[1]. Lower mass ions have a peak dE/dx at a lower kinetic energy. To this end, a small lithium (Li+) alumino-silicate source has been fabricated, and its emission limit has been measured. These surface ionization sources are heated to 1000-1150 C where they preferentially emit singly ionized alkali ions. Alumino-silicates sources of K+ and Cs+ have been used extensively in beam experiments, but there are additional challenges for the preparation of high-quality Li+ sources: There are tighter tolerances in preparing and sintering the alumino-silicate to the substrate to produce an emitter that gives uniform ion emission, sufficient current density and low beam emittance. We report on recent measurements ofhigh ( up to 35 mA/cm2) current density from a Li+ source. Ion species identification of possible contaminants is being verified with a Wien (E x B) filter, and via time-of-flight.

  12. CRYSTALLINE DESOXYRIBONUCLEASE

    PubMed Central

    Kunitz, M.

    1950-01-01

    A crystalline enzyme capable of digesting thymus nucleic acid (desoxyribonucleic acid) has been isolated from fresh beef pancreas. The enzyme called "desoxyribonuclease" is a protein of the albumin type. Its molecular weight is about 60,000 and its isoelectric point is near pH 5.0. It contains about 8 per cent tyrosine and 2 per cent tryptophane. It is readily denatured by heat. The denaturation is reversible if heated in dilute acid at pH about 3.0. The digestion of thymus nucleic acid by crystalline desoxyribonuclease is accompanied by a gradual increase in the specific absorption of ultraviolet light by the acid. The spectrophotometric measurement of the rate of increase in the light absorption can be conveniently used as a general method for estimating desoxyribonuclease activity. Details are given of the method for isolation of crystalline desoxyribonuclease and of the spectrophotometric procedure for the measurement of desoxyribonuclease activity. PMID:15406373

  13. Pioneering In Situ Recrystallization during Bead Milling: A Top-down Approach to Prepare Zeolite A Nanocrystals.

    PubMed

    Anand, Chokkalingam; Yamaguchi, Yudai; Liu, Zhendong; Ibe, Sayoko; Elangovan, Shanmugam P; Ishii, Toshihiro; Ishikawa, Tsuyoshi; Endo, Akira; Okubo, Tatsuya; Wakihara, Toru

    2016-07-05

    Top-down approach has been viewed as an efficient and straightforward method to prepare nanosized zeolites. Yet, the mechanical breaking of zeolite causes amorphization, which usually requires a post-milling recrystallization to obtain fully crystalline nanoparticles. Herein we present a facile methodology to prepare zeolite nanocrystals, where milling and recrystallization can be performed in situ. A milling apparatus specially designed to work under conditions of high alkalinity and temperature enables the in situ recrystallization during milling. Taking zeolite A as an example, we demonstrate its size reduction from ~3 μm to 66 nm in 30 min, which is quite faster than previous methods reported. Three functions, viz., miniaturization, amorphization and recrystallization were found to take effect concurrently during this one-pot process. The dynamic balance between these three functions was achieved by adjusting the milling period and temperature, which lead to the tuning of zeolite A particle size. Particle size and crystallinity of the zeolite A nanocrystals were confirmed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and water adsorption-desorption. This work presents a pioneering advancement in this field of nanosized zeolites, and will facilitate the mass production as well as boost the wide applications of nanosized zeolites.

  14. Pioneering In Situ Recrystallization during Bead Milling: A Top-down Approach to Prepare Zeolite A Nanocrystals

    PubMed Central

    Anand, Chokkalingam; Yamaguchi, Yudai; Liu, Zhendong; Ibe, Sayoko; Elangovan, Shanmugam P.; Ishii, Toshihiro; Ishikawa, Tsuyoshi; Endo, Akira; Okubo, Tatsuya; Wakihara, Toru

    2016-01-01

    Top-down approach has been viewed as an efficient and straightforward method to prepare nanosized zeolites. Yet, the mechanical breaking of zeolite causes amorphization, which usually requires a post-milling recrystallization to obtain fully crystalline nanoparticles. Herein we present a facile methodology to prepare zeolite nanocrystals, where milling and recrystallization can be performed in situ. A milling apparatus specially designed to work under conditions of high alkalinity and temperature enables the in situ recrystallization during milling. Taking zeolite A as an example, we demonstrate its size reduction from ~3 μm to 66 nm in 30 min, which is quite faster than previous methods reported. Three functions, viz., miniaturization, amorphization and recrystallization were found to take effect concurrently during this one-pot process. The dynamic balance between these three functions was achieved by adjusting the milling period and temperature, which lead to the tuning of zeolite A particle size. Particle size and crystallinity of the zeolite A nanocrystals were confirmed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and water adsorption-desorption. This work presents a pioneering advancement in this field of nanosized zeolites, and will facilitate the mass production as well as boost the wide applications of nanosized zeolites. PMID:27378145

  15. Pioneering In Situ Recrystallization during Bead Milling: A Top-down Approach to Prepare Zeolite A Nanocrystals

    NASA Astrophysics Data System (ADS)

    Anand, Chokkalingam; Yamaguchi, Yudai; Liu, Zhendong; Ibe, Sayoko; Elangovan, Shanmugam P.; Ishii, Toshihiro; Ishikawa, Tsuyoshi; Endo, Akira; Okubo, Tatsuya; Wakihara, Toru

    2016-07-01

    Top-down approach has been viewed as an efficient and straightforward method to prepare nanosized zeolites. Yet, the mechanical breaking of zeolite causes amorphization, which usually requires a post-milling recrystallization to obtain fully crystalline nanoparticles. Herein we present a facile methodology to prepare zeolite nanocrystals, where milling and recrystallization can be performed in situ. A milling apparatus specially designed to work under conditions of high alkalinity and temperature enables the in situ recrystallization during milling. Taking zeolite A as an example, we demonstrate its size reduction from ~3 μm to 66 nm in 30 min, which is quite faster than previous methods reported. Three functions, viz., miniaturization, amorphization and recrystallization were found to take effect concurrently during this one-pot process. The dynamic balance between these three functions was achieved by adjusting the milling period and temperature, which lead to the tuning of zeolite A particle size. Particle size and crystallinity of the zeolite A nanocrystals were confirmed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and water adsorption-desorption. This work presents a pioneering advancement in this field of nanosized zeolites, and will facilitate the mass production as well as boost the wide applications of nanosized zeolites.

  16. Determination of the crystalline structure of scale solids from the 16H evaporator gravity drain line to tank 38H

    SciTech Connect

    Oji, L. N.

    2015-10-01

    August 2015, scale solids from the 16H Evaporator Gravity Drain Line (GDL) to the Tank 38H were delivered to SRNL for analysis. The desired analytical goal was to identify and confirm the crystalline structure of the scale material and determine if the form of the aluminosilicate mineral was consistent with previous analysis of the scale material from the GDL.

  17. Mechanisms of zinc incorporation in aluminosilicate crystalline structures and the leaching behaviour of product phases.

    PubMed

    Tang, Yuanyuan; Shih, Kaimin

    2015-01-01

    This study quantitatively evaluates a waste-to-resource strategy of blending zinc-laden sludge and clay material for low-cost ceramic products. Using ZnO as the simulated zinc-laden sludge to sinter with kaolinite, both zinc aluminate spinel (ZnAl₂O₄) and willemite (Zn₂SiO₄) phases were formed during the sintering process. To analyse the details of zinc incorporation reactions, γ-Al₂O₃and quartz were further used as precursors to observe ZnAl₂O₄and Zn₂SiO₄formations. By firing the ZnO mixtures and their corresponding precursors at 750-1350°C for 3 h, the efficiency of zinc transformation was determined through Rietveld refinement analyses of X-ray diffraction data. The results also show different incorporation behaviour for kaolinite and mullite precursors during the formation of ZnAl2O₄and Zn2SiO₄in the system. In addition, with a competitive formation between ZnAl₂O₄and Zn₂SiO₄, the ZnAl₂O₄spinel phase is predominant at temperatures higher than 1050°C. This study used a prolonged leaching test modified from the US Environmental Protection Agency's toxicity characteristic leaching procedure to evaluate ZnO, ZnAl₂O₄, and Zn₂SiO₄product phases. The zinc concentrations in ZnO and Zn₂SiO₄leachates were about two orders of magnitude higher than that of ZnAl₂O₄ leachate at the end of the experiment, indicating that ZnAl₂O₄formation is the preferred stabilization mechanism for incorporating zinc in ceramic products.

  18. Fiber-optic exhaust-gas sensor based on the fluorescence characteristics of Cu containing zeolites

    NASA Astrophysics Data System (ADS)

    Remillard, Jeffrey

    2000-03-01

    A single catalyst in the exhaust system can reduce the concentration of toxic gases emitted by automobiles if the engine is operated close to the stoichiometric air-fuel ratio. This is accomplished through the use of an electrochemical oxygen sensor in the exhaust stream. Near the stoichiometric point, this sensor produces a step-function response when the exhaust gas transitions from an oxygen-poor to an oxygen-rich condition. This talk describes a different kind of sensor based on the use of copper-containing zeolites that produces a proportional output. Zeolites are a class of aluminosilicate materials that have an open 3D structure containing channels and cavities. The Al sites are negatively charged and are generally compensated by cations present during formation of the zeolite. Our experiments use a zeolite designated Cu-ZSM-5, which has the protons originally present in the ZSM-5 material replaced with cupric (Cu^+2) ions. Exposure of this zeolite to a reducing gas results in the conversion of some cupric ions to cuprous (Cu^+1) ions. Subsequent exposure of the zeolite to an oxidizing gas reverses this reaction. The use of this material as a gas sensor is based on the observation that cuprous ions produce a green fluorescent emission when exposed to blue light, whereas no fluorescence is observed from cupric ions. Monitoring the fluorescence of Cu-ZSM-5 placed in a gas stream can thus provide information on the gas's reductant-to-oxidant ratio. We present the results of high temperature in-situ fluorescence spectra, intensity, and reponse-time measurements performed on samples of Cu-ZSM-5 exposed to various O_2-reductant combinations and also discuss data obtained from a single-fiber prototype sensor fabricated using a sol-gel processing technique.(J.T. Remillard et al.), Appl. Opt. 38 5306 (1999).

  19. Zeolite crystal growth in space

    NASA Technical Reports Server (NTRS)

    Sacco, Albert, Jr.; Thompson, Robert W.; Dixon, Anthony G.

    1991-01-01

    The growth of large, uniform zeolite crystals in high yield in space can have a major impact on the chemical process industry. Large zeolite crystals will be used to improve basic understanding of adsorption and catalytic mechanisms, and to make zeolite membranes. To grow large zeolites in microgravity, it is necessary to control the nucleation event and fluid motion, and to enhance nutrient transfer. Data is presented that suggests nucleation can be controlled using chemical compounds (e.g., Triethanolamine, for zeolite A), while not adversely effecting growth rate. A three-zone furnace has been designed to perform multiple syntheses concurrently. The operating range of the furnace is 295 K to 473 K. Teflon-lined autoclaves (10 ml liquid volume) have been designed to minimize contamination, reduce wall nucleation, and control mixing of pre-gel solutions on orbit. Zeolite synthesis experiments will be performed on USML-1 in 1992.

  20. The effect of various treatment conditions on natural zeolites: ion exchange, acidic, thermal and steam treatments.

    PubMed

    Ates, Ayten; Hardacre, Christopher

    2012-04-15

    Two different natural zeolites having different phase compositions were obtained from different regions of Turkey and modified by ion-exchange (0.5M NH(4)NO(3)) and acid leaching using 1M HCl. The natural and modified samples were treated at low temperature (LT), high temperature (HT) and steam (ST) conditions and characterised by XRF, XRD, BET, FTIR, DR-UV-Vis, NH(3)-TPD and TGA. Ion-exchange with NH(4)(+) of natural zeolites results in the exchange of the Na(+) and Ca(2+) cations and the partial exchange of the Fe(3+) and Mg(2+) cations. However, steam and acidic treatments cause significant dealumination and decationisation, as well as loss of crystalline, sintering of phases and the formation of amorphous material. The presence of mordenite and quartz phases in the natural zeolites increases the stability towards acid treatment, whereas the structure of clinoptilolite-rich zeolites is mostly maintained after high temperature and steam treatments. The natural and modified zeolites treated at high temperature and in steam were found to be less stable compared with synthetic zeolites, resulting in a loss of crystallinity, a decrease in the surface area and pore volume, a decrease in the surface acidity as well as dealumination, and decationisation.

  1. Cesium Incorporation and Diffusion in Cancrinite, Soalite, Zeolite, and Allophane

    SciTech Connect

    Mon, Jarai; Deng, Youjun; Flury, Markus; Harsh, James B.

    2005-11-28

    At the US Department of Energy?s Hanford site, high level nuclear waste has leaked from under4 ground storage tanks. The waste consists of hyperalkaline solutions, which upon contact with the 5 sediments, caused dissolution of silicate minerals and precipitation of secondary aluminosilicate minerals. Cancrinite, sodalite, LTA zeolite, and allophane have been identified as the new mineral phases 7 in laboratory simulations. Cesium, the major radionuclide in the waste solutions, may be incorporated 8 into the structural framework of the precipitates. The objectives of this study were to determine the 9 resistance of incorporated Cs to ion exchange and the mobility and diffusion coefficient of Cs in the 10 minerals. The minerals were synthesized in solutions mimicking the tank waste and were washed with 11 deionized water. Two sets of experiments were conducted to test the resistance of Cs to ion exchange. 12 In the first set, Cs was exchanged three times at 80 C by 0.5 N Na, K, or Ca. The Cs remaining in 13 minerals was quantified after acid digestion. In the second set, we studied the Cs desorption kinetics 14 by using 0.1 M Na as ion exchanger. Cesium concentration in the solution phase was measured as a 15 function of time for 23 days. Cesium incorporated in sodalite and cancrinite was far more difficult to 16 replace than that in LTA zeolite and allophane. Most of the incorporated Cs (94?99%) in LTA zeolite 17 and allophane was readily exchangeable with Na or K; less than 20% of Cs in sodalite and <55% of 2 Cs in cancrinite could be exchanged. The fraction of desorbed Cs was also affected by the exchanging 19 ions; the ion with lowest dehydration energy (K) was the most effective in replacing Cs. The results 20 of the desorption kinetics experiments showed that Cs desorbed quickly from LTA zeolite and the Cs 21 diffusion coefficient was close to that in solution; i.e., about 10?9 m2/s. Solid-state NMR analysis 22 supported the high mobility of Cs in LTA zeolite

  2. IMPROVED CATALYSTS FOR HEAVY OIL UPGRADING BASED ON ZEOLITE Y NANOPARTICLES ENCAPSULATED IN STABLE NANOPOROUS HOST

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2005-03-31

    The objectives of this project are to synthesis nanocrystals of highly acidic zeolite Y, encapsulate them within the channels of mesoporous (nanoporous) silicates or nanoporous organosilicates and evaluate the ''zeolite Y/Nanoporous host'' composites as catalysts for the upgrading of heavy petroleum feedstocks. Our results to date are summarized as follows. The synthesis of high surface ordered nanoporous silica of expanded pore diameter of 25 nm (larger than the standard size of 8.4 nm) using trimethylbenzene as a pore size expander was accomplished. The synthesis of zeolite Y nanoparticles with median pore size of approximately 50 nm (smaller than the 80 nm typically obtained with TMAOH) using combined TMABr/TMAOH as organic additives was also accomplished. The successful synthesis of zeoliteY/Nanoporous host composite materials by sequential combination of zeolite precursors and nanoporous material precursor mixtures was implied based on results from various characterization techniques such as X-Ray diffraction, infrared spectra, thermal analysis, porosimetry data. The resulting materials showed pore sizes up to 11 nm, and infrared band at 570 cm{sup -1} suggesting the presence of both phases. New results indicated that good quality highly ordered nanoporous silica host can be synthesized in the presence of zeolite Y seed precursor depending on the amount of precursor added. Preliminary research on the catalytic performance of the materials is underway. Probe acid catalyzed reactions, such as the cracking of cumene is currently being conducted. Work in the immediate future will be focused on the following three areas: (1) Further characterization of all-silica and aluminosilicate mesoporous materials with expanded pore sizes up to 30 nm will continue; (2) Research efforts to reduce the average particle size of zeolite nanoparticles down to 35-30 nm will continue; (3) Further synthesis of ZeoliteY/Nanoporous host composite catalysts of improved structural and

  3. Abu Zenima synthetic zeolite for removing iron and manganese from Assiut governorate groundwater, Egypt

    NASA Astrophysics Data System (ADS)

    Farrag, Abd El Hay Ali; Abdel Moghny, Th.; Mohamed, Atef Mohamed Gad; Saleem, Saleem Sayed; Fathy, Mahmoud

    2016-06-01

    Groundwater in Upper Egypt especially in Assiut Governorate is considered the second source of fresh water and used for drinking, agriculture, domestic and industrial purposes. Unfortunately, it is characterized by high concentrations of iron and manganese ions. The study aimed at synthesizing zeolite-4A from kaolinite for removing the excess iron and manganese ions from Assiut Governorate groundwater wells. Therefor, the kaolinite was hydrothermally treated through the metakaolinization and zeolitization processes to produce crystalline zeolite-4A. The chemical composition of crystalline zeolite-4A and its morphology were then characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Then the column experiments were conducted to study the performance of crystalline salt-4A as ion exchange and investigate their operating parameters and regeneration conditions. Thomas and Yoon-Nelson models were applied to predict adsorption capacity and the time required for 50 % breakthrough curves. The effects of initial concentrations of 600 and 1000 mg L-1 for Fe2+ and Mn2+, feed flow rate of 10-30 ml/min, and height range of 0.4-1.5 cm on the breakthrough behavior of the adsorption system were determined. The obtained results indicated that the synthesized zeolite-A4 can remove iron and manganese ions from groundwater to the permissible limit according to the standards drinking water law.

  4. Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Ahlborg, Nadia L.; Zhu, Dongming

    2013-01-01

    The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

  5. Atomic Structure of a Cesium Aluminosilicate Geopolymer: A Pair Distribution Function Study

    SciTech Connect

    Bell, J.; Sarin, P; Provis, J; Haggerty, R; Driemeyer, P; Chupas, P; van Deventer, J; Kriven, W

    2008-01-01

    The atomic pair distribution function (PDF) method was used to study the structure of cesium aluminosilicate geopolymer. The geopolymer was prepared by reacting metakaolin with cesium silicate solution followed by curing at 50C for 24 h in a sealed container. Heating of Cs-geopolymer above 1000C resulted in formation of crystalline pollucite (CsAlSi{sub 2}O{sub 6}). PDF refinement of the pollucite phase formed displayed an excellent fit over the 10-30 {angstrom} range when compared with a cubic pollucite model. A poorer fit was attained from 1-10 {angstrom} due to an additional amorphous phase present in the heated geopolymer. On the basis of PDF analysis, unheated Cs-geopolymer displayed structural ordering similar to pollucite up to a length scale of 9 {angstrom}, despite some differences. Our results suggest that hydrated Cs{sup +} ions were an integral part of the Cs-geopolymer structure and that most of the water present was not associated with Al-OH or Si-OH bonds.

  6. Molecular Chemistry in a Zeolite: Genesis of a Zeolite Y-Supported Ruthenium Complex Catalyst

    SciTech Connect

    Ogino, I.; Gates, B.C.

    2009-05-22

    Dealuminated zeolite Y was used as a crystalline support for a mononuclear ruthenium complex synthesized from cis-Ru(acac){sub 2}(C{sub 2}H{sub 4}){sub 2}. Infrared (IR) and extended X-ray absorption fine structure spectra indicated that the surface species were mononuclear ruthenium complexes, Ru(acac)(C{sub 2}H{sub 4}){sub 2}{sup 2+}, tightly bonded to the surface by two Ru-O bonds at Al{sup 3+} sites of the zeolite. The maximum loading of the anchored ruthenium complexes was one complex per two Al{sup 3+} sites; at higher loadings, some of the cis-Ru(acac){sub 2}(C{sub 2}H{sub 4}){sub 2} was physisorbed. In the presence of ethylene and H{sub 2}, the surface-bound species entered into a catalytic cycle for ethylene dimerization and operated stably. IR data showed that at the start of the catalytic reaction, the acac ligand of the Ru(acac)(C{sub 2}H{sub 4}){sub 2}{sup 2+} species was dissociated and captured by an Al{sup 3+} site. Ethylene dimerization proceeded 600 times faster with a cofeed of ethylene and H{sub 2} than without H{sub 2}. These results provide evidence of the importance of the cooperation of the Al{sup 3+} sites in the zeolite and the H{sub 2} in the feed for the genesis of the catalytically active species. The results presented here demonstrate the usefulness of dealuminated zeolite Y as a nearly uniform support that allows precise synthesis of supported catalysts and detailed elucidation of their structures.

  7. A Novel Fluoride Route for the Synthesis of Aluminosilicate Nanotubes

    PubMed Central

    Chemmi, Atika; Brendlé, Jocelyne; Marichal, Claire; Lebeau, Bénédicte

    2013-01-01

    In this work we present a novel method for synthesis of aluminosilicate nanotubes: the fluoride route. F-containing imogolite (F-IMO) exhibits an improved crystallization rate and improved yield. The structure of F-IMO was investigated and compared with F-free imogolite (IMO) by means of X-ray diffraction (XRD) and Fourier transformed infrared spectroscopy (FTIR) confirming imogolite structure. Solid state nuclear magnetic resonance (NMR) analyses show an increased crystallization rate for F-IMO and confirm the incorporation of fluorine ion in the structure. PMID:28348325

  8. Characterisation of frequency doubling in Eu(2+) doped aluminosilicate fibres

    NASA Technical Reports Server (NTRS)

    Driscoll, T. J.; Lawandy, N. M.; Killian, A.; Rienhart, L.; Morse, T. F.

    1991-01-01

    The results of a series of experiments on efficient second-harmonic generation in a fiber with a Eu(2+)-doped aluminosilicate core are reported. The fiber was prepared by the seeding method with CW mode-locked radiation at 1.06 micron and produced ultrastable peak conversion efficiencies of 0.001 during mode-locked readout. Experiments were performed to determine the IR preparation intensity dependence, the stability of the output, and the type of erasure mechanisms which occur. The results are compared with those of germanosilicate fibers and some similarities and differences are discussed.

  9. Effect of metal loading processes on the stability and thermal transformation of Co{sup 2+}- and Cu{sup 2+}-zeolite Y prepared from Egyptian kaolin

    SciTech Connect

    EL-Mekkawi, Doaa M. Selim, Mohamed M.

    2012-07-15

    This paper aims to assess the effect of the transition metals (TM) loading procedure on the incorporation of Co{sup 2+} and Cu{sup 2+} in zeolite Y, and their relevance to stability of the zeolite, particularly with respect to the thermal transformation to the spinel phases. In this work, zeolite Y prepared from Egyptian kaolin was used. XRF, XRD, TEM, UV/visible absorption measurements, and atomic absorption analyses in addition to the visual observations are recorded. XRF has been used to investigate the materials composition. TEM and XRD indicate the presence of nanoparticle spinel upon the calcination of the TM-zeolites at 1000 Degree-Sign C. In addition to spinel particles, XRD shows the formation of metal oxides, SiO{sub 2} and alumino-silicate phases. According to the transition metal and the cation loading process, different phases were detected. UV/visible absorption measurements and the visual observations are used to determine the experimental condition of the highest spinel content. It has been noticed that the experimental conditions of the metal sorption processes greatly affect the phase transformation. Stability and thermal transformation of zeolite depend on the initial concentration of the transition cation solutions and the number of loading cycles. - Highlights: Black-Right-Pointing-Pointer We study the effects of loading procedure in the incorporation of TM in zeolite Y. Black-Right-Pointing-Pointer Synthetic zeolite Y prepared from Egyptian kaolin has been used. Black-Right-Pointing-Pointer The type of TM affects the stability and thermal transformation of zeolite. Black-Right-Pointing-Pointer Loading processes affect the stability and thermal transformation of zeolite.

  10. Tailoring Zeolite ZSM-5 Crystal Morphology/Porosity through Flexible Utilization of Silicalite-1 Seeds as Templates: Unusual Crystallization Pathways in a Heterogeneous System.

    PubMed

    Zhang, Hongbin; Zhao, Yang; Zhang, Hongxia; Wang, Peicheng; Shi, Zhangping; Mao, Jianjiang; Zhang, Yahong; Tang, Yi

    2016-05-17

    Diffusion limitation in micropores of zeolites leads to a demand for optimization of zeolite morphology and/or porosity. However, tailoring crystallization processes to realize targeted morphology/porosity is a major challenge in zeolite synthesis. On the basis of previous work on the salt-aided, seed-induced route, the template effect of seeds on the formation of micropores, mesopores and even macropores was further explored to selectively achieve desired hierarchical architectures. By carefully investigating the crystallization processes of two typical samples with distinct crystal morphologies, namely, 1) nanocrystallite-oriented self-assembled ZSM-5 zeolite and 2) enriched intracrystal mesoporous ZSM-5 zeolite, a detailed mechanism is proposed to clarify the role of silicalite-1 seeds in the formation of diverse morphologies in a salt-rich heterogeneous system, combined with the transformation of seed-embedded aluminosilicate gel. On the basis of these conclusions, the morphologies/porosities of products were precisely tailored by deliberately adjusting the synthesis parameters (KF/Si, tetrapropylammonium bromide/Si and H2 O/Si ratios and type of organic template) to regulate the kinetics of seed dissolution and seed-induced recrystallization. This work may not only provide a practical route to control zeolite crystallization for tailoring crystal morphology, but also expands the knowledge of crystal growth mechanisms in a heterogeneous system.

  11. RESULTS OF CAUSTIC DISSOLUTION OF ALUMINOSILICATE SCALE AND CHARACTERIZATION DATA FOR SAMPLES FROM THE EVAPORATOR POT AND GRAVITY DRAIN LINE

    SciTech Connect

    Wilmarth, B; Rita Sullivan, R; Chris Martino, C

    2006-08-21

    The build-up of sodium aluminosilicate scale in the 2H Evaporator system continues to cause operational difficulties. The use of a nitric acid cleaning operation proved successful in 2001. However, the operation required additional facilities to support spent cleaning solution neutralization and was quite costly. A proposed caustic cleaning flowsheet has many advantages over the acid flowsheet. Therefore, samples were retrieved from the evaporator system (gravity drain line and pot) for both chemical and radiological characterization and dissolution testing. The characterization of these scale samples showed the presence of nitrated cancrinite along with a dehydrated zeolite. Small amounts of depleted uranium were also found in these samples as expected and the amount of uranium ranged from 0.5 wt% to 2 wt%. Dissolution in sodium hydroxide solutions of various caustic concentrations showed that the scale slowly dissolves at elevated temperature (90 C). Data from similar testing indicate that the scale removed from the GDL in 2005 dissolves slower than that removed in 1997. Differences in the particle size of these samples of scale may well explain the measured dissolution rate differences.

  12. Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate

    NASA Astrophysics Data System (ADS)

    Geng, Guoqing; Myers, Rupert J.; Li, Jiaqi; Maboudian, Roya; Carraro, Carlo; Shapiro, David A.; Monteiro, Paulo J. M.

    2017-03-01

    The incorporation of Al and increased curing temperature promotes the crystallization and cross-linking of calcium (alumino)silicate hydrate (C-(A-)S-H), which is the primary binding phase in most contemporary concrete materials. However, the influence of Al-induced structural changes on the mechanical properties at atomistic scale is not well understood. Herein, synchrotron radiation-based high-pressure X-ray diffraction is used to quantify the influence of dreierketten chain cross-linking on the anisotropic mechanical behavior of C-(A-)S-H. We show that the ab-planar stiffness is independent of dreierketten chain defects, e.g. vacancies in bridging tetrahedra sites and Al for Si substitution. The c-axis of non-cross-linked C-(A-)S-H is more deformable due to the softer interlayer opening but stiffens with decreased spacing and/or increased zeolitic water and Ca2+ of the interlayer. Dreierketten chain cross-links act as ‘columns’ to resist compression, thus increasing the bulk modulus of C-(A-)S-H. We provide the first experimental evidence on the influence of the Al-induced atomistic configurational change on the mechanical properties of C-(A-)S-H. Our work advances the fundamental knowledge of C-(A-)S-H on the lowest level of its hierarchical structure, and thus can impact the way that innovative C-(A-)S-H-based cementitious materials are developed using a ‘bottom-up’ approach.

  13. Sol-gel derived aluminosilicate coatings on alumina as substrate for osteoblasts.

    PubMed

    Leivo, Jarkko; Meretoja, Ville; Vippola, Minnamari; Levänen, Erkki; Vallittu, Pekka; Mäntylä, Tapio A

    2006-11-01

    Rat bone marrow stromal cell differentiation on aluminosilicate 3Al(2)O(3)-2SiO(2) coatings was investigated. Thin ceramic coatings were prepared on alpha-alumina substrates by the sol-gel process and calcined in order to establish an amorphous aluminosilicate ceramic phase with and without nanosized transitional mullite crystals. In addition, coatings of thermally sprayed aluminosilicate and diphasic gamma-alumina-silica nanosized colloids were prepared. Cell culture testing by rat osteoblasts showed good biocompatibility for aluminosilicates with sustained normal osteoblast functions. Despite mutual disparities in physical and chemical nanostructures, the culture findings suggested fairly similar osteoblast response to all tested coatings. The results suggest that topographical frequency parameters and chemical uniformity are important parameters in determining the best conditions for osteoblasts on sol-gel derived aluminosilicate materials.

  14. Zeolite vitrification demonstration program: characterization of radioactive vitrified zeolite materials

    SciTech Connect

    Barner, J O; Daniel, J L; Marshall, R K

    1984-01-01

    The leach behavior of radioactive vitrified zeolite material was studied as part of the Three Mile Island (TMI) Zeolite Vitrification Program conducted by Pacific Northwest Laboratory (PNL). Experimental procedures, test results, and discussions of the results are presented. The leach behavior of material from three canisters of vitrified zeolite is discussed in terms of the normalized weight loss of the glass-formers and the normalized activity loss of the fission products cesium and strontium. The leach behavior of the radioactive vitrified zeolite material is also compared to the leach behavior of MCC 76-68 reference glass. The effects of changes in the surface microstructure of the vitrified zeolite that occurred during leaching are also presented. 3 references, 23 figures, 10 tables.

  15. Solid-state radioluminescent zeolite-containing composition and light sources

    DOEpatents

    Clough, Roger L.; Gill, John T.; Hawkins, Daniel B.; Renschler, Clifford L.; Shepodd, Timothy J.; Smith, Henry M.

    1992-01-01

    A new type of RL light source consisting of a zeolite crystalline material, the intralattice spaces of which a tritiated compound and a luminophore are sorbed, and which material is optionally further dispersed in a refractive index-matched polymer matrix.

  16. Zeolite formation from coal fly ash and its adsorption potential.

    PubMed

    Ruen-ngam, Duangkamol; Rungsuk, Doungmanee; Apiratikul, Ronbanchob; Pavasant, Prasert

    2009-10-01

    The possibility in converting coal fly ash (CFA) to zeolite was evaluated. CFA samples from the local power plant in Prachinburi province, Thailand, were collected during a 3-month time span to account for the inconsistency of the CFA quality, and it was evident that the deviation of the quality of the raw material did not have significant effects on the synthesis. The zeolite product was found to be type X. The most suitable weight ratio of sodium hydroxide (NaOH) to CFA was approximately 2.25, because this gave reasonably high zeolite yield with good cation exchange capacity (CEC). The silica (Si)-to-aluminum (Al) molar ratio of 4.06 yielded the highest crystallinity level for zeolite X at 79% with a CEC of 240 meq/100 g and a surface area of 325 m2/g. Optimal crystallization temperature and time were 90 degrees C and 4 hr, respectively, which gave the highest CEC of approximately 305 meq/100 g. Yields obtained from all experiments were in the range of 50-72%.

  17. Zeolite formation from coal fly ash and its adsorption potential

    SciTech Connect

    Duangkamol Ruen-ngam; Doungmanee Rungsuk; Ronbanchob Apiratikul; Prasert Pavasant

    2009-10-15

    The possibility in converting coal fly ash (CFA) to zeolite was evaluated. CFA samples from the local power plant in Prachinburi province, Thailand, were collected during a 3-month time span to account for the inconsistency of the CFA quality, and it was evident that the deviation of the quality of the raw material did not have significant effects on the synthesis. The zeolite product was found to be type X. The most suitable weight ratio of sodium hydroxide (NaOH) to CFA was approximately 2.25, because this gave reasonably high zeolite yield with good cation exchange capacity (CEC). The silica (Si)-to-aluminum (Al) molar ratio of 4.06 yielded the highest crystallinity level for zeolite X at 79% with a CEC of 240 meq/100 g and a surface area of 325 m{sup 2}/g. Optimal crystallization temperature and time were 90{sup o}C and 4 hr, respectively, which gave the highest CEC of approximately 305 meq/100 g. Yields obtained from all experiments were in the range of 50-72%. 29 refs., 5 tabs., 7 figs.

  18. Effective Sequestration of Clostridium difficile Protein Toxins by Calcium Aluminosilicate

    PubMed Central

    Pokusaeva, Karina; Carpenter, Robert

    2015-01-01

    Clostridium difficile is a leading cause of antibiotic-associated diarrhea and the etiologic agent responsible for C. difficile infection. Toxin A (TcdA) and toxin B (TcdB) are nearly indispensable virulence factors for Clostridium difficile pathogenesis. Given the toxin-centric mechanism by which C. difficile pathogenesis occurs, the selective sequestration with neutralization of TcdA and TcdB by nonantibiotic agents represents a novel mode of action to prevent or treat C. difficile-associated disease. In this preclinical study, we used quantitative enzyme immunoassays to determine the extent by which a novel drug, calcium aluminosilicate uniform particle size nonswelling M-1 (CAS UPSN M-1), is capable of sequestering TcdA and TcdB in vitro. The following major findings were derived from the present study. First, we show that CAS UPSN M-1 efficiently sequestered both TcdA and TcdB to undetectable levels. Second, we show that CAS UPSN M-1's affinity for TcdA is greater than its affinity for TcdB. Last, we show that CAS UPSN M-1 exhibited limited binding affinity for nontarget proteins. Taken together, these results suggest that ingestion of calcium aluminosilicate might protect gastrointestinal tissues from antibiotic- or chemotherapy-induced C. difficile infection by neutralizing the cytotoxic and proinflammatory effects of luminal TcdA and TcdB. PMID:26149988

  19. Preparation and gas permeabilities of zeolite membranes

    SciTech Connect

    Jinqu Wang; Yongfeng Wang; Shuanshi Fan

    1994-12-31

    Zeolites with less than 10 {angstrom} pore are desirable membrane materials, due to their crystallinity, resistance to high temperature, and chemical inertness. A variety of new membranous materials were synthesized composed of a continuous intergrowth of 5-50 micrometer type A, X, Y, or ZSM-5 crystals. The membranes were crystallized under hydrothermal conditions at 90 to 220{degrees}C on the external surface of a porous ceramics. The reagents used were aluminum sulphate, water glass (20.1 wt% SiO{sub 2}, 6.09 wt% Na{sub 2}O, 73.8 wt% water), sodium hydroxide, sulphuric acid, deionized water and templating agents. The molar composition was: 0.1-0.5 Na{sub 2}O:1 SiO{sub 2}:0.04-0.05 Al{sub 2}O{sub 3}:20-60H{sub 2}O.

  20. Zeolite membrane application in hydrocarbon processing

    SciTech Connect

    Suzuki, H.

    1988-06-01

    Zeolites are of great importance in hydrocarbon processing either as adsorbents or catalysts. This paper presents a research since 1973 about the transformation of zeolite into membrane zeolite, that dramatically contributes to the free world of peace and prosperity. Commercial and organic membranes are of two categories: anisotropic membrane, e.g. cellulose acetate, and composite membrane, e.g. plasma {und in}-{und situ} polymerization on polysulfone support. Zeolite membrane belongs to the latter category, zeolite {und in}-{und situ} hydrothermalization on porous glass. Basically zeolite membrane is consisted of three groups: (1) eight-oxygen ring window, zeolite A, (2) ten-oxygen ring window, Pentasil, and (3) twelve-oxygen ring window, Faujasite. The technology of zeolite membrane synthesis and subsequent treatment is almost transferred from the one applied to powder zeolites. Zeolite membrane is expected to play a major role in the field of hydrocarbon processing, that is, PSA, Distillation/Extraction, and Catalytic Reactions.

  1. Oxygen and hydrogen isotope geochemistry of zeolites

    NASA Technical Reports Server (NTRS)

    Karlsson, Haraldur R.; Clayton, Robert N.

    1990-01-01

    Oxygen and hydrogen isotope ratios for natural samples of the zeolites analcime, chabazite, clinoptilolite, laumontite, mordenite, and natrolite have been obtained. The zeolite samples were classified into sedimentary, hydrothermal, and igneous groups. The ratios for each species of zeolite are reported. The results are used to discuss the origin of channel water, the role of zeolites in water-rock interaction, and the possibility that a calibrated zeolite could be used as a low-temperature geothermometer.

  2. SODIUM ALUMINOSILICATE FOULING AND CLEANING OF DECONTAMINATED SALT SOLUTION COALESCERS

    SciTech Connect

    Poirier, M; Thomas Peters, T; Fernando Fondeur, F; Samuel Fink, S

    2008-10-28

    During initial non-radioactive operations at the Modular Caustic Side Solvent Extraction Unit (MCU), the pressure drop across the decontaminated salt solution coalescer reached {approx}10 psi while processing {approx}1250 gallons of salt solution, indicating possible fouling or plugging of the coalescer. An analysis of the feed solution and the 'plugged coalescer' concluded that the plugging was due to sodium aluminosilicate solids. MCU personnel requested Savannah River National Laboratory (SRNL) to investigate the formation of the sodium aluminosilicate solids (NAS) and the impact of the solids on the decontaminated salt solution coalescer. Researchers performed developmental testing of the cleaning protocols with a bench-scale coalescer container 1-inch long segments of a new coalescer element fouled using simulant solution. In addition, the authors obtained a 'plugged' Decontaminated Salt Solution coalescer from non-radioactive testing in the MCU and cleaned it according to the proposed cleaning procedure. Conclusions from this testing include the following: (1) Testing with the bench-scale coalescer showed an increase in pressure drop from solid particles, but the increase was not as large as observed at MCU. (2) Cleaning the bench-scale coalescer with nitric acid reduced the pressure drop and removed a large amount of solid particles (11 g of bayerite if all aluminum is present in that form or 23 g of sodium aluminosilicate if all silicon is present in that form). (3) Based on analysis of the cleaning solutions from bench-scale test, the 'dirt capacity' of a 40 inch coalescer for the NAS solids tested is calculated as 450-950 grams. (4) Cleaning the full-scale coalescer with nitric acid reduced the pressure drop and removed a large amount of solid particles (60 g of aluminum and 5 g of silicon). (5) Piping holdup in the full-scale coalescer system caused the pH to differ from the target value. Comparable hold-up in the facility could lead to less effective

  3. Template-free nanosized faujasite-type zeolites

    NASA Astrophysics Data System (ADS)

    Awala, Hussein; Gilson, Jean-Pierre; Retoux, Richard; Boullay, Philippe; Goupil, Jean-Michel; Valtchev, Valentin; Mintova, Svetlana

    2015-04-01

    Nanosized faujasite (FAU) crystals have great potential as catalysts or adsorbents to more efficiently process present and forthcoming synthetic and renewable feedstocks in oil refining, petrochemistry and fine chemistry. Here, we report the rational design of template-free nanosized FAU zeolites with exceptional properties, including extremely small crystallites (10-15 nm) with a narrow particle size distribution, high crystalline yields (above 80%), micropore volumes (0.30 cm3 g-1) comparable to their conventional counterparts (micrometre-sized crystals), Si/Al ratios adjustable between 1.1 and 2.1 (zeolites X or Y) and excellent thermal stability leading to superior catalytic performance in the dealkylation of a bulky molecule, 1,3,5-triisopropylbenzene, probing sites mostly located on the external surface of the nanosized crystals. Another important feature is their excellent colloidal stability, which facilitates a uniform dispersion on supports for applications in catalysis, sorption and thin-to-thick coatings.

  4. Synthesis of NaP zeolite at room temperature and short crystallization time by sonochemical method.

    PubMed

    Pal, Pameli; Das, Jugal K; Das, Nandini; Bandyopadhyay, Sibdas

    2013-01-01

    NaP zeolite nano crystals were synthesized by sonochemical method at room temperature with crystallization time of 3h. For comparison, to insure the effect of sonochemical method, the hydrothermal method at conventional synthesis condition, with same initial sol composition was studied. NaP zeolites are directly formed by ultrasonic treatment without the application of autogenous pressure and also hydrothermal treatment. The effect of ultrasonic energy and irradiation time showed that with increasing sonication energy, the crystallinity of the powders decreased but phase purity remain unchanged. The synthesized powders were characterized by XRD, IR, DTA TGA, FESEM, and TEM analysis. FESEM images revealed that 50 nm zeolite crystals were formed at room temperature by using sonochemical method. However, agglomerated particles having cactus/cabbage like structure was obtained by sonochemical method followed by hydrothermal treatment. In sonochemical process, formation of cavitation and the collapsing of bubbles produced huge energy which is sufficient for crystallization of zeolite compared to that supplied by hydrothermal process for conventional synthesis. With increasing irradiation energy and time, the crystallinity of the synthesized zeolite samples increased slightly.

  5. Catalytic performance of Metal-Organic-Frameworks vs. extra-large pore zeolite UTL in condensation reactions

    PubMed Central

    Shamzhy, Mariya; Opanasenko, Maksym; Shvets, Oleksiy; Čejka, Jiří

    2013-01-01

    Catalytic behavior of isomorphously substituted B-, Al-, Ga-, and Fe-containing extra-large pore UTL zeolites was investigated in Knoevenagel condensation involving aldehydes, Pechmann condensation of 1-naphthol with ethylacetoacetate, and Prins reaction of β-pinene with formaldehyde and compared with large-pore aluminosilicate zeolite beta and representative Metal-Organic-Frameworks Cu3(BTC)2 and Fe(BTC). The yield of the target product over the investigated catalysts in Knoevenagel condensation increases in the following sequence: (Al)beta < (Al)UTL < (Ga)UTL < (Fe)UTL < Fe(BTC) < (B)UTL < Cu3(BTC)2 being mainly related to the improving selectivity with decreasing strength of active sites of the individual catalysts. The catalytic performance of Fe(BTC), containing the highest concentration of Lewis acid sites of the appropriate strength is superior over large-pore zeolite (Al)beta and B-, Al-, Ga-, Fe-substituted extra-large pore zeolites UTL in Prins reaction of β-pinene with formaldehyde and Pechmann condensation of 1-naphthol with ethylacetoacetate. PMID:24790940

  6. Catalytic performance of Metal-Organic-Frameworks vs. extra-large pore zeolite UTL in condensation reactions.

    PubMed

    Shamzhy, Mariya; Opanasenko, Maksym; Shvets, Oleksiy; Cejka, Jiří

    2013-01-01

    Catalytic behavior of isomorphously substituted B-, Al-, Ga-, and Fe-containing extra-large pore UTL zeolites was investigated in Knoevenagel condensation involving aldehydes, Pechmann condensation of 1-naphthol with ethylacetoacetate, and Prins reaction of β-pinene with formaldehyde and compared with large-pore aluminosilicate zeolite beta and representative Metal-Organic-Frameworks Cu3(BTC)2 and Fe(BTC). The yield of the target product over the investigated catalysts in Knoevenagel condensation increases in the following sequence: (Al)beta < (Al)UTL < (Ga)UTL < (Fe)UTL < Fe(BTC) < (B)UTL < Cu3(BTC)2 being mainly related to the improving selectivity with decreasing strength of active sites of the individual catalysts. The catalytic performance of Fe(BTC), containing the highest concentration of Lewis acid sites of the appropriate strength is superior over large-pore zeolite (Al)beta and B-, Al-, Ga-, Fe-substituted extra-large pore zeolites UTL in Prins reaction of β-pinene with formaldehyde and Pechmann condensation of 1-naphthol with ethylacetoacetate.

  7. Amphiphilic properties of poly(oxyalkylene)amine-intercalated smectite aluminosilicates.

    PubMed

    Lin, Jiang-Jen; Chen, Yu-Min

    2004-05-11

    Layered aluminosilicates, including synthetic fluorine mica and natural montmorillonite (MMT), were intercalated with poly(oxypropylene)-polyamine quaternary salts with a 230-5000 molecular weight range. The X-ray basal spacing of these silicates had been expanded from 13.5 to 83.7 A for the synthetic mica and to 92.0 A for MMT. The relative silicate dimensions (300-1000 nm for synthetic mica and 80-100 nm for MMT) were ascertained by direct TEM observations in the case of the co-intercalated synthetic mica and MMT mixtures with Mw = 2000 quaternary ammonium salts. The tailored organic incorporation of synthetic mica and MMT clays could alter these hydrophilic clays, making them amphiphilic, and enable the lowering of toluene/water interfacial tension to 2.0 mN/m at the critical concentration of 0.1 wt %.

  8. Selective laser densification of lithium aluminosilicate glass ceramic tapes

    NASA Astrophysics Data System (ADS)

    Zocca, Andrea; Colombo, Paolo; Günster, Jens; Mühler, Thomas; Heinrich, Jürgen G.

    2013-01-01

    Tapes, cast by blade deposition of a lithium aluminosilicate glass slurry, were sintered using a YAG-fiber laser, with the aim of finding suitable parameters for an additive manufacturing process based on layer-wise slurry deposition and selective laser densification. The influence of the laser parameters (output power and scan velocity) on the sintering was evaluated, by scanning electron microscopy and by X-ray diffraction, on the basis of the quality of the processed layer. Well densified samples could be obtained only in a small window of values for the output power and the scan velocity. The measurement of the width of a set of single scanned lines allowed also to estimate the minimum resolution of the system along the layer plane.

  9. Sorption of cesium ions by nanostructured calcium aluminosilicates

    NASA Astrophysics Data System (ADS)

    Gordienko, P. S.; Shabalin, I. A.; Yarusova, S. B.; Suponina, A. P.; Zhevtun, I. G.

    2016-10-01

    Data on the sorption properties of synthetic calcium aluminosilicates (CASes) with Al: Si ratios of 2: 2, 2: 6, and 2: 10, fabricated within the multicomponent system CaCl2-AlCl3-KOM-SiO2-H2O, are presented. Isotherms of the sorption of Cs+ ions from aqueous solutions with Cs+ concentrations of 0.2 to 6.0 mmol L-1 are analyzed. The CAS maximum sorption capacity and the Langmuir constants are determined. Kinetic data are obtained, and the energy of cation-exchange activation upon the sorption of Cs+ ions is determined. The effect of a salt background (1% KCl + 6% NaCl) has on the values of distribution coefficient ( K d) and the degree of Cs+ ion removal is established.

  10. Laser control of zeolite nucleation.

    PubMed

    Navarro, Marta; Mayoral, Alvaro; Mateo, Ester; Lahoz, Ruth; de la Fuente, Germán F; Coronas, Joaquín

    2012-02-01

    Precursor solutions for the synthesis of zeolites are irradiated by means of a Nd-YAG laser. These solutions are subsequently submitted to a hydrothermal treatment and the results analyzed by X-ray diffraction and electron microscopy. Laser irradiation promotes the formation of silica nanoparticles that nucleate into zeolite (silicalite-1), following a hydrothermal treatment. The average crystal size (in the 0.6-3.6 μm range) of the zeolite exponentially decreases as a function of laser irradiation time. In addition, a longer irradiation time results in a narrower crystal size distribution.

  11. Radiation damage of a glass-bonded zeolite waste form using ion irradiation.

    SciTech Connect

    Allen, T. R.; Storey, B. G.

    1997-12-05

    Glass-bonded zeolite is being considered as a candidate ceramic waste form for storing radioactive isotopes separated from spent nuclear fuel in the electrorefining process. To determine the stability of glass-bonded zeolite under irradiation, transmission electron microscope samples were irradiated using high energy helium, lead, and krypton. The major crystalline phase of the waste form, which retains alkaline and alkaline earth fission products, loses its long range order under both helium and krypton irradiation. The dose at which the long range crystalline structure is lost is about 0.4 dpa for helium and 0.1 dpa for krypton. Because the damage from lead is localized in such a small region of the sample, damage could not be recognized even at a peak damage of 50 dpa. Because the crystalline phase loses its long range structure due to irradiation, the effect on retention capacity needs to be further evaluated.

  12. Single Molecule Nanospectroscopy Visualizes Proton-Transfer Processes within a Zeolite Crystal

    PubMed Central

    2016-01-01

    Visualizing proton-transfer processes at the nanoscale is essential for understanding the reactivity of zeolite-based catalyst materials. In this work, the Brønsted-acid-catalyzed oligomerization of styrene derivatives was used for the first time as a single molecule probe reaction to study the reactivity of individual zeolite H-ZSM-5 crystals in different zeolite framework, reactant and solvent environments. This was accomplished via the formation of distinct dimeric and trimeric fluorescent carbocations, characterized by their different photostability, as detected by single molecule fluorescence microscopy. The oligomerization kinetics turned out to be very sensitive to the reaction conditions and the presence of the local structural defects in zeolite H-ZSM-5 crystals. The remarkably photostable trimeric carbocations were found to be formed predominantly near defect-rich crystalline regions. This spectroscopic marker offers clear prospects for nanoscale quality control of zeolite-based materials. Interestingly, replacing n-heptane with 1-butanol as a solvent led to a reactivity decrease of several orders and shorter survival times of fluorescent products due to the strong chemisorption of 1-butanol onto the Brønsted acid sites. A similar effect was achieved by changing the electrophilic character of the para-substituent of the styrene moiety. Based on the measured turnover rates we have established a quantitative, single turnover approach to evaluate substituent and solvent effects on the reactivity of individual zeolite H-ZSM-5 crystals. PMID:27709925

  13. S +X-I + route to mesostructured materials from Fau and Beta zeolite precursors: A comparative study of their assembly behaviors in extremely acidic media

    NASA Astrophysics Data System (ADS)

    Zheng, Junlin; Zhai, Shangru; Wu, Dong; Sun, Yuhan

    2005-05-01

    Mesoporous molecular sieves were synthesized from Beta and Fau zeolite precursors through S +X-I + route under extremely acidic conditions in parallel (designated as MBeta and MFau, respectively). The textural properties of MFau were different from its MBeta counterpart but resembled normal MCM-41 silica from TEOS. Al content in MBeta was almost equivalent to that in the initial Beta zeolite precursors, whereas only trace Al species was present in MFau from elemental analysis results. The hydrothermal stability of MBeta after post-synthesis ammonia treatment was considerably improved compared with normal MCM-41 aluminosilicates, whereas the MFau after the same procedure was as unstable as normal MCM-41 silica. Thus, the assembly behaviors of Beta and Fau zeolite precursors were comparatively studied based on these results. The microstructure of Fau zeolite precursors were degraded by the extremely acidic condition, and Al species was dissolved into the synthesis mixture. However, Beta zeolite precursors survived the chemical attack of extremely acidic media and were incorporated into mesostructured framework as primary building units.

  14. Zeolite micropattern for biological applications.

    PubMed

    Sun, Wenqing; Lam, Koon Fung; Wong, Ling Wai; Yeung, King Lun

    2005-10-21

    A facile method was established using composition-gradient pattern on zeolite surface to guide the deposition and formation of chemical and biomolecular patterns with features as small as five microns.

  15. Ultrasonic assisted synthesis of Bikitaite zeolite: A potential material for hydrogen storage application.

    PubMed

    Roy, Priyanka; Das, Nandini

    2017-05-01

    Li containing Bikitaite zeolite has been synthesized by an ultrasound-assisted method and used as a potential material for hydrogen storage application. The Sonication energy was varied from 150W to 250W and irradiation time from 3h to 6h. The Bikitaite nanoparticles were characterized by X-ray diffraction (XRD), infrared (IR) spectral analysis, and field-emission scanning electron microscopy (FESEM) thermo-gravimetrical analysis and differential thermal analysis (TGA, DTA). XRD and IR results showed that phase pure, nano crystalline Bikitaite zeolites were started forming after 3h irradiation and 72h of aging with a sonication energy of 150W and nano crystalline Bikitaite zeolite with prominent peaks were obtained after 6h irradiation of 250W sonic energy. The Brunauer-Emmett-Teller (BET) surface area of the powder by N2 adsorption-desorption measurements was found to be 209m(2)/g. The TEM micrograph and elemental analysis showed that desired atomic ratio of the zeolite was obtained after 6h irradiation. For comparison, sonochemical method, followed by the hydrothermal method, with same initial sol composition was studied. The effect of ultrasonic energy and irradiation time showed that with increasing sonication energy, and sonication time phase formation was almost completed. The FESEM images revealed that 50nm zeolite crystals were formed at room temperature. However, agglomerated particles having woollen ball like structure was obtained by sonochemical method followed by hydrothermal treatment at 100°C for 24h. The hydrogen adsorption capacity of Bikitaite zeolite with different Li content, has been investigated. Experimental results indicated that the hydrogen adsorption capacities were dominantly related to their surface areas as well as total pore volume of the zeolite. The hydrogen adsorption capacity of 143.2c.c/g was obtained at 77K and ambient pressure of (0.11MPa) for the Bikitaite zeolite with 100% Li, which was higher than the reported values for

  16. Copper-containing zeolite catalysts

    DOEpatents

    Price, Geoffrey L.; Kanazirev, Vladislav

    1996-01-01

    A catalyst useful in the conversion of nitrogen oxides or in the synthesis of nitriles or imines from amines, formed by preparing an intimate mechanical mixture of a copper (II)-containing species, such as CuO or CuCl.sub.2, or elemental copper, with a zeolite having a pore mouth comprising 10 oxygen atoms, such as ZSM-5, converting the elemental copper or copper (II) to copper (I), and driving the copper (I) into the zeolite.

  17. Copper-containing zeolite catalysts

    DOEpatents

    Price, G.L.; Kanazirev, V.

    1996-12-10

    A catalyst useful in the conversion of nitrogen oxides or in the synthesis of nitriles or imines from amines, is formed by preparing an intimate mechanical mixture of a copper (II)-containing species, such as CuO or CuCl{sub 2}, or elemental copper, with a zeolite having a pore mouth comprising 10 oxygen atoms, such as ZSM-5, converting the elemental copper or copper (II) to copper (I), and driving the copper (I) into the zeolite.

  18. Selective preparation of zeolite X and A from flyash and its use as catalyst for biodiesel production.

    PubMed

    Volli, Vikranth; Purkait, M K

    2015-10-30

    This work discusses the utilization of flyash for synthesis of heterogeneous catalyst for transesterification. Different types of zeolites were synthesized from alkali fusion followed by hydrothermal treatment of coal flyash as source material. The synthesis conditions were optimized to obtain highly crystalline zeolite based on degree of crystallinity and cation exchange capacity (CEC). The effect of CEC, acid treatment, Si/Al ratio and calcination temperature (800, 900 and 1000 °C) on zeolite formation was also studied. Pure, single phase and highly crystalline zeolite was obtained at flyash/NaOH ratio (1:1.2), fusion temperature (550 °C), fusion time (1 h), hydrothermal temperature (110 °C) and hydrothermal time (12h). The synthesized zeolite was ion-exchanged with potassium and was used as catalyst for transesterification of mustard oil to obtain a maximum conversion of 84.6% with 5 wt% catalyst concentration, 12:1 methanol to oil molar ratio, reaction time of 7 h at 65 °C. The catalyst was reused for 3 times with marginal reduction in activity.

  19. The influence of sodium carbonate on sodium aluminosilicate crystallisation and solubility in sodium aluminate solutions

    NASA Astrophysics Data System (ADS)

    Zheng, Kali; Gerson, Andrea R.; Addai-Mensah, Jonas; Smart, Roger St. C.

    1997-01-01

    Isothermal batch precipitation experiments have been carried out in synthetic Bayer liquors to investigate the effects of sodium carbonate concentration on both silica solubility and the crystallisation of sodium aluminosilicates. At both 90 and 160°C cancrinite (generically defined as a sodium aluminosilicate of space group P6 3) is the stable solid phase. Sodalite (generically defined as a sodium aluminosilicate with space group P4¯3n seed transforms to cancrinite at both these temperatures. A high concentration of sodium carbonate in the synthetic liquor causes a decrease in the rate of conversion of sodalite to cancrinite. The solubility of both cancrinite and sodalite decreases as the concentration of sodium carbonate in the synthetic liquor is increased. For instance at 90°C and with 40.0 g dm -3 sodium carbonate in the synthetic liquor after 13 days the sodium aluminosilicate concentration is 0.52 g dm -3 compared to 0.85 g dm -3 with 4.6 g dm -3 of sodium carbonate in solution. At 160°C the sodium aluminosilicate concentration is 0.47 g dm -3 with 40.0 g dm -3 sodium carbonate in solution after 13 days and 0.79 g dm -3 with 4.6 g dm -3 sodium carbonate in solution. Throughout all these experiments a progressive loss of carbonate from the sodium aluminosilicate crystallisation products was observed as a function of time.

  20. Insulating phase of potassium clusters arrayed in low-silica-type zeolite FAU

    NASA Astrophysics Data System (ADS)

    Ikemoto, Y.; Nakano, T.; Kuno, M.; Nozue, Y.; Ikeda, T.

    2001-05-01

    Mutually interacting potassium clusters stabilized in supercages of aluminosilicate zeolite FAU (Si/Al=1), the so-called low-silica X, are investigated in terms of optical and magnetic properties. FAU is ion-exchanged to K, and denoted by K-FAU(1), hereafter. When metal K is adsorbed at the average loading density of 0.7±0.3 atom per supercage of FAU, the observed infrared absorption is more than one order weaker than that in similarly K-loaded samples of K-FAU(1.25) which is called X commonly. The Weiss temperature in K-loaded K-FAU(1) is -33±3 K. This value is several times larger than that in K-loaded K-FAU(1.25). The Mott insulator phase in K clusters in FAU(1), is thought to be realized differently from the metallic phase of K-FAU(1.25).

  1. Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate

    PubMed Central

    Geng, Guoqing; Myers, Rupert J.; Li, Jiaqi; Maboudian, Roya; Carraro, Carlo; Shapiro, David A.; Monteiro, Paulo J. M.

    2017-01-01

    The incorporation of Al and increased curing temperature promotes the crystallization and cross-linking of calcium (alumino)silicate hydrate (C-(A-)S-H), which is the primary binding phase in most contemporary concrete materials. However, the influence of Al-induced structural changes on the mechanical properties at atomistic scale is not well understood. Herein, synchrotron radiation-based high-pressure X-ray diffraction is used to quantify the influence of dreierketten chain cross-linking on the anisotropic mechanical behavior of C-(A-)S-H. We show that the ab-planar stiffness is independent of dreierketten chain defects, e.g. vacancies in bridging tetrahedra sites and Al for Si substitution. The c-axis of non-cross-linked C-(A-)S-H is more deformable due to the softer interlayer opening but stiffens with decreased spacing and/or increased zeolitic water and Ca2+ of the interlayer. Dreierketten chain cross-links act as ‘columns’ to resist compression, thus increasing the bulk modulus of C-(A-)S-H. We provide the first experimental evidence on the influence of the Al-induced atomistic configurational change on the mechanical properties of C-(A-)S-H. Our work advances the fundamental knowledge of C-(A-)S-H on the lowest level of its hierarchical structure, and thus can impact the way that innovative C-(A-)S-H-based cementitious materials are developed using a ‘bottom-up’ approach. PMID:28281635

  2. Cobalt and nickel supported on HY zeolite: Synthesis, characterization and catalytic properties

    SciTech Connect

    Garrido Pedrosa, Anne M. . E-mail: annemgp@yahoo.com; Souza, Marcelo J.B.; Melo, Dulce M.A.; Araujo, Antonio S.

    2006-06-15

    Bifunctional catalysts consisting of cobalt and nickel supported on HY zeolite were synthesized by solvent excess impregnation and characterized by X-ray diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, atomic absorption spectroscopy, thermogravimetric analysis and nitrogen adsorption. The profiles of metal reduction on zeolite were obtained by temperature-programmed reduction. The catalytic properties of the bifunctional catalysts were verified by n-hexane hydroconversion. X-ray diffraction and microstructural analyses showed the presence of crystalline phases in HY zeolite and in samples after impregnation. A decrease in the micropore surface area was observed by nitrogen adsorption experiments and attributed to a reduction in the accessibility to micropores. The catalysts showed catalytic activity in the hydroconversion of n-hexane with selectivity to branched hydrocarbons. Such catalytic activity was related to the acid and metallic properties of the bifunctional catalysts used.

  3. Surface functionalization of aluminosilicate nanotubes with organic molecules

    PubMed Central

    Ma, Wei; Yah, Weng On; Otsuka, Hideyuki

    2012-01-01

    Summary The surface functionalization of inorganic nanostructures is an effective approach for enriching the potential applications of existing nanomaterials. Inorganic nanotubes attract great research interest due to their one-dimensional structure and reactive surfaces. In this review paper, recent developments in surface functionalization of an aluminosilicate nanotube, “imogolite”, are introduced. The functionalization processes are based on the robust affinity between phosphate groups of organic molecules and the aluminol (AlOH) surface of imogolite nanotubes. An aqueous modification process employing a water soluble ammonium salt of alkyl phosphate led to chemisorption of molecules on imogolite at the nanotube level. Polymer-chain-grafted imogolite nanotubes were prepared through surface-initiated polymerization. In addition, the assembly of conjugated molecules, 2-(5’’-hexyl-2,2’:5’,2’’-terthiophen-5-yl)ethylphosphonic acid (HT3P) and 2-(5’’-hexyl-2,2’:5’,2’’-terthiophen-5-yl)ethylphosphonic acid 1,1-dioxide (HT3OP), on the imogolite nanotube surface was achieved by introducing a phosphonic acid group to the corresponding molecules. The optical and photophysical properties of these conjugated-molecule-decorated imogolite nanotubes were characterized. Moreover, poly(3-hexylthiophene) (P3HT) chains were further hybridized with HT3P modified imogolite to form a nanofiber hybrid. PMID:22428100

  4. Development of aluminosilicate polyelectrolytes for solid-state battery applications

    SciTech Connect

    Rawsky, G.C.; Henretta, K.J.; Shriver, D.F.; Lowrey, R.; Vaynman, S.

    1995-12-31

    The authors have synthesized and characterized a range of novel polyelectrolytes containing weakly basic aluminosilicate anions in the polymer backbone in order to achieve t{sub +} = 1 and high ionic mobility. Room-temperature conductivity is observed to increase in the series: [NaAl(OEOMe){sub 2} ((OE){sub x}O){sub 2/2}]{sub n} < [NaAl(OR){sub 2}(OSiMe{sub 2}(CH{sub 2}){sub 3}(OE){sub x}O(CH{sub 2}){sub 3}SiMe{sub 2}O){sub 2/2}]{sub n} < [NaAl(OSiR{sub 3})(OSiMe{sub 2}(CH{sub 2}){sub 3}(OE){sub x}O(CH{sub 2}){sub 3}SiMe{sub 2}O){sub 3/2}]{sub n}. This trend is ascribed to reduced ion pairing due to decreasing anion basicity, and lowered T{sub g} resulting from increasing siloxy character. The addition of cryptang [2.2.2] increases conductivity by 1--1.5 orders of magnitude. A maximum room-temperature conductivity is observed at a ratio of {approx}10 etheric oxygens/cation. Related lithium polymer electrolytes were evaluated in mechanically joined solid state Li{vert_bar}PE{vert_bar}[Li{sub x}Mn{sub 2}O{sub 4}-C-PE] cells.

  5. Ageing characteristics of aluminium alloy aluminosilicate discontinuous fiber reinforced composites

    SciTech Connect

    Nath, D.; Singh, V.

    1999-03-05

    Development of continuous fiber reinforced metal matrix composites is aimed at providing high specific strength and stiffness needed for aerospace and some critical high temperature structural applications. Considerable efforts have been made, during the last decade, to improve the strength of age-hardening aluminium alloy matrix composites by suitable heat treatment. It has also been well established that age-hardenable aluminium alloy composites show accelerated ageing behavior because of enhanced dislocation density at the fiber/matrix interface resulting from thermal expansion mismatch between ceramic fiber and the metal matrix. The accelerated ageing of aluminium alloy composites either from dislocation density or the residual stress, as a result of thermal expansion mismatch is dependent on the size of whisker and particulate. Investigations have also been made on the effect of volume fraction of particulate on the ageing behavior of aluminium alloys. The present investigation is concerned with characterization of age-hardening behavior of an Al-Si-Cu-Mg(AA 336) alloy alumino-silicate discontinuous fiber-reinforced composites (referred to as aluminium MMCs in the present text) being developed for automotive pistons. An effort is made to study the effect of volume fraction of the reinforcement on age-hardening behavior of this composite.

  6. SODIUM ALUMINOSILICATE SOLIDS AFFINITY FOR CESIUM AND ACTINIDES

    SciTech Connect

    Peters, T; Bill Wilmarth, B; Samuel Fink, S

    2007-07-31

    Washed sodium-aluminosilicate (NAS) solids at initial concentrations of 3.55 and 5.4 g/L sorb or uptake virtually no cesium over 288 hours, nor do any NAS solids generated during that time. These concentrations of solids are believed to conservatively bound current and near-term operations. Hence, the NAS solids should not have affected measurements of the cesium during the mass transfer tests and there is minimal risk of accumulating cesium during routine operations (and hence posing a gamma radiation exposure risk in maintenance). With respect to actinide uptake, it appears that NAS solids sorb minimal quantities of uranium - up to 58 mg U per kg NAS solid. The behavior with plutonium is less well understood. Additional study may be needed for radioactive operations relative to plutonium or other fissile component sorption or trapping by the solids. We recommend this testing be incorporated in the planned tests using samples from Tank 25F and Tank 49H to extend the duration to bound expected inventory time for solution.

  7. Zeolite membranes: microstructure characterization and permeation mechanisms.

    PubMed

    Yu, Miao; Noble, Richard D; Falconer, John L

    2011-11-15

    Since their first synthesis in the 1940s, zeolites have found wide applications in catalysis, ion-exchange, and adsorption. Although the uniform, molecular-size pores of zeolites and their excellent thermal and chemical stability suggest that zeolites could be an ideal membrane material, continuous polycrystalline zeolite layers for separations were first prepared in the 1990s. Initial attempts to grow continuous zeolite layers on porous supports by in situ hydrothermal synthesis have resulted in membranes with the potential to separate molecules based on differences in molecular size and adsorption strength. Since then, further synthesis efforts have led to the preparation of many types of zeolite membranes and better quality membranes. However, the microstructure features of these membranes, such as defect size, number, and distribution as well as structure flexibility were poorly understood, and the fundamental mechanisms of permeation (adsorption and diffusion), especially for mixtures, were not clear. These gaps in understanding have hindered the design and control of separation processes using zeolite membranes. In this Account, we describe our efforts to characterize microstructures of zeolite membranes and to understand the fundamental adsorption and diffusion behavior of permeating solutes. This Account will focus on the MFI membranes which have been the most widely used but will also present results on other types of zeolite membranes. Using permeation, x-ray diffraction, and optical measurements, we found that the zeolite membrane structures are flexible. The size of defects changed due to adsorption and with variations in temperature. These changes in defect sizes can significantly affect the permeation properties of the membranes. We designed methods to measure mixture adsorption in zeolite crystals from the liquid phase, pure component adsorption in zeolite membranes, and diffusion through zeolite membranes. We hope that better understanding can lead

  8. Structure-Directing Roles and Interactions of Fluoride and Organocations with Siliceous Zeolite Frameworks

    SciTech Connect

    Shayib, Ramzy M.; George, Nathan C.; Seshadri, Ram; Burton, Allen W.; Zones, Stacey I.; Chmelka, Bradley F.

    2012-02-06

    Interactions of fluoride anions and organocations with crystalline silicate frameworks are shown to depend subtly on the architectures of the organic species, which significantly influence the crystalline structures that result. One- and two-dimensional (2D) {sup 1}H, {sup 19}F, and {sup 29}Si nuclear magnetic resonance (NMR) spectroscopy measurements establish distinct intermolecular interactions among F{sup -} anions, imidazolium structure-directing agents (SDA{sup +}), and crystalline silicate frameworks for as-synthesized siliceous zeolites ITW and MTT. Different types and positions of hydrophobic alkyl ligands on the imidazolium SDA{sup +} species under otherwise identical zeolite synthesis compositions and conditions lead to significantly different interactions between the F{sup -} and SDA{sup +} ions and the respective silicate frameworks. For as-synthesized zeolite ITW, F{sup -} anions are established to reside in the double-four-ring (D4R) cages and interact strongly and selectively with D4R silicate framework sites, as manifested by their strong {sup 19}F{sup 29}Si dipolar couplings. By comparison, for as-synthesized zeolite MTT, F{sup -} anions reside within the 10-ring channels and interact relatively weakly with the silicate framework as ion pairs with the SDA{sup +} ions. Such differences manifest the importance of interactions between the imidazolium and F{sup -} ions, which account for their structure-directing influences on the topologies of the resulting silicate frameworks. Furthermore, 2D {sup 29}Si{l_brace}{sup 29}Si{r_brace} double-quantum NMR measurements establish {sup 29}Si-O-{sup 29}Si site connectivities within the as-synthesized zeolites ITW and MTT that, in conjunction with synchrotron X-ray diffraction analyses, establish insights on complicated order and disorder within their framework structures.

  9. Parameters influencing zeolite incorporation in PDMS membranes

    SciTech Connect

    Vankelecom, I.F.J.; Scheppers, E.; Heus, R.; Uytterhoeven, J.B. )

    1994-11-24

    The incorporation of several types of zeolite in PDMS membranes is studied, by measuring the tensile strength, xylene sorption, and density of the membranes. The zeolite is shown to be involved in the cross-linking of the membrane. The interaction between the PDMS matrix and the zeolites results in reinforced membranes in the case of zeolite Y. The parameters influencing the dispersion of the zeolite in the membrane are investigated, as well as several aspects of the preparation method. Finally, the idea of cross-linking is applied to explain the results of water/ethanol pervaporation. 25 refs., 9 figs., 4 tabs.

  10. High-performance zeolite NaA membranes on polymer-zeolite composite hollow fiber supports.

    PubMed

    Ge, Qinqin; Wang, Zhengbao; Yan, Yushan

    2009-12-02

    We report a new strategy: use of polymer-zeolite composite hollow fibers as supports. Zeolite membranes with high performance (flux = 8.0-9.0 kg m(-2) h(-1), alpha >10 000) can be synthesized directly on polymer-zeolite composite hollow fiber supports by a single in situ hydrothermal crystallization. The zeolite crystals imbedded in the polymer hollow fiber serve as seeds for the zeolite membrane growth, and they also "anchor" the zeolite membrane to the support to increase the adhesion of the zeolite membrane. Therefore, a separate and often complex seeding process can be omitted. A very uniform crystal distribution can be obtained easily, so continuous zeolite membranes can be prepared with high reproducibility. These composite hollow fibers can be produced simply by blending zeolite crystals into the polymer feed before the hollow fiber extrusion and thus are expected to be inexpensive.

  11. Improving the quality of patchouli oil by adsorption process using surfactant modified of natural zeolite

    NASA Astrophysics Data System (ADS)

    Kuntari, Purbaningtias, Tri Esti; Wiyantoko, Bayu; Kurniawati, Puji; Prasetyoko, Didik; Suprapto

    2017-03-01

    This research concerns with the development of natural material i.e. natural zeolite. Natural zeolite were modified by surfactant treatment. Material modification has been done using cetyltrimethyllammonium bromide as cationic surfactant for mesopore template. The physicochemical characters of natural material modified and unmodified was investigated by using XRD, FTIR, nitrogen physisorption, and SEM-EDX. The XRD was used to show crystallinity structure of natural material modified and unmodified. Surfactant treatment caused decreasing crystallinity of natural zeolite. The FTIR spectra showed characteristic peaks for natural zeolite modified and unmodified, the bands around 3400-3500 cm-1 and 1635-1641 cm-1 correspond to adsorbed water and bands around finger print area were characteristic for silica and alumina. Meanwhile physisorption nitrogen profiles gave information that the pore modification by surfactant. The morphologies of natural material modified and unmodified as well as chemical composition of the particles were shown by SEM-EDX. The usage of modified material decrease acidity number into 19.47% than unmodified material, which is 7,62%. The GC analysis showed that percentage of patchouli alcohol increases and new peaks were not identified indicated there was not any reaction appeared.

  12. Early stage reversed crystal growth of zeolite A and its phase transformation to sodalite.

    PubMed

    Greer, Heather; Wheatley, Paul S; Ashbrook, Sharon E; Morris, Russell E; Zhou, Wuzong

    2009-12-16

    Microstructural analysis of the early stage crystal growth of zeolite A in hydrothermal synthetic conditions revealed a revised crystal growth route from surface to core in the presence of the biopolymer chitosan. The mechanism of this extraordinary crystal growth route is discussed. In the first stage, the precursor and biopolymer aggregated into amorphous spherical particles. Crystallization occurred on the surface of these spheres, forming the typical cubic morphology associated with zeolite A with a very thin crystalline cubic shell and an amorphous core. With a surface-to-core extension of crystallization, sodalite nanoplates were crystallized within the amorphous cores of these zeolite A cubes, most likely due to an increase of pressure. These sodalite nanoplates increased in size, breaking the cubic shells of zeolite A in the process, leading to the phase transformation from zeolite A to sodalite via an Ostwald ripening process. Characterization of specimens was performed using scanning electron microscopy and transmission electron microscopy, supported by other techniques including X-ray diffraction, solid-state NMR, and N(2) adsorption/desorption.

  13. One-pot pseudomorphic crystallization of mesoporous porous silica to hierarchical porous zeolites

    SciTech Connect

    Xing, Jun-Ling; Jiang, Shu-Hua; Pang, Jun-Ling; Yuan, En-Hui; Ma, Xiao-Jing; Lam, Koon-Fung; Xue, Qing-Song; Zhang, Kun

    2015-09-15

    Hierarchically porous silica with mesopore and zeolitic micropore was synthesized via pseudomorphic crystallization under high-temperature hydrothermal treatment in the presence of cetyltrimethylammonium tosylate and tetrapropylammonium ions. A combined characterization using small-angle X-ray diffraction (XRD), nitrogen adsorption, high-resolution transmission electron microscopy (TEM), thermogravimetric analysis (TG), and elemental analysis showed that dual templates, CTA{sup +} and TPA{sup +} molecules, can work in a cooperative manner to synthesize mesoporous zeolite in a one-pot system by precisely tuning the reaction conditions, such as reaction time and temperature, and type and amount of heterometal atoms. It is found that the presence of Ti precursor is critical to the successful synthesis of such nanostructure. It not only retards the nucleation and growth of crystalline MFI domains, but also acts as nano-binder or nano-glue to favor the assembly of zeolite nanoblocks. - Graphical abstract: Display Omitted - Highlights: • A facile method to synthesize mesoporous zeolites with hierarchical porosity was presented. • It gives a new insight into keeping the balance between mesoscopic and molecular ordering in hierarchical porous materials. • A new understanding on the solid–solid transformation mechanism for the synthesis of titanosilicate zeolites was proposed.

  14. Nanocrystalline Zeolite Y: Synthesis and Characterization

    NASA Astrophysics Data System (ADS)

    Taufiqurrahmi, Niken; Rahman Mohamed, Abdul; Bhatia, Subhash

    2011-02-01

    Nanocrystalline zeolite has received significant attention in the catalysis community. Zeolites with a crystal size smaller than 100 nm are the potential replacement for existing zeolite catalysts due to its unique features with added advantages. Zeolite FAU type Y is one of the most studied framework of all zeolites, and has been used as catalysts for number of reactions in the refinery and petrochemical industry. The present paper covers the synthesis of nanocrystalline zeolite Y under hydrothermal conditions from clear synthesis mixtures. The crystal size of zeolite Y is influenced by temperature, aging time, alkalinity, and water content. The synthesized Y is characterized by X-ray diffraction (XRD), Fourier Transmission Infrared Sprectroscopy (FTIR), Transmission Electron Microscope (TEM), Scanning Electron Microscope (SEM) and Nitrogen Adsorption.

  15. Enhanced selectivity of zeolites by controlled carbon deposition

    DOEpatents

    Nenoff, Tina M.; Thoma, Steven G.; Kartin, Mutlu

    2006-05-09

    A method for carbonizing a zeolite comprises depositing a carbon coating on the zeolite pores by flowing an inert carrier gas stream containing isoprene through a regenerated zeolite at elevated temperature. The carbonized zeolite is useful for the separation of light hydrocarbon mixtures due to size exclusion and the differential adsorption properties of the carbonized zeolite.

  16. Metal immobilization in soils using synthetic zeolites.

    PubMed

    Oste, Leonard A; Lexmond, Theo M; Van Riemsdijk, Willem H

    2002-01-01

    In situ immobilization of heavy metals in contaminated soils is a technique to improve soil quality. Synthetic zeolites are potentially useful additives to bind heavy metals. This study selected the most effective zeolite in cadmium and zinc binding out of six synthetic zeolites (mordenite-type, faujasite-type, zeolite X, zeolite P, and two zeolites A) and one natural zeolite (clinoptilolite). Zeolite A appeared to have the highest binding capacity between pH 5 and 6.5 and was stable above pH 5.5. The second objective of this study was to investigate the effects of zeolite addition on the dissolved organic matter (DOM) concentration. Since zeolites increase soil pH and bind Ca, their application might lead to dispersion of organic matter. In a batch experiment, the DOM concentration increased by a factor of 5 when the pH increased from 6 to 8 as a result of zeolite A addition. A strong increase in DOM was also found in the leachate of soil columns, particularly in the beginning of the experiment. This resulted in higher metal leaching caused by metal-DOM complexes. In contrast, the free ionic concentration of Cd and Zn strongly decreased after the addition of zeolites, which might explain the reduction in metal uptake observed in plant growth experiments. Pretreatment of zeolites with acid (to prevent a pH increase) or Ca (to coagulate organic matter) suppressed the dispersion of organic matter, but also decreased the metal binding capacity of the zeolites due to competition of protons or Ca.

  17. Cation siting in low-silica zeolites with potential applications in pressure swing adsorption technology and structural studies of novel tectosilicates

    NASA Astrophysics Data System (ADS)

    Burton, Allen Wayne

    Adsorption and catalytic phenomena in zeolites are influenced by coulombic interactions within zeolite structure as well as by size restrictions imposed by zeolitic micropores. In the first part of this thesis, we investigate materials with potential applications in the selective adsorption of nitrogen. Studies have indicated the performance of LiX adsorbents correlates with the number of accessible lithium cations in the zeolite. However, in zeolite LiX only one-third of the lithium cations interact with adsorbed molecules. This prompted our investigation of other low-silica zeolites. The first zeolite examined was a cancrinite prepared in the presence of 1,3-butanediol. Neutron diffraction studies on the lithium-exchanged cancrinite suggest most of the lithium cations are ideally positioned within the micropores. However, our experiments show that carbonate anions are occluded within the micropores of this cancrinite. Another material examined in this study was zeolite (Ba,K)-GL. Neutron diffraction experiments show that 49 of the extraframework charges are located in the micropores. Unfortunately, less than 20% of these cations are replaced after lithium-exchange. We also attempted to directly synthesize a (Ba,Li)-GL. However, diffraction experiments and chemical analyses show that most of the extraframework charge is compensated by barium. Because of molecular size restrictions imposed by currently known zeolites, there is continued interest in the synthesis of materials that can be used for processing large molecules. This motivated our investigation of two tectosilicates MCM-61 and MCM-47. MCM-61 is an aluminosilicate made in the presence of the potassium-18-Crown-6 complex. Our structure solution shows MCM-61 is formed from novel [610412] polyhedral cage units that connect to form 18-membered-ring cages. The structure of MCM-61 suggests that crown ethers, azamacrocycles, and cryptands may be useful for the syntheses of extra-large pore zeolites. MCM-47 is

  18. Aqueous dissolution of sodium aluminosilicate geopolymers derived from metakaolin

    NASA Astrophysics Data System (ADS)

    Aly, Z.; Vance, E. R.; Perera, D. S.

    2012-05-01

    In dilute aqueous solutions, the elemental releases of Na, Al and Si from a metakaolin-based sodium aluminosilicate geopolymer were not very sensitive to pH in the range of 4-10 but increased outside this range, particularly on the acidic side. To minimise pH drifts, experiments were carried out using small amounts of graded powders in relatively large volumes of water. In deionised water, the Na dissolution rate in 7 days was dominant and increased by at least a factor of ˜4 on heating from 18 to 90 °C, with greater increases in the extractions of Al and Si. At 18 °C the elemental extractions in deionised water increased approximately linearly with time over the 1-7 days period. Further exposure led to a slower extraction into solution for Na and Si, with a decrease in extraction of Al. It was deduced that framework dissolution was important in significantly acidic or alkaline solutions, but that contributions from water transfer from pores to elemental extractions were present, even at low temperatures in neutral solutions. It was also deduced from the Na release data that the Na leaching kinetics of geopolymer in deionised water (dilute solutions) followed the pseudo-second-order kinetic model and the pseudo-second-order rate constant evaluated. Contact with KCl, KHCO3, and pH ˜6 and 10 potassium phthalate buffer solutions gave rise to a high degree of Na+ ↔ K+ exchange and rendered the framework ions less leachable in water.

  19. Crystalline and Crystalline International Disposal Activities

    SciTech Connect

    Viswanathan, Hari S.; Chu, Shaoping; Reimus, Paul William; Makedonska, Nataliia; Hyman, Jeffrey De'Haven; Karra, Satish; Dittrich, Timothy M.

    2015-12-21

    This report presents the results of work conducted between September 2014 and July 2015 at Los Alamos National Laboratory in the crystalline disposal and crystalline international disposal work packages of the Used Fuel Disposition Campaign (UFDC) for DOE-NE’s Fuel Cycle Research and Development program.

  20. In vitro evaluation of the capacity of zeolite and bentonite to adsorb aflatoxin B1 in simulated gastrointestinal fluids.

    PubMed

    Thieu, N Q; Pettersson, H

    2008-09-01

    Anin vitro study using single concentration and isotherm adsorption was carried out to evaluate the capacity of Vietnamese produced zeolite and bentonite to adsorb aflatoxin B1 (AFB1) in simulated gastrointestinal fluids (SGFs), and a commercial sorbent hydrated sodium calcium aluminosilicate (HSCAS) was used as reference. In this study, AFB1 solution was mixed with sorbents (0.3, 0.4 and 0.5% w/v) in SGFs at pH 3 and pH 7 and shaken for 8 h, centrifuged and the supernatant measured by Vicam fluorometer. Adsorption of AFB1 onto zeolite and bentonite varied according to the pH of SGFs and was lower than HSCAS. Linearity between the increased amount of AFB1 adsorbed on sorbents and the decrease of sorbent concentration was observed for bentonite and HSCAS, except for zeolite in SGFs at pH 7. The observed maximum amounts of AFB1 adsorbed on bentonite and HSCAS were 1.54 and 1.56 mg/g, respectively. The adsorption capacities of bentonite and HSCAS for AFB1 were 12.7 and 13.1 mg/g, respectively, from fitting the data to the Freundlich isotherm equation. Improvement in processing and purification for bentonite is needed to enhance the surface area, which would probably result in better adsorptive capacity for this sorbent.

  1. Multiple-quantum NMR studies of spin clusters in liquid crystals and zeolites

    SciTech Connect

    Pearson, J. . Dept. of Chemistry Lawrence Berkeley Lab., CA )

    1991-07-01

    This work will describe the use of MQ NMR to study spin clusters in anisotropic materials. A technique known as multiple-quantum spin counting was used to determine average spin cluster sizes liquid crystalline materials and in faujacitic zeolites containing aromatic hydrocarbons. The first half of the thesis will describe MQ NMR and the MQ spin counting technique, and the second half of the thesis will describe the actual experiments and their results.

  2. Superior performance of metal-organic frameworks over zeolites as solid acid catalysts in the Prins reaction: green synthesis of nopol.

    PubMed

    Opanasenko, Maksym; Dhakshinamoorthy, Amarajothi; Hwang, Young Kyu; Chang, Jong-San; Garcia, Hermenegildo; Čejka, Jiří

    2013-05-01

    The catalytic performance of a set of metal-organic frameworks [CuBTC, FeBTC, MIL-100(Fe), MIL-100(Cr), ZIF-8, MIL-53(Al)] was investigated in the Prins condensation of β-pinene with formaldehyde and compared with the catalytic behavior of conventional aluminosilicate zeolites BEA and FAU and titanosilicate zeolite MFI (TS-1). The activity of the investigated metal-organic frameworks (MOFs) increased with the increasing concentration of accessible Lewis acid sites in the order ZIF-8zeolites BEA and FAU, which showed significantly lower selectivity to the target nopol than the MOFs. Its high activity, the preservation of its structure and active sites, and the possibility to use it in at least three catalytic cycles without loss of activity make MIL-100 (Fe) the best performing catalyst of the series for the Prins condensation of β-pinene and paraformaldehyde. Our report exemplifies the advantages of MOFs over zeolites as solid catalysts in liquid-phase reactions for the production of fine chemicals.

  3. Hydrophobic high surface area zeolites derived from fly ash for oil spill remediation.

    PubMed

    Sakthivel, Tamilselvan; Reid, David L; Goldstein, Ian; Hench, Larry; Seal, Sudipta

    2013-06-04

    Fly ash, a coal combustion byproduct with a predominantly aluminosilicate composition, is modified to develop an inexpensive sorbent for oil spill remediation. The as-produced fly ash is a hydrophilic material with poor sorption capacity. A simple two-step chemical modification process is designed to improve the oil sorption capacity. First, the fly ash was transformed to a zeolitic material via an alkali treatment, which increased the specific surface area up to 404 m(2) g(-1). Then, the material was surface functionalized to form a hydrophobic material with high contact angle up to 147° that floats on the surface of an oil-water mixture. The reported oil sorption capacities of X-type zeolite sorbent with different surface functionalization (propyl-, octyl-, octadecyl-trimethoxysilane and esterification) were estimated to 1.10, 1.02, 0.86, and 1.15 g g(-1), respectively. Oil sorption was about five times higher than the as-received fly ash (0.19 g g(-1)) and also had high buoyancy critical for economic cleanup of oil over water.

  4. Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2006-09-30

    The addition of hydrothermally-aged zeolite Y precursor to an SBA-15 synthesis mixture under a mildly acidic condition resulted in the formation of mesoporous aluminosilicate catalyst, Al-SBA-15, containing strong Broensted acid sites and aluminum (Al) stabilized in a totally tetrahedral coordination. The physicochemical characteristics of the catalyst varied as a function of the synthesis conditions. The catalyst possessed surface areas ranging between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm, and pore volumes up 1.03 cm{sup 3}, which were comparable to the parent SBA-15 synthesized under similar conditions. Two wt% Al was present in the catalyst that was obtained from the reaction mixture that contained the highest Al content. The Al remained stable in totally tetrahedral coordination after calcination at 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and the activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. In preparation for the final phase of the project, the catalyst was embedded into psuedoboemite alumina (catapal B) matrix and then formed into pellets. In the final phase of the project, the pelletized catalyst will be evaluated for the conversion of heavy petroleum feedstocks to naphtha and middle distillates.

  5. Li{sup +} alumino-silicate ion source development for the neutralized drift compression experiment

    SciTech Connect

    Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W.; Seidl, Peter A.; Waldron, William L.; Wu, James K.

    2011-01-15

    We report results on lithium alumino-silicate ion source development in preparation for warm dense matter heating experiments on the new neutralized drift compression experiment II. The practical limit to the current density for a lithium alumino-silicate source is determined by the maximum operating temperature that the ion source can withstand before running into problems of heat transfer, melting of the alumino-silicate material, and emission lifetime. Using small prototype emitters, at a temperature of {approx_equal}1275 deg. C, a space-charge limited Li{sup +} beam current density of J {approx_equal}1 mA/cm{sup 2} was obtained. The lifetime of the ion source was {approx_equal}50 h while pulsing at a rate of 0.033 Hz with a pulse duration of 5-6 {mu}s.

  6. Evidence for lithium-aluminosilicate supersaturation of pegmatite-forming melts

    NASA Astrophysics Data System (ADS)

    Maneta, Victoria; Baker, Don R.; Minarik, William

    2015-07-01

    New experimental data on the solubility of lithium (Li) at spodumene (LiAlSi2O6) and petalite (LiAlSi4O10) saturation at 500 MPa and 550-750 °C reveal evidence for lithium supersaturation of pegmatite-forming melts before the formation of Li-aluminosilicates. The degree of Li enrichment in granitic melts can reach ~11,000 ppm above the saturation value before the crystallization of Li-aluminosilicate minerals at lower temperatures. Comparison of the experimental results with the spodumene-rich Moblan pegmatite (Quebec) is consistent with extreme Li enrichment of the pegmatite-forming melt prior to emplacement, which cannot be explained with equilibrium crystallization of Li-aluminosilicates from a common granitic melt. The results of this study support the model of disequilibrium fractional crystallization through liquidus undercooling as the most plausible mechanism for the generation of such Li-rich ore resources.

  7. The effects of ochratoxin/aluminosilicate interaction on the tissues and humoral immune response of broilers.

    PubMed

    Santin, Elizabeth; Paulillo, Antonio C; Maiorka, Paulo C; Alessi, Antonio C; Krabbe, Everton L; Maiorka, Alex

    2002-02-01

    This study aimed to evaluate the effect of dietary ochratoxin, in the presence or absence of aluminosilicate, on the histology of the bursa of Fabricius, liver and kidneys, and on the humoral immune response of broilers vaccinated against Newcastle disease virus. The exposure of birds to 2 p.p.m. ochratoxin, in the presence or absence of aluminosilicate, reduced their humoral immune response and the number of mitotic cells in the bursa. The relative weight of the livers of the birds exposed to this toxin was increased and, microscopically, there was hepatocyte vacuolation and megalocytosis with accompanying hyperplasia of the biliary epithelium. The kidneys showed hypertrophy of the renal proximal tubular epithelium, with thickening of the glomerular basement membrane. Aluminosilicate did not ameliorate the deleterious effects of the ochratoxin.

  8. Li+ alumino-silicate ion source development for the Neutralized Drift Compression Experiment (NDCX)

    SciTech Connect

    Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W.; Seidl, Peter A.; Waldron, William L.; Wu, James K.

    2010-10-01

    We report results on lithium alumino-silicate ion source development in preparation for warmdense-matter heating experiments on the new Neutralized Drift Compression Experiment (NDCXII). The practical limit to the current density for a lithium alumino-silicate source is determined by the maximum operating temperature that the ion source can withstand before running into problems of heat transfer, melting of the alumino-silicate material, and emission lifetime. Using small prototype emitters, at a temperature of ~;;1275 oC, a space-charge-limited Li+ beam current density of J ~;;1 mA/cm2 was obtained. The lifetime of the ion source was ~;;50 hours while pulsing at a rate of 0.033 Hz with a pulse duration of 5-6 mu s.

  9. Synthesis and immobilization of silver nanoparticles on aluminosilicate nanotubes and their antibacterial properties

    NASA Astrophysics Data System (ADS)

    Ipek Yucelen, G.; Connell, Rachel E.; Terbush, Jessica R.; Westenberg, David J.; Dogan, Fatih

    2016-04-01

    A novel colloidal method is presented to synthesize silver nanoparticles on aluminosilicate nanotubes. The technique involves decomposition of AgNO3 solution to Ag nanoparticles in the presence of aluminosilicate nanotubes at room temperature without utilizing of reducing agents or any organic additives. Aluminosilicate nanotubes are shown to be capable of providing a unique chemical environment, not only for in situ conversion of Ag+ into Ag0, but also for stabilization and immobilization of Ag nanoparticles. The synthesis strategy described here could be implemented to obtain self-assembled nanoparticles on other single-walled metal oxide nanotubes for unique applications. Finally, we demonstrated that nanotube/nanoparticle hybrid show strong antibacterial activity toward Gram-positive Staphylococcus epidermidis and Gram-negative Escherichia coli.

  10. Modeling the Formation of Alkali Aluminosilicate Gels at the Mesoscale Using Coarse-Grained Monte Carlo.

    PubMed

    Yang, Kengran; White, Claire E

    2016-11-08

    Alkali-activated materials (AAMs) are currently being pursued as viable alternatives to conventional ordinary Portland cement because of their lower carbon footprint and established mechanical performance. However, our understanding of the mesoscale morphology (∼1 to 100 nm) of AAMs and related amorphous aluminosilicate gels, including the development of the three-dimensional aluminosilicate network and nanoscale porosity, is severely limited. This study investigates the structural changes that occur during the formation of AAM gels at the mesoscale by utilizing a coarse-grained Monte Carlo (CGMC) modeling technique that exploits density functional theory calculations. The model is capable of simulating the reaction of an aluminosilicate particle in a highly alkaline solution (sodium hydroxide or sodium silicate). Two precursor morphologies have been investigated (layered alumina and silica sheets mimicking metakaolin and spherical aluminosilicate particles reminiscent of coal-derived fly ash) to determine if the precursor morphology has an impact on the structural evolution of the resulting alkali-activated aluminosilicate gel. The CGMC model can capture the three major stages of the alkali-activation process-dissolution, polycondensation, and reorganization-revealing that the dissolved silicate and aluminate species, ranging from monomers to nanoprecipitates (100s of monomers in size), exist in the pore solution of the hardened gel. The model also reveals that the silica concentration of the activating solution controls the extent of dissolution of the precursor particle. From the analysis of the aluminosilicate cluster size distributions, the mechanisms of AAM gel growth have been elucidated, revealing that Ostwald ripening occurs in systems containing free silica at the start of the reaction. On the other hand, growth of the hydroxide-activated systems (metakaolin and fly ash) occurs via the formation of intermediate-sized clusters in addition to continual

  11. UTILITY OF ZEOLITES IN HAZARDOUS METAL REMOVAL FROM WATER

    EPA Science Inventory

    Zeolites are well known for their ion exchange, adsorption and acid catalysis properties. Different inorganic pollutants have been removed from water at room temperature by using synthetic zeolites. Zeolite Faujasite Y has been used to remove inorganic pollutants including arseni...

  12. Hydrogen Selective Exfoliated Zeolite Membranes

    SciTech Connect

    Tsapatsis, Michael; Daoutidis, Prodromos; Elyassi, Bahman; Lima, Fernando; Iyer, Aparna; Agrawal, Kumar; Sabnis, Sanket

    2015-04-06

    The objective of this project was to develop and evaluate an innovative membrane technology at process conditions that would be representative of Integrated Gasification Combined Cycle (IGCC) advanced power generation with pre-combustion capture of carbon dioxide (CO2). This research focused on hydrogen (H2)-selective zeolite membranes that could be utilized to separate conditioned syngas into H2-rich and CO2-rich components. Both experiments and process design and optimization calculations were performed to evaluate the concept of ultra-thin membranes made from zeolites nanosheets. In this work, efforts in the laboratory were made to tackle two fundamental challenges in application of zeolite membranes in harsh industrial environments, namely, membrane thickness and membrane stability. Conventional zeolite membranes have thicknesses in the micron range, limiting their performance. In this research, we developed a method for fabrication of ultimately thin zeolite membranes based on zeolite nanosheets. A range of layered zeolites (MWW, RWR, NSI structure types) suitable for hydrogen separation was successfully exfoliated to their constituent nanosheets. Further, membranes were made from one of these zeolites, MWW, to demonstrate the potential of this group of materials. Moreover, long-term steam stability of these zeolites (up to 6 months) was investigated in high concentrations of steam (35 mol% and 95 mole%), high pressure (10 barg), and high temperatures (350 °C and 600 °C) relevant to conditions of water-gas-shift and steam methane reforming reactions. It was found that certain nanosheets are stable, and that stability depends on the concentration of structural defects. Additionally, models that represent a water-gas-shift (WGS) membrane reactor equipped with the zeolite membrane were developed for systems studies. These studies had the aim of analyzing the effect of the membrane reactor integration into IGCC plants

  13. Calculation of the Aluminosilicate Half-Life Formation Time in the 2H Evaporator

    SciTech Connect

    Fondeur, F.F.

    2000-09-21

    The 2H Evaporator contains large quantities of aluminosilicate solids deposited on internal fixtures. The proposed cleaning operations will dissolve the solids in nitric acid. Operations will then neutralize the waste prior to transfer to a waste tank. Combining recent calculations of heat transfer for the 2H Evaporator cleaning operations and laboratory experiments for dissolution of solid samples from the pot, the authors estimated the re-formation rate for aluminosilicates during cooling. The results indicate a half-life formation of 17 hours when evaporator solution cools from 60 degrees C and 9 hours when cooled from 90 degrees C.

  14. Tailored zeolites for the removal of metal oxyanions: overcoming intrinsic limitations of zeolites.

    PubMed

    Figueiredo, Hugo; Quintelas, Cristina

    2014-06-15

    This review aims to present a global view of the efforts conducted to convert zeolites into efficient supports for the removal of heavy metal oxyanions. Despite lacking affinity for these species, due to inherent charge repulsion between zeolite framework and anionic species, zeolites have still received considerable attention from the scientific community, since their versatility allowed tailoring them to answer specific requirements. Different processes for the removal and recovery of toxic metals based on zeolites have been presented. These processes resort to modification of the zeolite surface to allow direct adsorption of oxyanions, or by combination with reducing agents for oxyanions that allow ion-exchange with the converted species by the zeolite itself. In order to testify zeolite versatility, as well as covering the wide array of physicochemical constraints that oxyanions offer, chromium and arsenic oxyanions were selected as model compounds for a review of treatment/remediation strategies, based on zeolite modification.

  15. The impact of aqueous medium on zeolite framework integrity

    SciTech Connect

    Vjunov, Aleksei; Fulton, John L.; Camaioni, Donald M.; Hu, Jian Z.; Burton, Sarah D.; Arslan, Ilke; Lercher, Johannes A.

    2015-05-12

    Understanding the zeolite framework stability in aqueous phase is crucial to develop stable catalysts. Al K–edge, extended X–ray absorption fine structure and 27Al MAS NMR spectroscopies in combination with DFT calculations have been used to monitor both qualitative and quantitative structural changes of two well–characterized samples with BEA structure. The effects of various properties on stability were explored, including Al concentration, Al distribution, particle size and structural defects. As the samples were degraded by treatment in hot liquid water, the local structure about the Al T–site remained mostly intact, including the Al–O–Si angles and bond distances, while the nano–scale crystalline structure as measured by XRD and TEM was disrupted. The combined data suggest a three–step mechanism in which, initially, the HBEA framework crystallinity decreases via hydrolysis of T–O bonds along polymorph stacking faults and inter–grain boundaries in a mode similar to crack propagation in glass. With prolonged exposure, amorphization occurs via hydrolysis of surface Si–OH groups propagating inward through the zeolite lattice. In parallel, cracks propagate within the crystalline micro–domains along paths through specific T–O–T groups. Authors thank B. W. Arey (PNNL) for HIM measurements, T. Huthwelker for support during Al XAFS measurements at the Swiss Light Source (PSI, Switzerland) and M. Y. Hu (PNNL) for support during NMR experiments. This work was supported by the U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. NMR experiments were performed at the Environmental Molecular Science Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research, and Physical Science Laboratory both located at Pacific Northwest National Laboratory (PNNL). PNNL is a multi–program national laboratory

  16. Enhancing Nitrification at Low Temperature with Zeolite in a Mining Operations Retention Pond

    PubMed Central

    Miazga-Rodriguez, Misha; Han, Sukkyun; Yakiwchuk, Brian; Wei, Kai; English, Colleen; Bourn, Steven; Bohnert, Seth; Stein, Lisa Y.

    2012-01-01

    Ammonium nitrate explosives are used in mining operations at Diavik Diamond Mines Inc. in the Northwest Territories, Canada. Residual nitrogen is washed into the mine pit and piped to a nearby retention pond where its removal is accomplished by microbial activity prior to a final water treatment step and release into the sub-Arctic lake, Lac de Gras. Microbial removal of ammonium in the retention pond is rapid during the brief ice-free summer, but often slows under ice cover that persists up to 9 months of the year. The aluminosilicate mineral zeolite was tested as an additive to retention pond water to increase rates of ammonium removal at 4°C. Water samples were collected across the length of the retention pond monthly over a year. The structure of the microbial community (bacteria, archaea, and eukarya), as determined by denaturing gradient gel electrophoresis of PCR-amplified small subunit ribosomal RNA genes, was more stable during cold months than during July–September, when there was a marked phytoplankton bloom. Of the ammonia-oxidizing community, only bacterial amoA genes were consistently detected. Zeolite (10 g) was added to retention pond water (100 mL) amended with 5 mM ammonium and incubated at 12°C to encourage development of a nitrifying biofilm. The biofilm community was composed of different amoA phylotypes from those identified in gene clone libraries of native water samples. Zeolite biofilm was added to fresh water samples collected at different times of the year, resulting in a significant increase in laboratory measurements of potential nitrification activity at 4°C. A significant positive correlation between the amount of zeolite biofilm and potential nitrification activity was observed; rates were unaffected in incubations containing 1–20 mM ammonium. Addition of zeolite to retention ponds in cold environments could effectively increase nitrification rates year-round by concentrating active nitrifying biomass. PMID:22866052

  17. Synthesis, characterization and catalytic activity of indium substituted nanocrystalline Mobil Five (MFI) zeolite

    SciTech Connect

    Shah, Kishor Kr.; Nandi, Mithun; Talukdar, Anup K.

    2015-06-15

    Highlights: • In situ modification of the MFI zeolite by incorporation of indium. • The samples were characterized by XRD, FTIR, TGA, UV–vis (DRS), SAA, EDX and SEM. • The incorporation of indium was confirmed by XRD, FT-IR, UV–vis (DRS), EDX and TGA. • Hydroxylation of phenol reaction was studied on the synthesized catalysts. - Abstract: A series of indium doped Mobil Five (MFI) zeolite were synthesized hydrothermally with silicon to aluminium and indium molar ratio of 100 and with aluminium to indium molar ratios of 1:1, 2:1 and 3:1. The MFI zeolite phase was identified by XRD and FT-IR analysis. In XRD analysis the prominent peaks were observed at 2θ values of around 6.5° and 23° with a few additional shoulder peaks in case of all the indium incorporated samples suggesting formation of pure phase of the MFI zeolite. All the samples under the present investigation were found to exhibit high crystallinity (∼92%). The crystallite sizes of the samples were found to vary from about 49 to 55 nm. IR results confirmed the formation of MFI zeolite in all cases showing distinct absorbance bands near 1080, 790, 540, 450 and 990 cm{sup −1}. TG analysis of In-MFI zeolites showed mass losses in three different steps which are attributed to the loss due to adsorbed water molecules and the two types TPA{sup +} cations. Further, the UV–vis (DRS) studies reflected the position of the indium metal in the zeolite framework. Surface area analysis of the synthesized samples was carried out to characterize the synthesized samples The analysis showed that the specific surface area ranged from ∼357 to ∼361 m{sup 2} g{sup −1} and the pore volume of the synthesized samples ranged from 0.177 to 0.182 cm{sup 3} g{sup −1}. The scanning electron microscopy studies showed the structure of the samples to be rectangular and twinned rectangular shaped. The EDX analysis was carried out for confirmation of Si, Al and In in zeolite frame work. The catalytic activities of

  18. Increased thermal conductivity monolithic zeolite structures

    DOEpatents

    Klett, James; Klett, Lynn; Kaufman, Jonathan

    2008-11-25

    A monolith comprises a zeolite, a thermally conductive carbon, and a binder. The zeolite is included in the form of beads, pellets, powders and mixtures thereof. The thermally conductive carbon can be carbon nano-fibers, diamond or graphite which provide thermal conductivities in excess of about 100 W/mK to more than 1,000 W/mK. A method of preparing a zeolite monolith includes the steps of mixing a zeolite dispersion in an aqueous colloidal silica binder with a dispersion of carbon nano-fibers in water followed by dehydration and curing of the binder is given.

  19. Equilibrium CO2 adsorption on zeolite 13X prepared from natural clays

    NASA Astrophysics Data System (ADS)

    Garshasbi, Vahid; Jahangiri, Mansour; Anbia, Mansoor

    2017-01-01

    Zeolite 13X was successfully synthesized by hydrothermal treatment using natural clays extracted from Iranian resources. The preliminary natural materials and the final zeolite 13X samples were characterized by X-ray Diffraction (XRD), Fourier-Transfer Infrared (FTIR) spectroscopy, Scanning Electron Microscopy (SEM) and N2 adsorption-desorption isotherm. The effects of various factors such as NaOH addition amount and aging time on the crystalline products were studied during the synthesis process. The optimum conditions related to the synthesis of zeolite 13X were set. Accordingly, NaOH concentration was equal to 4 M. It was further crystallized at 65 °C for 72 h after its homogenization by agitation at room temperature for 120 h. In this study, the zeolite 13X prepared from natural kaolin (13X-K) showed a high BET surface area of 591 m2/g with higher micropore volume (0.250 cm3/g) than other materials. Adsorption equilibrium isotherms of CO2 were investigated using a static, volumetric method. In addition, pressures for the pure component data extended up to 20 bar. The adsorption equilibrium data of CO2 was fitted to Langmuir, Freundlich, Lamgmuir-Freundlich, Toth and BET isotherm models. It was found that the Langmuir-Freundlich model was more suitable than other models for CO2 description. The results showed that the synthetic zeolite has higher equilibrium selectivity for CO2. Also, the CO2 uptake by zeolite 13X-K was equal to 6.9 mmol/g.

  20. Mechanical-structural investigation of chemical strengthening aluminosilicate glass through introducing phosphorus pentoxide

    NASA Astrophysics Data System (ADS)

    Zeng, Huidan; Wang, Ling; Ye, Feng; Yang, Bin; Chen, Jianding; Chen, Guorong; Sun, Luyi

    2016-11-01

    Chemical strengthening of aluminosilicate glasses through K+-Na+ ion exchange has attracted tremendous attentions because of the accelerating demand for high strength and damage resistance glasses. However, a paramount challenge still exists to fabricate glasses with a higher strength and greater depth of ion-exchange layer. Herein, aluminosilicate glasses with different contents of P2O5 were prepared and the influence of P2O5 on the increased compressive stress and depth of ion-exchange layer was investigated by micro-Raman technique. It was noticed that the hardness, compressive stress, as well as the depth of ion-exchange layer substantially increased with an increasing concentration of P2O5 varied from 1 to 7 mol%. The obtained micro-Raman spectra confirmed the formation of relatively depolymerized silicate anions that accelerated the ion exchange. Phosphorus containing aluminosilicate glasses with a lower polymerization degree exhibited a higher strength and deeper depth of ion-exchange layer, which suggests that the phosphorus containing aluminosilicate glasses have promising applications in flat panel displays, windshields, and wafer sealing substrates.

  1. EFFECT OF IMPURITIES ASSOCIATED WITH ALUMINOSILICATES ON ARSENIC SORPTION AND OXIDATION

    EPA Science Inventory

    Arsenite, As(III), and arsenate, As(V), are of increasing environmental concern. Risk assessment and risk management of arsenic contaminated sites requires a better understanding of arsenic-mineral interactions. Aluminosilicate minerals, such as feldspars and clays, are the mos...

  2. Zeolites Remove Sulfur From Fuels

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E.; Sharma, Pramod K.

    1991-01-01

    Zeolites remove substantial amounts of sulfur compounds from diesel fuel under relatively mild conditions - atmospheric pressure below 300 degrees C. Extracts up to 60 percent of sulfur content of high-sulfur fuel. Applicable to petroleum refineries, natural-gas processors, electric powerplants, and chemical-processing plants. Method simpler and uses considerably lower pressure than current industrial method, hydro-desulfurization. Yields cleaner emissions from combustion of petroleum fuels, and protects catalysts from poisoning by sulfur.

  3. Porosity of microporous zeolites A, X and ZSM-5 studied by small angle X-ray scattering and nitrogen adsorption

    NASA Astrophysics Data System (ADS)

    Du, Xiaoming; Wu, Erdong

    2007-09-01

    Small-angle X-ray scattering (SAXS) using synchrotron radiation and nitrogen adsorption have been applied to characterizations of porosities and microporous structures for the zeolites of NaA, KA, CaA, NaX and ZSM-5. Besides the information on the external morphology of the particles of the zeolites, the complementation of the two techniques has revealed rich and consistent structural and surface information on the molecular scale crystalline pores of these zeolites. Analyses of the data suggest that the determined sizes of the micropores imply the pore spaces occupied by the probe molecules of water in the SAXS and nitrogen in adsorption techniques, respectively. The microporous information of NaA and KA are difficult to obtain from nitrogen adsorption, due to the blocking of nitrogen by their narrow channels, but have been satisfactorily measured by SAXS. The factors causing variations of the measured values of the parameters in different analysis methods have been discussed.

  4. Soil Crystallinity As a Climate Indicator: Field Experiments on Earth and Mars

    NASA Technical Reports Server (NTRS)

    Horgan, Briony; Scudder, Noel; Rampe, Elizabeth; Rutledge, Alicia

    2016-01-01

    Soil crystallinity is largely determined by leaching rates, as high leaching rates favor the rapid precipitation of short order or poorly-crystalline phases like the aluminosilicate allophane. High leaching rates can occur due to high precipitation rates, seasonal monsoons, or weathering of glass, but are also caused by the rapid onset of seasonal melting of snow and ice in cold environments. Thus, cold climate soils are commonly dominated by poorly crystalline phases, which mature into kaolin minerals over time. Thus, we hypothesize that, in some contexts, soils with high abundances of poorly crystalline phases could indicate formation under cold climatic conditions. This model could be helpful in interpreting the poorly-constrained paleoclimate of ancient Mars, as the crystallinity of ancient soils and soil-derived sediments appears to be highly variable in time and space. While strong signatures of crystalline phyllosilicates have been identified in possible ancient paleosols on Mars, Mars Science Laboratory rover investigations of diverse ancient sediments at Gale Crater has shown that they can contain very high abundances (40-50 wt%) of poorly crystalline phases. We hypothesize that these poorly crystalline phases could be the result of weathering by ice/snow melt, perhaps providing support for sustained cold climates on early Mars punctuated by more limited warm climates. Furthermore, such poorly crystalline soils could be highly fertile growth media for future human exploration and colonization on Mars. To test this hypothesis, we are currently using rover-like instrumentation to investigate the mineralogy and chemistry of weathering products generated by snow and ice melt in a Mars analog alpine environment: the glaciated Three Sisters volcanic complex in central Oregon. Alteration in this glacial environment generates high abundances of poorly crystalline phases, many of which have compositions distinct from those identified in previous terrestrial

  5. [Spectroscopic analysis of the crystallization mechanism of synthesized zeolite with XRD and FTIR approaches].

    PubMed

    Fan, Chun-hui; Ma, Hong-rui; Hua, Li

    2012-04-01

    Zeolites were synthesized from fly ash using modified one-stage method. The changes in cation exchange capacity (CEC) and chemical elements of zeolite were investigated during the synthesis process to reveal the materials and elements transformation in solid-liquid system. The approaches of XRD, SEM and FTIR were used to indicate the crystallization characteristics and mechanism. The zeolite NaP1 was synthesized, and the CEC value reached to the maximum of 135 mmol/100g at 24 h. After the hydrothermal reaction for 12 h, the characteristic peak and metastable crystalline structure of zeolite NaP1 appeared, then the hydroxy sodalite products formed at 48 h. The crystallization process was the result of materials transformation: the elements of fly ash released into the liquid system for the melting effect of alkali solution, and the solid system played the role of skeleton in crystallization process, being the "source" and the "sink" of the reaction, respectively, and the achievements presented the crystallization mechanism of liquid-phase and solid-phase transformation.

  6. Enhancement of the CO(2) retention capacity of X zeolites by Na- and Cs-treatments.

    PubMed

    Díaz, Eva; Muñoz, Emilio; Vega, Aurelio; Ordóñez, Salvador

    2008-02-01

    Adsorption of carbon dioxide on alkaline modified X zeolites was investigated by temperature programmed desorption (TPD) analysis of these materials previously saturated with CO(2) at 50, 100 and 200 degrees C. Parent X zeolite (in its sodium form) was treated with different sodium and cesium aqueous solutions, using both carbonates and hydroxides as precursors. The resulting materials were characterised by nitrogen physisorption, XRD, and NH(3)-TPD, in order to determine their morphological, crystallographic and chemical properties. Slight desilication phenomena were observed using hydroxides as precursors, whereas the treatment with Cs salts lead to higher crystallinity losses. Several successive adsorption-desorption cycles were carried out in order to check the regenerability of the adsorbents. Cesium-treated zeolites present higher carbon dioxide retention capacities than the sodium treated and than the parent material. When working with these Cs-modified materials, the desorption takes place mainly at temperatures between 250 and 400 degrees C, results of great practical interest, since it allows the use these kinds of materials for adsorption-desorption cycles. The evolution of the retention capacity with temperature is also markedly more positive for Cs-treated zeolite, especially when carbonate is used as the precursor. These materials maintain high retention capacities at 100 degrees C (10mg g(-1)) and even at 200 degrees C (3mg g(-1)), temperatures at which the most of the adsorbents are inactive.

  7. UTILITY OF ZEOLITES IN ARSENIC REMOVAL FROM WATER

    EPA Science Inventory

    Zeolites are well known for their ion exchange and adsorption properties. So far the cation exchanger properties of zeolites have been extensively studied and utilized. The anion exchanger properties of zeolites are less studied. Zeolite Faujasite Y has been used to remove arseni...

  8. Coating crystalline nuclear waste forms to improve inertness

    SciTech Connect

    Stinton, D.P.; Angelini, P.; Caputo, A.J.; Lackey, W.J.

    1981-01-01

    Crystalline waste forms of high simulated waste loading were successfully coated with layers of pyrolytic carbon and silicon carbide. Sol-gel technology was used to produce microspheres that contained simulated waste. A separate process for cesium immobilization was developed, which loads 5 wt % Cs onto zeolite particles for subsequent coating. The chemical vapor deposition process was developed for depositing thin layers of carbon and silicon carbide onto particles in a fluidized-bed coater. Pyrolytic carbon-coated particles were extremely inert in numerous leach tests. Aqueous leach test results of coated waste forms were below detection limits of such sensitive analytical techniques as atomic absorption and inductively coupled plasma atomic emission.

  9. In-situ application of Ultrasonic Pulse Velocity measurements to determine the degree of zeolitic alteration of ignimbrites

    NASA Astrophysics Data System (ADS)

    Evren Çubukçu, H.; Yurdakul, Yasin; Erkut, Volkan; Akkaş, Efe; Akın, Lütfiye; Ulusoy, İnan; Şen, Erdal

    2016-04-01

    The velocity of P-waves passing through a rock body is strongly dependent on the petrographical properties such as texture, crystallinity, porosity and fracture network. For this reason, the measurement of ultrasonic pulse velocities (UPV) has been widely used in various applications interested in mechanical properties of solid rock bodies. An ignimbrite is a deposit of pyroclastic density current originating from an explosive volcanic eruption and comprises of vitric volcanic ash, free crystals, juvenile magma fragments (pumice) and accidental xenoliths. The complex nature of the componentry of ignimbrites also exhibits spatial variation depending on the location of deposition. Furthermore, both syn- and post-depositional processes (i.e. welding, alteration etc.) may have drastic impact on the mechanical characteristics of the ignimbrites. Alteration can be defined as the devitrification and the crystallization of vitric components and the transformation of pre-existing minerals of the ignimbrite into new minerals under changing thermodynamic conditions. In this context, zeolitization is an alteration process in which metastable (vitric) components of an ignimbrite body are replaced by zeolite group of minerals under low temperature and pressure induced by hydrothermal activity. The crystallization of zeolite minerals in the pore space promotes an increase in crystallinity and therefore a decrease in porosity. Hence, the velocity of P-waves passing through a zeolitized ignimbrite will be considerably higher compared to those in unaltered counterparts. Within the scope of a TUBİTAK project (No:113Y439) in which the alteration properties of Cappadocian Ignimbrites (Nevşehir, Turkey) are being investigated, in-situ UPV measurements have been performed using a portable pulse test instrument. The acquired velocity data has been correlated with the modal proportions of secondary zeolite minerals obtained by SEM-EDS. The results demonstrate that the measured P

  10. The Zeolite Deposit of Hekimhan in the Malatya Basin

    NASA Astrophysics Data System (ADS)

    Önal, Mehmet; Depci, Tolga; Ceylan, Cigdem; Kizilkaya, Nilgun

    2016-10-01

    Zeolite deposits in the Malatya Basin which is formed of the Yüksekova Group were investigated in the present study. The zeolites were occurred in the two layers: the lower zeolite layer and the upper zeolite layer of the Sankiz Formation of Campanian-Maastrichtian age within the flysch like sediments at Hekimhan in the northern part of the Malatya Basin. Characterization studies of the zeolite samples were done by XRF, XRD and SEM images and the results showed that the main structures of the zeolites were clinoptilolite-(Cs), heulandite and calcite and the geological occurrences of zeolite is in marine environments.

  11. Zeolitic materials with hierarchical porous structures.

    PubMed

    Lopez-Orozco, Sofia; Inayat, Amer; Schwab, Andreas; Selvam, Thangaraj; Schwieger, Wilhelm

    2011-06-17

    During the past several years, different kinds of hierarchical structured zeolitic materials have been synthesized due to their highly attractive properties, such as superior mass/heat transfer characteristics, lower restriction of the diffusion of reactants in the mesopores, and low pressure drop. Our contribution provides general information regarding types and preparation methods of hierarchical zeolitic materials and their relative advantages and disadvantages. Thereafter, recent advances in the preparation and characterization of hierarchical zeolitic structures within the crystallites by post-synthetic treatment methods, such as dealumination or desilication; and structured devices by in situ and ex situ zeolite coatings on open-cellular ceramic foams as (non-reactive as well as reactive) supports are highlighted. Specific advantages of using hierarchical zeolitic catalysts/structures in selected catalytic reactions, such as benzene to phenol (BTOP) and methanol to olefins (MTO) are presented.

  12. Crystalline boron nitride aerogels

    DOEpatents

    Zettl, Alexander K.; Rousseas, Michael; Goldstein, Anna P.; Mickelson, William; Worsley, Marcus A.; Woo, Leta

    2017-04-04

    This disclosure provides methods and materials related to boron nitride aerogels. In one aspect, a material comprises an aerogel comprising boron nitride. The boron nitride has an ordered crystalline structure. The ordered crystalline structure may include atomic layers of hexagonal boron nitride lying on top of one another, with atoms contained in a first layer being superimposed on atoms contained in a second layer.

  13. Salt-thermal zeolitization of fly ash.

    PubMed

    Choi, C L; Park, M; Lee, D H; Kim, I E; Park, B Y; Choi, J

    2001-07-01

    The molten-salt method has been recently proposed as a new approach to zeolitization of fly ash. Unlike the hydrothermal method, this method employs salt mixtures as the reaction medium without any addition of water. In this study, systematic investigation has been conducted on zeolitization of fly ash in a NaOH-NaNO3 system in order to elucidate the mechanism of zeolite formation and to achieve its optimization. Zeolitization of fly ash was conducted by thermally treating a powder mixture of fly ash, NaOH, and NaNO3. Zeolitization of fly ash took place above 200 degrees C, a temperature lower than the melting points of salt and base in the NaOH-NaNO3 system. However, it was uncertain whether the reactions took place in a local molten state or in a solid state. Therefore, the proposed method is renamed the "salt-thermal" method rather than the "molten-salt" method. Mainly because of difficulty in mobility of components in salt mixtures, zeolitization seems to occur within a local reaction system. In situ rearrangement of activated components seems to lead to zeolite formation. Particle growth, rather than crystal growth through agglomeration, resulted in no distinct morphologies of zeolite phases. Following are the optimal zeolitization conditions of the salt-thermal method: temperature, 250-350 degrees C; time, 3-12 h; weight ratio of NaOH/NaNO3, 0.3-0.5; weight ratio of NaNO3/fly ash, 0.7-1.4. Therefore, it is clear from this work that the salt-thermal method could be applied to massive zeolitization of fly ash as a new alternative method for recycling this waste.

  14. Detecting Nanophase Weathering Products with CheMin: Reference Intensity Ratios of Allophane, Aluminosilicate Gel, and Ferrihydrite

    NASA Technical Reports Server (NTRS)

    Rampe, E. B.; Bish, D. L.; Chipera, S. J.; Morris, R. V.; Achilles, C. N.; Ming, D W.; Blake, D. F.; Anderson, R. C.; Bristow, T. F.; Crisp, A.; DesMarais, D. J.; Downs, R. T.; Farmer, J. D.; Morookian, J. M.; Morrison, S. M.; Sarrazin, P.; Spanovich, N.; Stolper, E. M.; Treiman, A. H.; Vaniman, D. T.; Yen, A. S.

    2013-01-01

    X-ray diffraction (XRD) data collected of the Rocknest samples by the CheMin instrument on Mars Science Laboratory suggest the presence of poorly crystalline or amorphous materials [1], such as nanophase weathering products or volcanic and impact glasses. The identification of the type(s) of X-ray amorphous material at Rocknest is important because it can elucidate past aqueous weathering processes. The presence of volcanic and impact glasses would indicate that little chemical weathering has occurred because glass is highly susceptible to aqueous alteration. The presence of nanophase weathering products, such as allophane, nanophase iron-oxides, and/or palagonite, would indicate incipient chemical weathering. Furthermore, the types of weathering products present could help constrain pH conditions and identify which primary phases altered to form the weathering products. Quantitative analysis of phases from CheMin data is achieved through Reference Intensity Ratios (RIRs) and Rietveld refinement. The RIR of a mineral (or mineraloid) that relates the scattering power of that mineral (typically the most intense diffraction line) to the scattering power of a separate mineral standard such as corundum [2]. RIRs can be calculated from XRD patterns measured in the laboratory by mixing a mineral with a standard in known abundances and comparing diffraction line intensities of the mineral to the standard. X-ray amorphous phases (e.g., nanophase weathering products) have broad scattering signatures rather than sharp diffraction lines. Thus, RIRs of X-ray amorphous materials are calculated by comparing the area under one of these broad scattering signals with the area under a diffraction line in the standard. Here, we measured XRD patterns of nanophase weathering products (allophane, aluminosilicate gel, and ferrihydrite) mixed with a mineral standard (beryl) in the CheMinIV laboratory instrument and calculated their RIRs to help constrain the abundances of these phases in

  15. Studies on the formation of hierarchical zeolite T aggregates with well-defined morphology in different template systems

    NASA Astrophysics Data System (ADS)

    Yin, Xiaoyan; Chu, Naibo; Lu, Xuewei; Li, Zhongfang; Guo, Hong

    2016-01-01

    In this paper, the disk-like and pumpkin-like hierarchical zeolite T aggregates consisted of primary nano-grains have been hydrothermally synthesized with and without the aid of the second template. The first template is used with tetramethylammonium hydroxide (TMAOH) and the second template is used with triethanolamine (TEA) or polyving akohol (PVA). A combination of characterization techniques, including XRD, SEM, TEM and N2 adsorption-desorption to examine the crystal crystallinity, morphology and surface properties of hierarchical zeolite T aggregates. In the single-template preparation process, the two-step varying-temperature treatment has been used to improve the meso-porosity of zeolite T aggregates. In the double-template preparation process, the amounts of PVA or TEA on the crystallinity, morphology and meso-porosity of zeolite T aggregates have been studied. It has been proved that the interstitial voids between the primary grains of aggregates are the origin of additional mesopores of samples. The micro- and meso-porosities of samples prepared with and without the second template have been contrasted in detail at last. In particular, the sample synthesized with the addition of PVA presents a hierarchical pore structure with the highest Sext value of 122 m2/g and Vmeso value of 0.255 cm3/g.

  16. CuO nanoparticles incorporated in hierarchical MFI zeolite as highly active electrocatalyst for non-enzymatic glucose sensing.

    PubMed

    Dong, Junping; Tian, Taolei; Ren, Linxiao; Zhang, Yuan; Xu, Jiaqiang; Cheng, Xiaowei

    2015-01-01

    A hierarchical MFI zeolite, with typical micro/meso bimodal pore structures, was prepared by desilication method. CuO nanoparticles (NPs) were incorporated into the hierarchical MFI zeolite by impregnation method. CuO/hierarchical zeolite composites were characterized by X-ray diffraction, transmission electron microscopy and nitrogen sorption. It is shown that the CuO nanoparticles are mostly dispersed in the mesopores with remaining of the crystallinity and morphology of the host zeolite. CuO nanoparticles located in hierarchical zeolite exhibit the excellent electrocatalytic performances to oxidation of glucose in alkaline media. The electrocatalytic activity enhances with increasing the loading content of CuO from 5% to 15%. The composites were fabricated for nonenzyme glucose sensing. Under the optimal conditions, the sensor shows a wide linear range from 5×10(-7) to 1.84×10(-2) M with a low detection limit of 3.7×10(-7) M. The sensor also exhibits good repeatability, long-term stability as well as high selectivity against interfering species.

  17. Influence of Boehmite Precursor on Aluminosilicate Aerogel Pore Structure, Phase Stability and Resistance to Densification at High Temperatures

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.; Guo, Haiquan; Newlin, Katy N.

    2011-01-01

    Aluminosilicate aerogels are of interest as constituents of thermal insulation systems for use at temperatures higher than those attainable with silica aerogels. It is anticipated that their effectiveness as thermal insulators will be influenced by their morphology, pore size distribution, physical and skeletal densities. The present study focuses on the synthesis of aluminosilicate aerogel from a variety of Boehmite (precursors as the Al source, and tetraethylorthosilicate (TEOS) as the Si source, and the influence of starting powder on pore structure and thermal stability.

  18. Formation and structure of Langmuir-Blodgett films of organo-modified aluminosilicate with high surface coverage.

    PubMed

    Fujimori, Atsuhiro; Arai, Shuntaro; Kusaka, Jun-ichi; Kubota, Munehiro; Kurosaka, Kei-ichi

    2013-02-15

    We have developed an effective organo-modification method at the organic solvent/distilled water interface of natural aluminosilicate clay surfaces. We also investigated the molecular arrangement of organo-modified aluminosilicate with high surface coverage in Langmuir-Blodgett films (LB) by performing out-of-plane and in-plane X-ray diffraction (XRD) measurements. In addition, the surface morphology of mixed monolayers of organo-modified aluminosilicate and several biodegradable polymers (e.g., poly(L-lactide), PLLA) was also characterized by atomic force microscopy (AFM). The in-plane XRD results of multilayers of organo-modified aluminosilicate formed by the LB method indicate the formation of a two-dimensional lattice of hydrocarbons on the aluminosilicate surface. These hydrocarbons of organo-modified reagents packed hexagonal or orthorhombic in films. Based on our experimental findings, the LB technique enabled the formation of a densely packed organo-modified aluminosilicate monolayer at the water surface. Furthermore, for mixed monolayer systems comprising an organo-modified clay with high surface coverage and biodegradable polymers, a miscible surface was observed by AFM on a mesoscopic scale, whereas those with low surface coverage formed phase-separated structures.

  19. Studies on sorption properties of zeolite derived from Indian fly ash.

    PubMed

    Mishra, T; Tiwari, S K

    2006-09-01

    Indian fly ash has been completely converted to crystalline porous 13X zeolite by NaOH fusion at 600 degrees C followed by hydrothermal treatment at 105 degrees C for 20 h. Obtained materials were characterized by XRD, SEM and surface area measurement. Prepared material was used for the sorption study of different metal ions (Cu(2+), Co(2+) and Ni(2+)) at different pH, temperature. Thermodynamic data (DeltaS, DeltaH and DeltaG) corresponding to different metal ion uptake were evaluated from Langmuir equation. In all the experiment sorption capacity of prepared zeolite was found to be quite high than that of fly ash at acidic pH. However, the uptake selectivity order for both the materials is Cu(2+)>Co(2+)>Ni(2+).

  20. Highly efficient and recyclable basic mesoporous zeolite catalyzed condensation, hydroxylation, and cycloaddition reactions.

    PubMed

    Sarmah, Bhaskar; Satpati, Biswarup; Srivastava, Rajendra

    2017-05-01

    Crystalline mesoporous ZSM-5 zeolite was prepared in the presence of 1,4-diazabicyclo[2.2.2]octane derived multi-cationic structure directing agent. The calcined form of the mesoprous zeolite was treated with NH4OH to obtain basic mesoporous ZSM-5. Catalyst was characterized by the complementary combination of X-ray diffraction, N2-adsorption, electron microscopes, and temperature programme desorption techniques. Catalytic activity of the basic mesoporous ZSM-5 was systematically assessed using Knoevenagel condensation reaction for the synthesis a wide range of substituted styrene. Applications of the catalyst were investigated in the benzamide hydroxylation for the synthesis of carbinolamides and one-pot, multi-component condensation reaction for the synthesis of naphthopyrans. Finally, the catalyst was evaluated in the cycloaddition of CO2 to epoxide for the synthesis of cyclic carbonates. Recycling study shows that no significant decrease in the catalytic activity was observed after five recycles.

  1. [Assessment of carcinogenic effect of aluminosilicate ceramic fibers produced in Poland. Animal experiments].

    PubMed

    Krajnow, A; Lao, I

    2000-01-01

    The effect of aluminosilicate ceramic fibres produced in Poland was assessed. The experiment was performed on two animal species: Wistar rats and BALB/C mice. The animals were administered intraperitoneally the studied fibres and krokidolit UICC--in doses of 25 and 5 mg and left for survival. All dead and sacrificed animals were examined histopathologically. Carcinogenic properties of ceramic aluminosilicate fibres were found to be rather weak. Only in 1 (2.5%) of 39 rats under study benign mesothelioma of tunica vagiualis testis was diagnosed. Peritoneal mesothelioma was found in none of 50 mice studied. For comparison the effect of krokidolit UICC was assessed. Krokidolit UICC is characterised by strong carcinogenic properties. It induced peritoneal mesothelioma in 43 mice (44.2%) and in 29 (80.5%) of 36 rats under study.

  2. Zeolites on Mars: Prospects for Remote Sensing

    NASA Technical Reports Server (NTRS)

    Gaffney, E. S.; Singer, R. B.; Kunkle, T. D.

    1985-01-01

    The Martian surface composition measured by Viking can be represented by several combinations of minerals incorporating major fractions of zeolites known to occur in altered mafic rocks and polar soils on Earth. The abundant occurrence of zeolites on Mars is consistent with what is known about both the physical and chemical environment of that planet. The laboratory reflectance spectra (0.65 to 2.55 microns) of a number of relatively pure zeolite minerals and some naturally occurring zeolite-clay soils were measured. All of the spectra measured are dominated by strong absorption near 1.4 and 1.9 microns and a steep reflectance drop longward of about 2.2 microns, all of which are due to abundant H2O. Weaker water overtone bands are also apparent, and in most cases there is spectral evidence for minor Fe(3+). In these features the zeolite spectra are similar to spectra of smectite clays which have abundant interlayer water. The most diagnostic difference between clay and zeolite spectra is the total absence in the zeolites of the weak structural OH absorption.

  3. The role of zeolite in the Fischer-Tropsch synthesis over cobalt-zeolite catalysts

    NASA Astrophysics Data System (ADS)

    Sineva, L. V.; Asalieva, E. Yu; Mordkovich, V. Z.

    2015-11-01

    The review deals with the specifics of the Fischer-Tropsch synthesis for the one-stage syncrude production from CO and H2 in the presence of cobalt-zeolite catalytic systems. Different types of bifunctional catalysts (hybrid, composite) combining a Fischer-Tropsch catalyst and zeolite are reviewed. Special attention focuses on the mechanisms of transformations of hydrocarbons produced in the Fischer-Tropsch process on zeolite acid sites under the synthesis conditions. The bibliography includes 142 references.

  4. One-step synthesis of hydrothermally stable mesoporous aluminosilicates with strong acidity

    NASA Astrophysics Data System (ADS)

    Yang, Dongjiang; Xu, Yao; Wu, Dong; Sun, Yuhan

    2008-09-01

    Using tetraethylorthosilicate (TEOS), polymethylhydrosiloxane (PMHS) and aluminium isopropoxide (AIP) as the reactants, through a one-step nonsurfactant route based on PMHS-TEOS-AIP co-polycondensation, hydrothermally stable mesoporous aluminosilicates with different Si/Al molar ratios were successfully prepared. All samples exclusively showed narrow pore size distribution centered at 3.6 nm. To assess the hydrothermal stability, samples were subjected to 100 °C distilled water for 300 h. The boiled mesoporous aluminosilicates have nearly the same N 2 adsorption-desorption isotherms and the same pore size distributions as those newly synthesized ones, indicating excellent hydrothermal stability. The 29Si MAS NMR spectra confirmed that PMHS and TEOS have jointly condensed and CH 3 groups have been introduced into the materials. The 27Al MAS NMR spectra indicated that Al atoms have been incorporated in the mesopore frameworks. The NH 3 temperature-programmed desorption showed strong acidity. Due to the existence of large amount of CH 3 groups, the mesoporous aluminosilicates obtained good hydrophobicity. Owing to the relatively large pore and the strong acidity provided by the uniform four-coordinated Al atoms, the excellent catalytic performance for 1,3,5-triisopropylbenzene cracking was acquired easily. The materials may be a profitable complement for the synthesis of solid acid catalysts.

  5. Impact Of Sodium Oxalate, Sodium Aluminosilicate, and Gibbsite/Boehmite on ARP Filter Performance

    SciTech Connect

    Poirier, M.; Burket, P.

    2015-11-01

    The Savannah River Site (SRS) is currently treating radioactive liquid waste with the Actinide Removal Process (ARP) and the Modular Caustic Side Solvent Extraction Unit (MCU). Recently, the low filter flux through the ARP of approximately 5 gallons per minute has limited the rate at which radioactive liquid waste can be treated. Salt Batch 6 had a lower processing rate and required frequent filter cleaning. Savannah River Remediation (SRR) has a desire to understand the causes of the low filter flux and to increase ARP/MCU throughput. SRR requested SRNL to conduct bench-scale filter tests to evaluate whether sodium oxalate, sodium aluminosilicate, or aluminum solids (i.e., gibbsite and boehmite) could be the cause of excessive fouling of the crossflow or secondary filter at ARP. The authors conducted the tests by preparing slurries containing 6.6 M sodium Salt Batch 6 supernate, 2.5 g MST/L slurry, and varying concentrations of sodium oxalate, sodium aluminosilicate, and aluminum solids, processing the slurry through a bench-scale filter unit that contains a crossflow primary filter and a dead-end secondary filter, and measuring filter flux and transmembrane pressure as a function of time. Among the conclusions drwn from this work are the following: (1) All of the tests showed some evidence of fouling the secondary filter. This fouling could be from fine particles passing through the crossflow filter. (2) The sodium oxalate-containing feeds behaved differently from the sodium aluminosilicate- and gibbsite/boehmite-containing feeds.

  6. Origins of saccharide-dependent hydration at aluminate, silicate, and aluminosilicate surfaces

    PubMed Central

    Smith, Benjamin J.; Rawal, Aditya; Funkhouser, Gary P.; Roberts, Lawrence R.; Gupta, Vijay; Israelachvili, Jacob N.; Chmelka, Bradley F.

    2011-01-01

    Sugar molecules adsorbed at hydrated inorganic oxide surfaces occur ubiquitously in nature and in technologically important materials and processes, including marine biomineralization, cement hydration, corrosion inhibition, bioadhesion, and bone resorption. Among these examples, surprisingly diverse hydration behaviors are observed for oxides in the presence of saccharides with closely related compositions and structures. Glucose, sucrose, and maltodextrin, for example, exhibit significant differences in their adsorption selectivities and alkaline reaction properties on hydrating aluminate, silicate, and aluminosilicate surfaces that are shown to be due to the molecular architectures of the saccharides. Solid-state 1H, 13C, 29Si, and 27Al nuclear magnetic resonance (NMR) spectroscopy measurements, including at very high magnetic fields (19 T), distinguish and quantify the different molecular species, their chemical transformations, and their site-specific adsorption on different aluminate and silicate moieties. Two-dimensional NMR results establish nonselective adsorption of glucose degradation products containing carboxylic acids on both hydrated silicates and aluminates. In contrast, sucrose adsorbs intact at hydrated silicate sites and selectively at anhydrous, but not hydrated, aluminate moieties. Quantitative surface force measurements establish that sucrose adsorbs strongly as multilayers on hydrated aluminosilicate surfaces. The molecular structures and physicochemical properties of the saccharides and their degradation species correlate well with their adsorption behaviors. The results explain the dramatically different effects that small amounts of different types of sugars have on the rates at which aluminate, silicate, and aluminosilicate species hydrate, with important implications for diverse materials and applications. PMID:21562207

  7. Structural and compositional heterogeneities in liquid aluminosilicate: insight from a grain structure model

    NASA Astrophysics Data System (ADS)

    Van Nguyen, Hong; Tran, Duong Thuy; Pham, Hung Khac

    2017-02-01

    Network structure as well as structural and compositional heterogeneities in aluminosilicate (Al2O3-2SiO2) under compression is investigated by analysis and visualization of simulation data. Structural and compositional heterogeneities are clarified through analysis of topology structure and size distribution of TO x -clusters ( T = Si, Al; x = 3, 4, 5, 6) as well as O T y -clusters ( y = 2, 3, 4). The TO x -cluster can be considered as TO x -grains. It appears that the structure of aluminosilicate is the mixture of TO x -grains with a different short-range order structure and this is the origin of structural heterogeneity. Regarding their composition, the OSi y - and OAl y -clusters can be considered as silica- and alumina-grains respectively, and the structure of aluminosilicate can thus be considered to be formed from silica- and alumina-grains. This results in compositional heterogeneity. Moreover, the degree of polymerization and polyamorphism as well as dynamic heterogeneity is also discussed in detail.

  8. Studies of Potential Inhibitors of Sodium Aluminosilicate Scales in High-Level Waste Evaporation

    SciTech Connect

    Oji, L.N.; Fellinger, T.L.; Hobbs, D.T.; Badheka, N.P.; Wilmarth, W.R.

    2008-07-01

    The Savannah River Site (SRS) has 49 underground storage tanks used to store High Level Waste (HLW). The tank space in these tanks must be managed to support the continued operation of key facilities. The reduction of the tank volumes in these tanks are accomplished through the use of three atmospheric pressure HLW evaporators. For a decade, evaporation of highly alkaline HLW containing dissolved aluminate and silicate has produced sodium aluminosilicate scales causing both operation and criticality hazards in the 2H Evaporator System. Segregation of aluminum-rich wastes from silicate-rich wastes minimizes the amount of scale produced and reduces cleaning expenses, but does not eliminate the scaling nor increases operation flexibility in waste process. Similar issues have affected the aluminum refining industry for many decades. Over the past several years, successful commercial products have been identified to eliminate aluminosilicate fouling in the aluminum industry, but have not been utilized in a nuclear environment. Laboratory quantities of three proprietary aluminosilicate scale inhibitors have been produced and been shown to prevent formation of scales. SRNL has been actively testing these potential inhibitors to examine their radiation stability, radiolytic degradation behaviors, and downstream impacts to determine their viability within the HLW system. One of the tested polymers successfully meets the established criteria for application in the nuclear environment. This paper will describe a summary of the methodology used to prioritize laboratory testing protocols based on potential impacts/risks identified for inhibitor deployment at SRS. (authors)

  9. The effects of intrapleural injections of alumina and aluminosilicate (ceramic) fibres.

    PubMed

    Pigott, G H; Ishmael, J

    1992-04-01

    Groups of rats, 24 male and 24 female, approximately 8 weeks old, were dosed by a single intrapleural injection with a saline suspension of refractory alumina fibres (Saffil fibres ICI plc) either as manufactured or after extensive thermal ageing; or one of two aluminosilicate ('ceramic') fibres with different diameter distributions. Similar groups were dosed with a suspension of UICC chrysotile A asbestos or saline solution to serve as positive and negative controls respectively. Rats were maintained to 85% mortality and all decedents and terminal sacrifices were closely examined for the presence of mesothelioma. Malignant mesothelioma was diagnosed in ten rats, seven dosed with asbestos and three dosed with aluminosilicate fibre B. No mesothelioma was detected in any rat dosed with Saffil fibres or aluminosilicate fibre A or in negative controls. The results support the predicted inert nature of Saffil alumina fibres and provide further evidence for the importance of fibre dimension in the induction of mesothelioma. The implication of the results for inhalation exposures is discussed.

  10. The effects of intrapleural injections of alumina and aluminosilicate (ceramic) fibres.

    PubMed Central

    Pigott, G. H.; Ishmael, J.

    1992-01-01

    Groups of rats, 24 male and 24 female, approximately 8 weeks old, were dosed by a single intrapleural injection with a saline suspension of refractory alumina fibres (Saffil fibres ICI plc) either as manufactured or after extensive thermal ageing; or one of two aluminosilicate ('ceramic') fibres with different diameter distributions. Similar groups were dosed with a suspension of UICC chrysotile A asbestos or saline solution to serve as positive and negative controls respectively. Rats were maintained to 85% mortality and all decedents and terminal sacrifices were closely examined for the presence of mesothelioma. Malignant mesothelioma was diagnosed in ten rats, seven dosed with asbestos and three dosed with aluminosilicate fibre B. No mesothelioma was detected in any rat dosed with Saffil fibres or aluminosilicate fibre A or in negative controls. The results support the predicted inert nature of Saffil alumina fibres and provide further evidence for the importance of fibre dimension in the induction of mesothelioma. The implication of the results for inhalation exposures is discussed. PMID:1571274

  11. STUDIES OF POTENTIAL INHIBITORS OF SODIUM ALUMINOSILICATE SCALES IN HIGH-LEVEL WASTE EVAPORATION

    SciTech Connect

    Wilmarth, B; Lawrence Oji, L; Terri Fellinger, T; David Hobbs, D; Nilesh Badheka, N

    2008-02-27

    The Savannah River Site (SRS) has 49 underground storage tanks used to store High Level Waste (HLW). The tank space in these tanks must be managed to support the continued operation of key facilities. The reduction of the tank volumes in these tanks are accomplished through the use of three atmospheric pressure HLW evaporators. For a decade, evaporation of highly alkaline HLW containing aluminum and silicates has produced sodium aluminosilicate scales causing both operation and criticality hazards in the 2H Evaporator System. Segregation of aluminum-rich wastes from silicate-rich wastes minimizes the amount of scale produced and reduces cleaning expenses, but does not eliminate the scaling nor increases operation flexibility in waste process. Similar issues have affected the aluminum refining industry for many decades. Over the past several years, successful commercial products have been identified to eliminate aluminosilicate fouling in the aluminum industry, but have not been utilized in a nuclear environment. Laboratory quantities of three proprietary aluminosilicate scale inhibitors have been produced and been shown to prevent formation of scales. SRNL has been actively testing these potential inhibitors to examine their radiation stability, radiolytic degradation behaviors, and downstream impacts to determine their viability within the HLW system. One of the tested polymers successfully meets the established criteria for application in the nuclear environment. This paper will describe a summary of the methodology used to prioritize laboratory testing protocols based on potential impacts/risks identified for inhibitor deployment at SRS.

  12. Ammonia removal from wastewaters using natural Australian zeolite. 1: Characterization of the zeolite

    SciTech Connect

    Cooney, E.L.; Booker, N.A.; Shallcross, D.C.; Stevens, G.W.

    1999-09-01

    This study considered the potential of a natural Australian zeolite, clinoptilolite, to remove ammonium from water. Ammonium-exchange capacity and rates of adsorption are critical to the assessment of the feasibility of the zeolite for application to continuous wastewater treatment. A laboratory study was undertaken, using pure solutions, to investigate the equilibria and kinetic characteristics of ammonium exchange in the zeolite. Binary equilibrium experiments provided information on the adsorption characteristics of the zeolite in terms of ammonia capacity at varying solution concentrations. These experiments also revealed that the highest ammonium removal efficiency was achieved when the zeolite`s exchange sites were converted to the sodium form. Multicomponent equilibrium experiments were carried out to determine the effects of competing cations on the ammonium-exchange capacity of the zeolite. The laboratory study indicated the zeolite`s selectivity for ammonium ions over other cations typically present in sewage (calcium, magnesium, and potassium), and provided information relevant to the design and operation of a continuous process.

  13. Copper-Exchanged Zeolite L Traps Oxygen

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K.; Seshan, Panchalam K.

    1991-01-01

    Brief series of simple chemical treatments found to enhance ability of zeolite to remove oxygen from mixture of gases. Thermally stable up to 700 degrees C and has high specific surface area which provides high capacity for adsorption of gases. To increase ability to adsorb oxygen selectively, copper added by ion exchange, and copper-exchanged zeolite reduced with hydrogen. As result, copper dispersed atomically on inner surfaces of zeolite, making it highly reactive to oxygen, even at room temperature. Reactivity to oxygen even greater at higher temperatures.

  14. Tetraethylenepentamine embedded zeolite A for carbon dioxide adsorption.

    PubMed

    Kim, Young-Ki; Mo, Yong-Hwan; Lee, Jun; You, Hyo-Sang; Yi, Chang-Keun; Park, Young Cheol; Park, Sang-Eon

    2013-04-01

    Tetraethylenepentamine (TEPA) embedded zeolite A crystals were synthesized by using TEPA and the preformed zeolite A precursor under the microwave irradiation. The presence of TEPA in zeolite A crystal was confirmed by TG analysis and FTIR, Raman spectra. The CO2 adsorptive behavior of TEPA embedded zeolite A samples was investigated by CO2 isotherms measured at 25 degrees C comparing with zeolite A. The optimum CO2 sorption capacity was found in the case of 7.5% TEPA embedded zeolite A, which showed 3.75 mmol g(-1) where as the zeolite A showed less CO2 adsorption capacity of 2.88 mmol g(-1). The adsorption capacity of TEPA embedded Zeolite A was sustained up to 90% during 4 cycles of temperature swing adsorption (TSA) from 40 degrees C to 140 degrees C, indicating that the TEPA embedded Zeolite A was found to be useful as one of the application to solid amine adsorbent for CO2.

  15. Crystalline Silica Primer

    USGS Publications Warehouse

    ,

    1992-01-01

    substance and will present a nontechnical overview of the techniques used to measure crystalline silica. Because this primer is meant to be a starting point for anyone interested in learning more about crystalline silica, a list of selected readings and other resources is included. The detailed glossary, which defines many terms that are beyond the scope of this publication, is designed to help the reader move from this presentation to a more technical one, the inevitable next step.

  16. Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2007-03-31

    The addition of hydrothermally-aged zeolite Y precursor to an SBA-15 synthesis mixture under a mildly acidic condition resulted in the formation of a mesoporous aluminosilicate catalyst, AlSBA-15. The Al-SBA-15 mesoporous catalyst contains strong Br{umlt o}nsted acid sites and aluminum (Al) stabilized in a totally tetrahedral coordination. The physicochemical characteristics of the catalyst varied as a function of the synthesis conditions. The catalyst possessed surface areas ranging between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm, and pore volumes up 1.03 cm{sup 3}, which were comparable to the parent SBA-15 synthesized under similar conditions. Two wt % Al was present in the catalyst that was obtained from the reaction mixture that contained the highest Al content. The Al remained stable in totally tetrahedral coordination after calcination at a temperature of 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and the activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. In preparation for the final phase of the project, the catalyst was embedded into a psuedoboemite alumina (catapal B) matrix and then formed into pellets. In the final phase of the project, the pelletized catalyst is being evaluated for the conversion of a heavy petroleum feedstock to naphtha and middle distillates. This phase was significantly delayed during the past six months due to a serious malfunction of the fume hoods in the Clark Atlanta University's Research Center for Science and Technology, where the project is being conducted. The fume hood system was repaired and the catalyst evaluation is now underway.

  17. The active site of low-temperature methane hydroxylation in iron-containing zeolites

    NASA Astrophysics Data System (ADS)

    Snyder, Benjamin E. R.; Vanelderen, Pieter; Bols, Max L.; Hallaert, Simon D.; Böttger, Lars H.; Ungur, Liviu; Pierloot, Kristine; Schoonheydt, Robert A.; Sels, Bert F.; Solomon, Edward I.

    2016-08-01

    An efficient catalytic process for converting methane into methanol could have far-reaching economic implications. Iron-containing zeolites (microporous aluminosilicate minerals) are noteworthy in this regard, having an outstanding ability to hydroxylate methane rapidly at room temperature to form methanol. Reactivity occurs at an extra-lattice active site called α-Fe(II), which is activated by nitrous oxide to form the reactive intermediate α-O; however, despite nearly three decades of research, the nature of the active site and the factors determining its exceptional reactivity are unclear. The main difficulty is that the reactive species—α-Fe(II) and α-O—are challenging to probe spectroscopically: data from bulk techniques such as X-ray absorption spectroscopy and magnetic susceptibility are complicated by contributions from inactive ‘spectator’ iron. Here we show that a site-selective spectroscopic method regularly used in bioinorganic chemistry can overcome this problem. Magnetic circular dichroism reveals α-Fe(II) to be a mononuclear, high-spin, square planar Fe(II) site, while the reactive intermediate, α-O, is a mononuclear, high-spin Fe(IV)=O species, whose exceptional reactivity derives from a constrained coordination geometry enforced by the zeolite lattice. These findings illustrate the value of our approach to exploring active sites in heterogeneous systems. The results also suggest that using matrix constraints to activate metal sites for function—producing what is known in the context of metalloenzymes as an ‘entatic’ state—might be a useful way to tune the activity of heterogeneous catalysts.

  18. Optimizing the crystallinity and acidity of H-SAPO-34 by fluoride for synthesizing Cu/SAPO-34 NH3-SCR catalyst.

    PubMed

    Ma, Jing; Si, Zhichun; Wu, Xiaodong; Weng, Duan; Ma, Yue

    2016-03-01

    A series of H-SAPO-34 zeolites were synthesized by a hydrothermal method in fluoride media. The as-synthesized H-SAPO-34 zeolites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 physisorption, temperature-programmed desorption of NH3 (NH3-TPD) and nuclear magnetic resonance (NMR) measurements. The results showed that a certain concentration of F(-) anions promoted the nucleation and crystallization of H-SAPO-34. The H-SAPO-34 synthesized in the fluoride media showed high crystallinity, uniform particle size distribution, large specific surface area and pore volume, and enhanced acidity. Therefore, Cu/SAPO-34 based on the fluoride-assisted zeolite showed a broadened temperature window for the selective catalytic reduction of NO by NH3 (NH3-SCR) reaction due to the enhanced acidity of the zeolite and the improved dispersion of copper species.

  19. Factors affecting drug adsorption on beta zeolites.

    PubMed

    Pasti, Luisa; Sarti, Elena; Cavazzini, Alberto; Marchetti, Nicola; Dondi, Francesco; Martucci, Annalisa

    2013-05-01

    The adsorption behaviour of three commonly used drugs, namely ketoprofen, hydrochlorothiazide and atenolol, from diluted aqueous solutions on beta zeolites with different SiO2/Al2O3 ratio (i.e. 25, 38 and 360) was investigated by changing the ionic strength and the pH, before and after thermal treatment of the adsorbents. The selective adsorption of drugs was confirmed by thermogravimetry and X-ray diffraction. The adsorption capacity of beta zeolites was strongly dependent on both the solution pH and the alumina content of the adsorbent. Such a remarkable difference was interpreted as a function of the interactions between drug molecules and zeolite surface functional groups. Atenolol was readily adsorbed on the less hydrophobic zeolite, under pH conditions in which electrostatic interactions were predominant. On the other hand, ketoprofen adsorption was mainly driven by hydrophobic interactions. For undissociated molecules the adsorption capability increased with the increase of hydrophobicity.

  20. Zeolitic catalytic conversion of alochols to hydrocarbons

    DOEpatents

    Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

    2017-01-03

    A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.

  1. A new method for As(V) removal from waters by precipitation of mimetite Pb5(AsO4)3Cl on Pb-activated zeolite

    NASA Astrophysics Data System (ADS)

    Manecki, Maciej; Buszkiewicz, Urszula

    2016-04-01

    A new method for removal of arsenate AsO43- ions from aqueous solutions is proposed. The principle of the method stems from precipitation of very insoluble crystalline lead arsenate apatite (mimetite Pb5(AsO4)3Cl) induced by bringing in contact Pb-activated zeolite and As-contaminated water in the presence of Cl-. Zeolite is activated by sorption of Pb2+ followed by washing with water to remove the excess of Pb and to desorbe weakly adsorbed ions. Lead adsorbed on zeolite is bound strong enough to prevent desorption by water but weak enough to undergo desorption induced by heterogeneous precipitation of mimetite nanocrystals on the surface of zeolite. The experiment consisted of two steps. In the first step, aliquots of 0.5 g of natural clinoptilolite zeolite (from Zeocem a.s., Bystré, Slovak Republic) were reacted with 40 mL of solutions containing 20, 100, 500, and 2000 mg Pb/L (pH =4.5; reaction for 30 minutes followed by centrifugation). The amount of Pb sorbed was calculated from the drop of Pb concentration in solution. Centrifuged zeolite was washed three times by mixing with 10 mL of DDI water, followed by centrifugation. No Pb was detected in the water after second washing. Wet pulp resulting from this stage was exposed to solutions containing 70 mg/L Cl- and various concentrations of AsO43- (2 and 100 mg As/L; pH=4). Complete removal of As was observed for 2 mg As/L solutions mixed with zeolite-20 and zeolite-100. The precipitation of mimetite Pb5(AsO4)3Cl in the form of hexagonal crystals ca. 0.25 μm in size was observed using SEM/EDS. This work is partially funded by AGH research grant no 11.11.140.319.

  2. Thermodynamic modeling of natural zeolite stability

    SciTech Connect

    Chipera, S.J.; Bish, D.L.

    1997-06-01

    Zeolites occur in a variety of geologic environments and are used in numerous agricultural, commercial, and environmental applications. It is desirable to understand their stability both to predict future stability and to evaluate the geochemical conditions resulting in their formation. The use of estimated thermodynamic data for measured zeolite compositions allows thermodynamic modeling of stability relationships among zeolites in different geologic environments (diagenetic, saline and alkaline lakes, acid rock hydrothermal, basic rock, deep sea sediments). This modeling shows that the relative cation abundances in both the aqueous and solid phases, the aqueous silica activity, and temperature are important factors in determining the stable zeolite species. Siliceous zeolites (e.g., clinoptilolite, mordenite, erionite) present in saline and alkaline lakes or diagenetic deposits formed at elevated silica activities. Aluminous zeolites (e.g., natrolite, mesolite/scolecite, thomsonite) formed in basic rocks in association with reduced silica activities. Likewise, phillipsite formation is favored by reduced aqueous silica activities. The presence of erionite, chabazite, and phillipsite are indicative of environments with elevated potassium concentrations. Elevated temperature, calcic water conditions, and reduced silica activity help to enhance the laumontite and wairakite stability fields. Analcime stability increases with increased temperature and aqueous Na concentration, and/or with decreased silica activity.

  3. Liquid crystalline composites containing phyllosilicates

    DOEpatents

    Chaiko, David J.

    2004-07-13

    The present invention provides phyllosilicate-polymer compositions which are useful as liquid crystalline composites. Phyllosilicate-polymer liquid crystalline compositions of the present invention can contain a high percentage of phyllosilicate while at the same time be transparent. Because of the ordering of the particles liquid crystalline composite, liquid crystalline composites are particularly useful as barriers to gas transport.

  4. [Influence of zeolite A supplementation during the dry period of dairy cows on feed intake, on the macro and trace element metabolism around calving and milk yield in the following lactation].

    PubMed

    Grabherr, Hilde; Spolders, Markus; Flachowsky, Gerhard; Fürll, Manfred

    2008-01-01

    The object of the present study was to determine the influence of zeolite A, a calcium binder from the group of the aluminosilicate, on feed intake, macro and trace element metabolism as well as the milk yield in the following lactation in dairy cows. 46 cows were allotted to 2 groups (A--control group and B--experimental group). They were fed a total mixed ration (TMR) ad libitum 2 weeks before calving. Additionally the cows in group B received 90 g zeolite A/kg dry matter (DM). The individually feed intake was registered daily. The serum was analysed for Ca, Mg, and Pi (inorganic phosphate), Fe, FFA (free fatty acid) and beta-HB (hydroxybutyrate) and the plasma for the trace elements Cu, Zn, and Mn. After calving the milk yield (FCM) and the milk composition (fat, protein, lactose and urea) were analysed. Feed intake of group B, amounting to 6.2 +/- 1.3 kg DM/d was around 48% lower as compared to 12.0 +/- 1.4 kg DM/d for group A. The zeolite addition into the TMR showed a stabilizing effect on the average Ca concentration in the serum around calving. This effect led to a significantly lower Mg concentration on the day of calving and 1 day post partum. The Pi concentration was significantly lower already after the 1st week of zeolite supplementation and on the day of calving as compared to group A. There was no essential effect of zeolite A on the trace element concentration. The depression of feed intake for group B led to a significant increase of FFA one week after beginning zeolite supplementation and of beta-HB around calving. The feed intake post partum as well as the milk yield were not affected by zeolite supplementation. Because decreased feed intake of group B after zeolite supplementation and the occurred hypophosphatemia, it is not acceptable to use zeolite A in the proved dose for preventing milk fever.

  5. Effect of different glasses in glass bonded zeolite

    SciTech Connect

    Lewis, M.A.; Ackerman, J.P.; Verma, S.

    1995-05-01

    A mineral waste form has been developed for chloride waste salt generated during the pyrochemical treatment of spent nuclear fuel. The waste form consists of salt-occluded zeolite powders bound within a glass matrix. The zeolite contains the salt and immobilizes the fission products. The zeolite powders are hot pressed to form a mechanically stable, durable glass bonded zeolite. Further development of glass bonded zeolite as a waste form requires an understanding of the interaction between the glass and the zeolite. Properties of the glass that enhance binding and durability of the glass bonded zeolite need to be identified. Three types of glass, boroaluminosilicate, soda-lime silicate, and high silica glasses, have a range of properties and are now being investigated. Each glass was hot pressed by itself and with an equal amount of zeolite. MCC-1 leach tests were run on both. Soda-lime silicate and high silica glasses did not give a durable glass bonded zeolite. Boroaluminosilicate glasses rich in alkaline earths did bind the zeolite and gave a durable glass bonded zeolite. Scanning electron micrographs suggest that the boroaluminosilicate glasses wetted the zeolite powders better than the other glasses. Development of the glass bonded zeolite as a waste form for chloride waste salt is continuing.

  6. One-step synthesis of hierarchical aluminosilicate aggregates using bifunctional alkanolamine as single template

    NASA Astrophysics Data System (ADS)

    Chen, Li; Zhu, Shu Yan; Wang, Hai Man; Wang, Yi Meng

    2011-11-01

    Highly active, hierarchical zeolite ZSM-5 aggregates have been prepared in a one-step synthesis using alkanolamine as single template. The effects of SiO 2/Al 2O 3, pH and H 2O/SiO 2 on the aggregate morphology of the ZSM-5 nanocrystals were investigated. The obtained aggregate zeolites characterized by SEM, TEM and BET possessed significant textual porosity (up to 0.22 cm 3/g), which could be tuned by the number of substituents in the alkanolamine molecules and the amount of aluminum in the synthetic mixtures. These zeolite aggregates showed high activities for Friedel-Crafts alkylations and may curtail the filtration difficulties during the synthesis and applications to some extent.

  7. The human crystallin gene families

    PubMed Central

    2012-01-01

    Crystallins are the abundant, long-lived proteins of the eye lens. The major human crystallins belong to two different superfamilies: the small heat-shock proteins (α-crystallins) and the βγ-crystallins. During evolution, other proteins have sometimes been recruited as crystallins to modify the properties of the lens. In the developing human lens, the enzyme betaine-homocysteine methyltransferase serves such a role. Evolutionary modification has also resulted in loss of expression of some human crystallin genes or of specific splice forms. Crystallin organization is essential for lens transparency and mutations; even minor changes to surface residues can cause cataract and loss of vision. PMID:23199295

  8. The catalytic diversity of zeolites: confinement and solvation effects within voids of molecular dimensions.

    PubMed

    Gounder, Rajamani; Iglesia, Enrique

    2013-05-04

    chemical composition, thus enabling voids of a given size and shape to provide the "right fit" for a given elementary step, defined as that which minimizes Gibbs free energies of activation. Tighter confinement is preferred at low temperatures because enthalpic gains prevail over concomitant entropic losses, while looser fits are favored at high temperatures because entropy gains offset losses in enthalpic stabilization. Confinement and solvation by van der Waals forces are not directly involved in the making or breaking of strong chemical bonds; yet, they confer remarkable diversity to zeolites, in spite of their structural rigidity and their common aluminosilicate composition. A single zeolite can itself contain a range of local void environments, each with distinct reactivity and selectivity; as a result, varying the distribution of protons among these locations within a given framework or modifying a given location by partial occlusion of the void space can extend the range of catalytic opportunities for zeolites. Taken together with theoretical tools that accurately describe van der Waals interactions between zeolite voids and confined guests and with synthetic protocols that place protons or space-filling moieties at specific locations, these concepts promise to broaden the significant impact and catalytic diversity already shown by microporous solids.

  9. The zeolite deposits of Greece

    USGS Publications Warehouse

    Stamatakis, M.G.; Hall, A.; Hein, J.R.

    1996-01-01

    Zeolites are present in altered pyroclastic rocks at many localities in Greece, and large deposits of potential economic interest are present in three areas: (1) the Evros region of the province of Thrace in the north-eastern part of the Greek mainland; (2) the islands of Kimolos and Poliegos in the western Aegean; and (3) the island of Samos in the eastern Aegean Sea. The deposits in Thrace are of Eocene-Oligocene age and are rich in heulandite and/or clinoptilolite. Those of Kimolos and Poliegos are mainly Quaternary and are rich in mordenite. Those of Samos are Miocene, and are rich in clinoptilolite and/or analcime. The deposits in Thrace are believed to have formed in an open hydrological system by the action of meteoric water, and those of the western Aegean islands in a similar way but under conditions of high heat flow, whereas the deposits in Samos were formed in a saline-alkaline lake.

  10. Methylene blue removal from contaminated waters using O3, natural zeolite, and O3/zeolite.

    PubMed

    Valdés, H; Tardón, R F; Zaror, C A

    2009-01-01

    This paper compares experimental results on methylene blue (MB) removal systems based on ozone oxidation, zeolite adsorption, and simultaneous adsorption-oxidation using ozone in the presence of natural zeolite. The effect of pH (2-8), and the presence of radical scavengers (sodium acetate) on process rates and removal efficiencies are assessed at laboratory scale. The experimental system consisted of a 1 L differential circular flow reactor and an ozone generator rated at 5 g O3/h. Results show that ozone oxidation combined with zeolite adsorption increases the overall MB oxidation rate with respect to ozonation process and zeolite adsorption. In presence of free radical scavenger, only a 25% of reduction on MB removal rate are observed in the simultaneous treatment, as compared with 70% when ozonation treatment is used, suggesting that MB oxidation reactions take mainly place on the zeolite surface.

  11. Elastic and structural properties of zeolites: Sodalite and dehydrated zeolite A

    SciTech Connect

    Kim, S.; Keskar, N.R.; McCormick, A.V.; Chelikowsky, J.R.; Davis, H.T.

    1995-06-01

    A pairwise interatomic potential has been used to investigate elastic and structural properties of two cubic zeolites: sodalite and dehydrated zeolite A. Constant volume energy minimization has been used to determine the variation of lattice constants and atomic coordinates with pressure. The calculated structures of sodalite and dehydrated zeolite A obtained at zero pressure are in reasonably good agreement with the available experimental values. We find that the structures at zero pressure are largely determined by the Coulomb potential. The pressure dependence of bond lengths and bond angles show that both sodalite and dehydrated zeolite A are easily deformed by bending the Si--O--Al angles. As expected for a less dense crystal, the dehydrated zeolite A is softer than the sodalite. We have also obtained the equation of state of these materials.

  12. Topological nonsymmorphic crystalline superconductors

    NASA Astrophysics Data System (ADS)

    Wang, Qing-Ze; Liu, Chao-Xing

    2016-01-01

    Topological superconductors possess a nodeless superconducting gap in the bulk and gapless zero energy modes, known as "Majorana zero modes," at the boundary of a finite system. In this work, we introduce a new class of topological superconductors, which are protected by nonsymmorphic crystalline symmetry and thus dubbed "topological nonsymmorphic crystalline superconductors." We construct an explicit Bogoliubov-de Gennes type of model for this superconducting phase in the D class and show how Majorana zero modes in this model are protected by glide plane symmetry. Furthermore, we generalize the classification of topological nonsymmorphic crystalline superconductors to the classes with time reversal symmetry, including the DIII and BDI classes, in two dimensions. Our theory provides guidance to search for new topological superconducting materials with nonsymmorphic crystal structures.

  13. Topological Nonsymmorphic Crystalline Superconductors

    NASA Astrophysics Data System (ADS)

    Wang, Qing-Ze; Liu, Chao-Xing

    Topological superconductors possess a nodeless superconducting gap in the bulk and gapless zero energy modes, known as ``Majorana zero modes'', at the boundary of a finite system. In this work, we introduce a new class of topological superconductors, which are protected by nonsymmorphic crystalline symmetry and thus dubbed ``topological nonsymmorphic crystalline superconductors''. We construct an explicit Bogoliubov-de Gennes type of model for this superconducting phase in the D class and show how Majorana zero modes in this model are protected by glide symmetry. Furthermore, we generalize the classification of topological nonsymmorphic crystalline superconductors to the classes with time reversal symmetry, including the DIII and BDI classes, in two dimensions. Our theory provides a guidance to search for new topological superconducting materials with nonsymmorphic crystal structures.

  14. Crystalline molecular flasks.

    PubMed

    Inokuma, Yasuhide; Kawano, Masaki; Fujita, Makoto

    2011-05-01

    A variety of host compounds have been used as molecular-scale reaction vessels, protecting guests from their environment or restricting the space available around them, thus favouring particular reactions. Such molecular 'flasks' can endow guest molecules with reactivities that differ from those in bulk solvents. Here, we extend this concept to crystalline molecular flasks, solid-state crystalline networks with pores within which pseudo-solution-state reactions can take place. As the guest molecules can spontaneously align along the walls and channels of the hosts, structural changes in the substrates can be directly observed by in situ X-ray crystallography during reaction. Recently, this has enabled observation of the molecular structures of transient intermediates and other labile species, in the form of sequential structural snapshots of the chemical transformation. Here, we describe the principles, development and applications of crystalline molecular flasks.

  15. Nanocrystalline zeolite beta and zeolite Y as catalysts in used palm oil cracking for the production of biofuel

    NASA Astrophysics Data System (ADS)

    Taufiqurrahmi, Niken; Mohamed, Abdul Rahman; Bhatia, Subhash

    2011-08-01

    Nanocrystalline zeolites with crystal size smaller than 100 nm are potential replacement for conventional zeolite catalysts due to their unique characteristics and advantages. In this study, the synthesis of nanocrystalline zeolite Y (FAU) and nanocrystalline zeolite beta (BEA) under hydrothermal conditions is reported. The effect of crystal size on the physico-chemical characteristics of the zeolite, Y (FAU), and beta (BEA) is reported. The properties of nanocrystalline zeolites Y and Beta with crystal size around 50 nm are compared with the microcrystalline zeolite Y and microcrystalline zeolite beta, respectively. The performance of the nanocrystalline zeolite as a catalyst was investigated in the cracking of used palm oil for the production of biofuel. The nanocrystalline zeolite catalytic activity was compared with the activity of microcrystalline zeolite in order to study the effect of crystal size on the catalytic activity. Both nanocrystalline zeolites gave better performance in terms of conversion of used palm oil as well as selectivity for the formation of gasoline fraction. The increase in surface area and improved accessibility of the reactant in nanocrystalline zeolites enhanced the cracking activity as well as the desired product selectivity.

  16. Synthesis and catalytic properties of metal clusters encapsulated within small-pore (SOD, GIS, ANA) zeolites.

    PubMed

    Goel, Sarika; Wu, Zhijie; Zones, Stacey I; Iglesia, Enrique

    2012-10-24

    The synthesis protocols for encapsulation of metal clusters reported here expand the diversity in catalytic chemistries made possible by the ability of microporous solids to select reactants, transition states, and products on the basis of their molecular size. We report a synthesis strategy for the encapsulation of noble metals and their oxides within SOD (Sodalite, 0.28 nm × 0.28 nm), GIS (Gismondine, 0.45 nm × 0.31 nm), and ANA (Analcime, 0.42 nm × 0.16 nm) zeolites. Encapsulation was achieved via direct hydrothermal synthesis for SOD and GIS using metal precursors stabilized by ammonia or organic amine ligands, which prevent their decomposition or precipitation as colloidal hydroxides at the conditions of hydrothermal synthesis (<380 K) and favor interactions between metal precursors and incipient aluminosilicate nuclei during self-assembly of microporous frameworks. The synthesis of ANA requires higher crystallization temperatures (~415 K) and high pH (>12), thereby causing precipitation of even ligand-stabilized metal precursors as hydroxides. As a result, encapsulation was achieved by the recrystallization of metal clusters containing GIS into ANA, which retained these metal clusters within voids throughout the GIS-ANA transformation.

  17. Magnetic and Mössbauer study of metal-zeolite interaction in catalysts

    NASA Astrophysics Data System (ADS)

    Pannaparayil, Thomas; Oskooie-Tabrizi, M.; Lo, C.; Mulay, L. N.; Melson, G. A.; Rao, V. U. S.

    1984-03-01

    Molecular sieve aluminosilicates, such as ZSM-5 and mordenite, when impregnated with highly dispersed Fe, yield catalysts for the selective conversion of coal-derived syngas (CO+H2) to liquid hydrocarbon fuels. Fe performs the primary Fischer-Tropsch (FT) syngas to yield light olefins which are converted by the acidic (H+) and shape-selective function of the zeolite to high octane gasoline components. The physical aspects of the Fe-mordenite interaction studied by magnetic measurements, Mössbauer, and IR spectroscopy are reported and correlations with the catalytic properties are drawn. Mordenite samples with [SiO2/Al2O3] ratio in the range 12 - 60 were impregnated with 15 wt. % Fe using Fe3(CO)12; decarbonylation yielded superparamagmetic dispersions of γ-Fe2O3, in the range 1.4-5.0 nm; the smallest particles were obtained for a ratio=17. Hydrogen chemisorption also revealed a similar trend in Fe dispersions. No samples, other than the one with a ratio=60 and containing the largest particles could be carbided under usual conditions. The acidity of the mordenite and the aromatics fraction in liquid hydrocarbons from syngas conversion also showed maxima at a ratio=17. The presence of a strong metal-support interaction between Fe and mordenite was thus influenced by the varying ratios in the mordenite in a manner that paralleled the acidity and catalytic activity.

  18. Fenten chemistry of Fe(III)-exchanged zeolitic minerals treated with antioxidants.

    PubMed

    Ruda, Toni A; Dutta, Prabir K

    2005-08-15

    Respirable mineral fibers, such as asbestos, are known to cause pleural mesothelioma, pulmonary fibrosis, and bronchial carcinoma, often years after exposure. Erionite and mordenite, two mineral aluminosilicates (zeolites) with different toxicities, can be used as models to help understand asbestos toxicity. Erionite is carcinogenic, while mordenite is relatively benign. No iron is typically present in erionite or mordenite, but because of their ion-exchange properties they can acquire iron after inhalation. The iron is typically in the Fe(III) form and will need to be reduced prior to any Fenton activity. Lung lining fluid contains antioxidants, such as glutathione (GSH) and ascorbic acid (AA), which can reduce Fe(III) to Fe(II). In this study, we have compared the Fenton reactivity of Fe(III)-exchanged erionite and mordenite after treatment with antioxidants. The Fenton assay involved the reaction of hydroxyl radicals with dimethyl sulfoxide. Fenton reactivity was most marked with AA followed by GSH, and hydrogen peroxide also exhibited minor reactivity. Erionite generated an order of magnitude greater hydroxyl radicals than mordenite, normalized to the surface iron content, providing support for the hypothesis that the iron coordination at the mineral surface plays a significant role in bioactivity.

  19. 11. EASTERN END OF ZEOLITE BUILDING. NOTE DIAL TO LEFT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    11. EASTERN END OF ZEOLITE BUILDING. NOTE DIAL TO LEFT OF CLOCK GAUGING TOTAL ZEOLITE INFLUENT IN MILLIONS OF GALLONS PER DAY. - F. E. Weymouth Filtration Plant, 700 North Moreno Avenue, La Verne, Los Angeles County, CA

  20. Calculation of the 13C NMR shieldings of the C0 2 complexes of aluminosilicates

    NASA Astrophysics Data System (ADS)

    Tossell, J. A.

    1995-04-01

    13C NMR shieldings have been calculated using the random-phase-approximation, localized-orbital local-origins version of ab initio coupled Hartree-Fuck perturbation theory for CO 2 and and for several complexes formed by the reaction of CO 2 with molecular models for aluminosilicate glasses, H 3TOT'H3 3-n, T,T' = Si,Al. Two isomeric forms of the CO 2-aluminosilicate complexes have been considered: (1) "CO 2-like" complexes, in which the CO 2 group is bound through carbon to a bridging oxygen and (2) "CO 3-like" complexes, in which two oxygens of a central CO 3 group form bridging bonds to the two TH 3 groups. The CO 2-like isomer of CO 2-H 3SiOSiH 3 is quite weakly bonded and its 13C isotropic NMR shielding is almost identical to that in free CO 2. As Si is progressively replaced by Al in the - H terminated aluminosilicate model, the CO 2-like isomers show increasing distortion from the free CO 2 geometry and their 13C NMR shieldings decrease uniformly. The calculated 13C shielding value for H 3AlO(CO 2)AlH 3-2 is only about 6 ppm larger than that calculated for point charge stabilized CO 3-2. However, for a geometry of H 3SiO(CO 2) AlH 3-1, in which the bridging oxygen to C bond length has been artificially increased to that found in the - OH terminated cluster (OH) 3SiO(CO 2)Al(OH) 3-1, the calculated 13C shielding is almost identical to that for free CO 2. The CO 3-like isomers of the CO 2-aluminosili-cate complexes show carbonate like geometries and 13C NMR shieldings about 4-9 ppm larger than those of carbonate for all T,T' pairs. For the Si,Si tetrahedral atom pair the CO 2-like isomer is more stable energetically, while for the Si,Al and Al,Al cases the CO 3-like isomer is more stable. Addition of Na + ions to the CO 3-2 or H 3AlO(CO 2)AlH 3-2 complexes reduces the 13C NMR shieldings by about 10 ppm. Complexation with either Na + or CO 2 also reduces the 29Si NMR shieldings of the aluminosilicate models, while the changes in 27Al shielding with Na + or CO 2

  1. Method for the preparation of catalyst composition for use in cracking hydrocarbons

    SciTech Connect

    Nishimura, Y.; Ogata, M.; Ida, T.

    1987-01-13

    A method is described for preparing a catalyst composition for cracking hydrocarbons, which consists essentially of: spray drying an aqueous slurry containing (i) flash calcined alumina particles which have been prepared by contacting aluminum hydroxide which has been made by the Bayer process, with hot air having a temperature in the range of 350/sup 0/ to 700/sup 0/C., for 5 seconds or less, (ii) kaolin, (iii) a precursor of a siliceous inorganic oxide matrix, and (iv) a crystalline aluminosilicate zeolite, to obtain catalyst particles consisting essentially of from 10 to 30 wt. % of the flash-calcined alumina, from 30 to 55 wt. % of the kaolin, from 3 to 40 wt. % crystalline aluminosilicate zeolite and the balance is the siliceous inorganic oxide matrix. A method is also described in which the zeolite is rare earth exchange zeolite Y or hydrogen exchanged zeolite Y.

  2. On the induction of homogeneous bulk crystallization in Eu-doped calcium aluminosilicate glass by applying simultaneous high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Muniz, R. F.; de Ligny, D.; Le Floch, S.; Martinet, C.; Rohling, J. H.; Medina, A. N.; Sandrini, M.; Andrade, L. H. C.; Lima, S. M.; Baesso, M. L.; Guyot, Y.

    2016-06-01

    From initial calcium aluminosilicate glass, transparent glass-ceramics have been successfully synthesized under simultaneous high pressure and temperature (SHPT). Possible homogeneous volumetric crystallization of this glassy system, which was not achieved previously by means of conventional heat treatment, has been put in evidence with a SHPT procedure. Structural, mechanical, and optical properties of glass and glass-ceramic obtained were investigated. Raman spectroscopy and X-ray diffraction allowed to identify two main crystalline phases: merwinite [Ca3Mg(SiO4)2] and diopside [CaMgSi2O6]. A Raman scanning profile showed that the formation of merwinite is quite homogeneous over the bulk sample. However, the sample surface also contains significant diopside crystals. Instrumented Berkovich nanoindentation was applied to determine the effect of SHPT on hardness from glass to glass-ceramic. For Eu-doped samples, the broadband emission due to 4f65d1 → 4f7 transition of Eu2+ was studied in both host systems. Additionally, the 5D0 → 7FJ transition of Eu3+ was used as an environment probe in the pristine glass and the glass-ceramic.

  3. Effects of Fiber Content on Mechanical Properties of CVD SiC Fiber-Reinforced Strontium Aluminosilicate Glass-Ceramic Composites

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.

    1996-01-01

    Unidirectional CVD SiC(f)(SCS-6) fiber-reinforced strontium aluminosilicate (SAS) glass-ceramic matrix composites containing various volume fractions, approximately 16 to 40 volume %, of fibers were fabricated by hot pressing at 1400 C for 2 h under 27.6 MPa. Monoclinic celsian, SrAl2Si2O8, was the only crystalline phase formed, with complete absence of the undesired hexacelsian phase, in the matrix. Room temperature mechanical properties were measured in 3-point flexure. The matrix microcracking stress and the ultimate strength increased with increase in fiber volume fraction, reached maximum values for V(sub f) approximately equal to 0.35, and degraded at higher fiber loadings. This degradation in mechanical properties is related to the change in failure mode, from tensile at lower V(sub f) to interlaminar shear at higher fiber contents. The extent of fiber loading did not have noticeable effect on either fiber-matrix debonding stress, or frictional sliding stress at the interface. The applicability of micromechanical models in predicting the mechanical properties of the composites was also examined. The currently available theoretical models do not appear to be useful in predicting the values of the first matrix cracking stress, and the ultimate strength of the SCS-6/SAS composites.

  4. Contribution of Aluminas and Aluminosilicates to the Formation of PCDD/Fs on Fly Ashes

    PubMed Central

    Potter, Phillip M.; Dellinger, Barry; Lomnicki, Slawomir M.

    2015-01-01

    Chlorinated aromatics undergo surface-mediated reactions with metal oxides to form Environmentally Persistent Free Radicals (EPFRs) which can further react to produce polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Previous work using laboratory-made fly ash surrogates composed of transition metal oxides deposited on silica powder has confirmed their ability to mimic fly ash in the production of PCDD/Fs. However, little is known about the propensity of aluminas and aluminosilicates, other components of fly ash, to form PCDD/Fs. A fly ash sample containing both alumina and mullite, an aluminosilicate, was tested for PCDD/F formation ability and compared to PCDD/F yields from the thermal degradation of 2-monochlorophenol (2-MCP) precursor over γ-alumina, α-alumina, and mullite. A packed-bed flow reactor was used to investigate the thermal degradation of 2-MCP over the various catalysts at 200–600 °C. Fly ash gave similar PCDD/F yields to surrogates made with similar transition metal content. γ-alumina, which is thermodynamically unfavorable, was very catalytically active and gave low PCDD/F yields despite a high destruction of 2-MCP. Mullite and α-alumina, the thermodynamically favorable form of alumina, yielded higher concentrations of dioxins and products with a higher degree of chlorine substitution than γ-alumina. The data suggest that certain aluminas and aluminosilicates, commonly found in fly ash, are active catalytic surfaces in the formation of PCDD/Fs in the post-flame cool zones of combustion systems and should be considered as additional catalytic surfaces active in the process. PMID:26615490

  5. In vitro osteogenic/dentinogenic potential of an experimental calcium aluminosilicate cement

    PubMed Central

    Eid, Ashraf A.; Niu, Li-na; Primus, Carolyn M.; Opperman, Lynne A.; Watanabe, Ikuya; Pashley, David H.; Tay, Franklin R.

    2013-01-01

    Introduction Calcium aluminosilicate cements are fast-setting, acid-resistant, bioactive cements that may be used as root-repair materials. This study examined the osteogenic/dentinogenic potential of an experimental calcium aluminosilicate cement (Quick-Set) using a murine odontoblast-like cell model. Methods Quick-Set and white ProRoot MTA (WMTA) were mixed with the proprietary gel or deionized water, allowed to set completely in 100% relative humidity and aged in complete growth medium for 2 weeks until rendered non-cytotoxic. Similarly-aged Teflon discs were used as negative control. The MDPC-23 cell-line was used for evaluating changes in mRNA expressions of genes associated with osteogenic/dentinogenic differentiation and mineralization (qRT-PCR) alkaline phosphatase enzyme production and extracellular matrix mineralization (Alizarin red-S staining). Results After MDPC-23 cells were incubated with the materials in osteogenic differentiation medium for 1 week, both cements showed upregulation in ALP and DSPP expression. Fold increases in these two genes were not significantly different between Quick-Set and WMTA. Both cements showed no statistically significant upregulation/downregulation in RUNX2, OCN, BSP and DMP1 gene expression compared with Teflon. Alkaline phosphatase activity of cells cultured on Quick-Set and WMTA were not significantly different at 1 week or 2 weeks, but were significantly higher (p<0.05) than Teflon in both weeks. Both cements showed significantly higher calcium deposition compared with Teflon after 3 weeks of incubation in mineralizing medium (p<0.001). Differences between Quick-Set and WMTA were not statistically significant. Conclusions The experimental calcium aluminosilicate cement exhibits similar osteogenic/dentinogenic properties to WMTA and may be a potential substitute for commercially-available tricalcium silicate cements. PMID:23953291

  6. Metallic nanoparticles and their medicinal potential. Part II: aluminosilicates, nanobiomagnets, quantum dots and cochleates.

    PubMed

    Loomba, Leena; Scarabelli, Tiziano

    2013-09-01

    Metallic miniaturization techniques have taken metals to nanoscale size where they can display fascinating properties and their potential applications in medicine. In recent years, metal nanoparticles such as aluminium, silicon, iron, cadmium, selenium, indium and calcium, which find their presence in aluminosilicates, nanobiomagnets, quantum dots (Q-dots) and cochleates, have caught attention of medical industries. The increasing impact of metallic nanoparticles in life sciences has significantly advanced the production techniques for these nanoparticles. In this Review, the various methods for the synthesis of nanoparticles are outlined, followed by their physicochemical properties, some recent applications in wound healing, diagnostic imaging, biosensing, assay labeling, antimicrobial activity, cancer therapy and drug delivery are listed, and finally their toxicological impacts are revised. The first half of this article describes the medicinal uses of two noble nanoparticles - gold and silver. This Review provides further information on the ability of aluminum, silicon, iron, selenium, indium, calcium and zinc to be used as nanoparticles in biomedical sciences. Aluminosilicates find their utility in wound healing and antibacterial growth. Iron-oxide nanoparticles enhance the properties of MRI contrast agents and are also used as biomagnets. Cadmium, selenium, tellurium and indium form the core nanostructures of tiny Q-dots used in cellular assay labeling, high-resolution cell imaging and biosensing. Cochleates have the bivalent nano ions calcium, magnesium or zinc imbedded in their structures and are considered to be highly effective agents for drug and gene delivery. The aluminosilicates, nanobiomagnets, Q-dots and cochleates are discussed in the light of their properties, synthesis and utility.

  7. Fly ash zeolite catalyst support for Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Campen, Adam

    This dissertation research aimed at evaluating a fly ash zeolite (FAZ) catalyst support for use in heterogeneous catalytic processes. Gas phase Fischer-Tropsch Synthesis (FTS) over a fixed-bed of the prepared catalyst/FAZ support was identified as an appropriate process for evaluation, by comparison with commercial catalyst supports (silica, alumina, and 13X). Fly ash, obtained from the Wabash River Generating Station, was first characterized using XRD, SEM/EDS, particle size, and nitrogen sorption techniques. Then, a parametric study of a two-step alkali fusion/hydrothermal treatment process for converting fly ash to zeolite frameworks was performed by varying the alkali fusion agent, agent:flyash ratio, fusion temperature, fused ash/water solution, aging time, and crystallization time. The optimal conditions for each were determined to be NaOH, 1.4 g NaOH: 1 g fly ash, 550 °C, 200 g/L, 12 hours, and 48 hours. This robust process was applied to the fly ash to obtain a faujasitic zeolite structure with increased crystallinity (40 %) and surface area (434 m2/g). Following the modification of fly ash to FAZ, ion exchange of H+ for Na+ and cobalt incipient wetness impregnation were used to prepare a FTS catalyst. FTS was performed on the catalysts at 250--300 °C, 300 psi, and with a syngas ratio H2:CO = 2. The HFAZ catalyst support loaded with 11 wt% cobalt resulted in a 75 % carbon selectivity for C5 -- C18 hydrocarbons, while methane and carbon dioxide were limited to 13 and 1 %, respectively. Catalyst characterization was performed by XRD, N2 sorption, TPR, and oxygen pulse titration to provide insight to the behavior of each catalyst. Overall, the HFAZ compared well with silica and 13X supports, and far exceeded the performance of the alumina support under the tested conditions. The successful completion of this research could add value to an underutilized waste product of coal combustion, in the form of catalyst supports in heterogeneous catalytic processes.

  8. Hydrothermal conversion of FAU zeolite into LEV zeolite in the presence of non-calcined seed crystals

    NASA Astrophysics Data System (ADS)

    Yashiki, Ayako; Honda, Koutaro; Fujimoto, Ayumi; Shibata, Shohei; Ide, Yusuke; Sadakane, Masahiro; Sano, Tsuneji

    2011-06-01

    Hydrothermal conversion of Faujasite-type (FAU) zeolite into Levynite (LEV) zeolite without the use of an organic structure-directing agent (OSDA) was successfully achieved in the presence of non-calcined seed crystals. The interzeolite conversion depended strongly upon the alkalinity (OH -/SiO 2) of the starting gel, the Si/Al ratio of the starting FAU zeolite and the type of alkaline metal employed. Successful conversion of FAU zeolites into pure LEV zeolite was achieved only for FAU zeolites with Si/Al ratios in the range of 19-26, under highly alkaline conditions (OH -/SiO 2=0.6) by using NaOH as an alkali source. Although the yield of LEV zeolite prepared by this method was lower (18-26%) than that of the conventional hydrothermal synthesis with the use of SDA, the obtained LEV zeolite exhibited a unique core/shell structure.

  9. Production of biofuel from waste cooking palm oil using nanocrystalline zeolite as catalyst: process optimization studies.

    PubMed

    Taufiqurrahmi, Niken; Mohamed, Abdul Rahman; Bhatia, Subhash

    2011-11-01

    The catalytic cracking of waste cooking palm oil to biofuel was studied over different types of nano-crystalline zeolite catalysts in a fixed bed reactor. The effect of reaction temperature (400-500 °C), catalyst-to-oil ratio (6-14) and catalyst pore size of different nanocrystalline zeolites (0.54-0.80 nm) were studied over the conversion of waste cooking palm oil, yields of Organic Liquid Product (OLP) and gasoline fraction in the OLP following central composite design (CCD). The response surface methodology was used to determine the optimum value of the operating variables for maximum conversion as well as maximum yield of OLP and gasoline fraction, respectively. The optimum reaction temperature of 458 °C with oil/catalyst ratio=6 over the nanocrystalline zeolite Y with pore size of 0.67 nm gave 86.4 wt% oil conversion, 46.5 wt% OLP yield and 33.5 wt% gasoline fraction yield, respectively. The experimental results were in agreement with the simulated values within an experimental error of less than 5%.

  10. Improving Stability of Zeolites in Aqueous Phase via Selective Removal of Structural Defects

    SciTech Connect

    Prodinger, Sebastian; Derewinski, Miroslaw A.; Vjunov, Aleksei; Burton, Sarah D.; Arslan, Ilke; Lercher, Johannes A.

    2016-03-13

    This work reports significant improvement in the hydrothermal stability of a well-characterized BEA zeolite via the selective removal of structural defects. Recent work suggests that the presence of silanol defects destabilizes the framework integrity of most zeolites and makes them susceptible to hydrolysis of the siloxy bonds by hot liquid water. The described approach allows for a key removal of silanols as shown with 29Si-MAS-NMR. Subsequently, the material stability in hot liquid water, measured by retention of its crystallinity with X-ray diffraction (XRD), is found to be superior to defective zeolites. In addition, N2-sorption measurements (BET) and transmission electron microscopy (TEM) show the formation of different types of mesoporosity for water-treated stabilized and unmodified materials. While the sorption capacity for untreated materials drops, related to re-precipitation of dissolved silica and pore blocking, the stabilized material retains its microporosity and improves its overall sorption capacity. The authors would like to thank B. W. Arey (PNNL) for HIM measurements and I. Arslan for TEM imaging. This work was supported by the U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. SP and MD acknowledge support by the Materials Synthesis and Simulation Across Scales (MS3 Initiative) conducted under Laboratory Directed Research & Development Program at PNNL.

  11. Dynamics of Oxidation of a Fe2+-Bearing Aluminosilicate (Basaltic) Melt

    PubMed

    Cooper; Fanselow; Weber; Merkley; Poker

    1996-11-15

    Rutherford backscattering spectroscopy (RBS) and microscopy demonstrate that the approximately 1400°C oxidation of levitated droplets of a natural Fe2+-bearing aluminosilicate (basalt) melt occurs by chemical diffusion of Fe2+ and Ca2+ to the free surface of the droplet; internal oxidation of the melt results from the required counterflux of electron holes. Diffusion of an oxygen species is not required. Oxidation causes the droplets to go subsolidus; magnetite (Fe3O4) forms at the oxidation-solidification front with a morphology suggestive of a Liesegang-band nucleation process.

  12. Tensile and creep behavior of a silicon carbide fiber-reinforced aluminosilicate composite

    SciTech Connect

    Khobaib, M.; Zawada, L.

    1991-08-01

    Tensile and tensile creep tests were conducted with a Nicalon/aluminosilicate (Si-C-O/1723) glass composite. Tensile tests were conducted at room temperature, and the creep tests were conducted at 600, 700, and 750 C. Room temperature tensile test failure features exhibited a tortuous crack path and extensive fiber pull-out. The failure features in creep were characterized by flat fracture and little fiber pull-out. The environment appeared to play a significant role in creep failure of this composite system. 6 refs.

  13. DuraLith Alkali-Aluminosilicate Geopolymer Waste Form Testing for Hanford Secondary Waste

    SciTech Connect

    Gong, W. L.; Lutz, Werner; Pegg, Ian L.

    2011-07-21

    The primary objective of the work reported here was to develop additional information regarding the DuraLith alkali aluminosilicate geopolymer as a waste form for liquid secondary waste to support selection of a final waste form for the Hanford Tank Waste Treatment and Immobilization Plant secondary liquid wastes to be disposed in the Integrated Disposal Facility on the Hanford Site. Testing focused on optimizing waste loading, improving waste form performance, and evaluating the robustness of the waste form with respect to waste variability.

  14. Physical chemical studies of dispersed aluminosilicate wastes for obtaining the burned building materials

    NASA Astrophysics Data System (ADS)

    Iuriev, I. Y.; Skripnikova, N. K.; Volokitin, G. G.; Volokitin, O. G.; Lutsenko, A. V.; Kosmachev, P. V.

    2015-01-01

    This paper presents results of the studies that determined that grinding can be one of the ways to modify aluminosilicate wastes. The optimal grinding modes were defined in laboratory conditions. Physical and chemical studies of modified ashes were carried out by means of X-ray phase analysis, differential thermal analysis and microscopy. The results have shown that modified ashes of thermal power stations when being applied in production of ceramic brick influence positively the processing properties of raw materials and the ready products.

  15. Potential Sites for Ice Nucleation on Aluminosilicate Clay Minerals and Related Materials.

    PubMed

    Freedman, Miriam Arak

    2015-10-01

    Few aerosol particles in clouds nucleate the formation of ice. The surface sites available for nucleus formation, which can include surface defects and functional groups, determine in part the activity of an aerosol particle toward ice formation. Although ice nucleation on particles has been widely studied, exploration of the specific sites at which the initial germ forms has been limited, but is important for predicting the microphysical properties of clouds, which impact climate. This Perspective focuses on what is currently known about surface sites for ice nucleation on aluminosilicate clay minerals, which are commonly found in ice residuals, as well as related materials.

  16. Improving the osteointegration of Ti6Al4V by zeolite MFI coating

    SciTech Connect

    Li, Yong; Jiao, Yilai; Li, Xiaokang; Guo, Zheng

    2015-05-01

    Osteointegration is crucial for success in orthopedic implantation. In recent decades, there have been numerous studies aiming to modify titanium alloys, which are the most widely used materials in orthopedics. Zeolites are solid aluminosilicates whose application in the biomedical field has recently been explored. To this end, MFI zeolites have been developed as titanium alloy coatings and tested in vitro. Nevertheless, the effect of the MFI coating of biomaterials in vivo has not yet been addressed. The aim of the present work is to evaluate the effects of MFI-coated Ti6Al4V implants in vitro and in vivo. After surface modification, the surface was investigated using field emission scanning electron microscopy (FE-SEM) and energy dispersive spectroscopy (EDS). No difference was observed regarding the proliferation of MC3T3-E1 cells on the Ti6Al4V (Ti) and MFI-coated Ti6Al4V (M−Ti) (p > 0.05). However, the attachment of MC3T3-E1 cells was found to be better in the M−Ti group. Additionally, ALP staining and activity assays and quantitative real-time RT-PCR indicated that MC3T3-E1 cells grown on the M−Ti displayed high levels of osteogenic differentiation markers. Moreover, Van-Gieson staining of histological sections demonstrated that the MFI coating on Ti6Al4V scaffolds significantly enhanced osteointegration and promoted bone regeneration after implantation in rabbit femoral condylar defects at 4 and 12 weeks. Therefore, this study provides a method for modifying Ti6Al4V to achieve improved osteointegration and osteogenesis. - Highlights: • Osteointegration is a crucial factor for orthopedic implants. • We coated MFI zeolite on Ti6Al4V substrates and investigated the effects in vitro and in vivo. • The MFI coating displayed good biocompatibility and promoted osteogenic differentiation in vitro. • The MFI coating promoted osteointegration and osteogenesis peri-implant in vivo.

  17. Determination of trace elements in zeolites by laser ablation ICP-MS.

    PubMed

    Pickhardt, C; Brenner, I B; Becker, J S; Dietze, H J

    2000-09-01

    Laser ablation inductively coupled plasma mass spectrometry using a quadrupole-based mass spectrometer (LA-ICP-QMS) was applied for the analysis of powdered zeolites (microporous aluminosilicates) used for clean-up procedures. For the quantitative determination of trace element concentrations three geological reference materials, granite NIM-G, lujavrite NIM-L and syenite NIM-S, from the National Institute for Metallurgy (South Africa) with a matrix composition corresponding to the zeolites were employed. Both the zeolites and reference materials were fused with a lithium borate mixture to increase the homogeneity and to eliminate mineralogical effects. In order to compare two different approaches for the quantification of analytical results in LA-ICP-MS relative sensitivity coefficients (RSCs) of chemical elements and calibration curves were measured using the geostandards. The experimentally obtained RSCs are in the range of 0.2-6 for all elements of interest. Calibration curves for trace elements were measured without and with Li or Ti as internal standard element. With a few exceptions the regression coefficients of the calibration curves are better than 0.993 with internal standardization. NIM-G granite reference material was employed to evaluate the accuracy of the technique. Therefore, the measured concentrations were corrected with RSCs which were determined using lujavrite reference material NIM-L. This quantification method provided analytical results with deviations of 1-11% from the recommended and proposed values in granite reference material NIM-G, except for Co, Cs, La and Tb. The relative standard deviation (RSD) of the determination of the trace element concentration (n = 5) is about 1% to 6% using Ti as internal standard element. Detection limits of LA-ICP-QMS in the lower microg/g range (from 0.03 microg/g for Lu, Ta and Th to 7.3 microg/g for Cu, with the exception of La) have been achieved for all elements of interest. Under the laser ablation

  18. Preparation, Processing, and Characterization of Oriented Polycrystalline Zeolite and Aluminophosphate Membranes

    NASA Astrophysics Data System (ADS)

    Stoeger, Jared Andrew

    Since the advent of zeolite membranes, speculation on their industrial applicability has been closely monitored, although widespread commercialization has been hampered by limitations in fabrication and post-synthesis processing. Economical, energy-efficient technology breakthroughs require an evaluation of a range of material candidates which show robustness and reliability. Straightforward manufacturing techniques should be devised to generate thousands of square meters of membrane area; however, this demands control of structural characteristics on the scale of nanometers. As described in this dissertation, the path forward will be forged by exploiting the intrinsic crystalline properties of zeolites or aluminophosphates for the next advancement in membrane technology. A facile method is described for the preparation of silicalite-1 (MFI zeolite type) membranes using the secondary growth technique on symmetric porous stainless steel tubes. Activation through rapid thermal processing (RTP), a lamp-based heat-treatment process used as a critical fabrication step in silicon integrated circuit manufacturing, is proven to reduce the density of non-zeolitic transport pathways which are detrimental to high-resolution molecular sieving. RTP-treated membranes are shown to have enhanced performance in the binary separation of vapor-phase isomers (p-/o-xylene), gas-phase isomers (n-/i-butane), and alcohol/water when compared to membranes activated at a much slower heating rate but otherwise similarly-prepared. The performance is discussed in the context of the market potential for industrially-attractive separations: the recovery of p-xylene from an isomeric mixture or alcohol biofuels from aqueous post-fermentation streams. Hydrothermal growth techniques for the preparation and characterization of continuous aluminophosphate (AFI zeolite type) membranes with a preferential crystallographic alignment on porous alpha-Al2O3 disc supports are demonstrated. A mechanism is

  19. (Na{sub 4}BH{sub 4}){sup 3+} guests inside aluminosilicate, gallosilicate and aluminogermanate sodalite host frameworks studied by {sup 1}H, {sup 11}B, and {sup 23}Na MAS NMR spectroscopy

    SciTech Connect

    Buhl, J.-Ch.; Murshed, M.M.

    2009-07-01

    We report tetrahydroborate aluminosilicate, gallosilicate and aluminogermanate sodalites studied by {sup 11}B, {sup 1}H and {sup 23}Na MAS NMR spectroscopy. The spectral parameters are consistent with the local environments of each investigated nucleus obtained from the crystal structures. The {sup 11}B MAS NMR spectra exhibit a sharp narrow line at about -49.0 ppm, which is assigned to BH{sub 4}{sup -} enclathrated into the sodalite framework matrix. The lineshape of the signal shows no quadrupolar interactions due to discreteness and high symmetry of the BH{sub 4}{sup -} unit as well as possible fast dynamic site exchange of hydrogen atoms. The {sup 23}Na MAS NMR signals also show a narrow Gaussian lineshape, which clearly indicates a single type of sodium coordination, and a centrosymmetrical charge distribution around the sodium atom. The {sup 1}H MAS NMR spectra can clearly distinguish between hydrogen in BH{sub 4}{sup -} anions (-0.6 ppm), H{sub 3}O{sub 2}{sup -} anions (1.2 ppm) and H{sub 2}O molecules (5.0 ppm). The structural properties of BH{sub 4}{sup -} intercalation into sodalite framework matrix help connect the microporous materials to hydride-containing A, X and Y type zeolites.

  20. Zeolites as catalysts in oil refining.

    PubMed

    Primo, Ana; Garcia, Hermenegildo

    2014-11-21

    Oil is nowadays the main energy source and this prevalent position most probably will continue in the next decades. This situation is largely due to the degree of maturity that has been achieved in oil refining and petrochemistry as a consequence of the large effort in research and innovation. The remarkable efficiency of oil refining is largely based on the use of zeolites as catalysts. The use of zeolites as catalysts in refining and petrochemistry has been considered as one of the major accomplishments in the chemistry of the XXth century. In this tutorial review, the introductory part describes the main features of zeolites in connection with their use as solid acids. The main body of the review describes important refining processes in which zeolites are used including light naphtha isomerization, olefin alkylation, reforming, cracking and hydrocracking. The final section contains our view on future developments in the field such as the increase in the quality of the transportation fuels and the coprocessing of increasing percentage of biofuels together with oil streams. This review is intended to provide the rudiments of zeolite science applied to refining catalysis.

  1. Controlling chemistry with cations: photochemistry within zeolites.

    PubMed

    Ramamurthy, V; Shailaja, J; Kaanumalle, Lakshmi S; Sunoj, R B; Chandrasekhar, J

    2003-08-21

    The alkali ions present in the supercages of zeolites X and Y interact with included guest molecules through quadrupolar (cation-pi), and dipolar (cation-carbonyl) interactions. The presence of such interactions can be inferred through solid-state NMR spectra of the guest molecules. Alkali ions, as illustrated in this article, can be exploited to control the photochemical and photophysical behaviors of the guest molecules. For example, molecules that rarely phosphoresce can be induced to do so within heavy cation-exchanged zeolites. The nature (electronic configuration) of the lowest triplet state of carbonyl compounds can be altered with the help of light alkali metal ions. This state switch (n pi*-pi pi*) helps to bring out reactivity that normally remains dormant. Selectivity obtained during the singlet oxygen oxidation of olefins within zeolites illustrates the remarkable control that can be exerted on photoreactions with the help of a confined medium that also has active sites. The reaction cavities of zeolites, like enzymes, are not only well-defined and confined, but also have active sites that closely guide the reactant molecule from start to finish. The examples provided here illustrate that zeolites are far more useful than simple shape-selective catalysts.

  2. A Site-Isolated Iridium Diethylene Complex Supported on Highly Dealuminated Y Zeolite: Synthesis And Characterization

    SciTech Connect

    Uzun, A.; Bhirud, V.A.; Kletnieks, P.W.; Haw, J.F.; Gates, B.C.

    2009-06-04

    Highly dealuminated Y zeolite-supported mononuclear iridium complexes with reactive ethylene ligands were synthesized by chemisorption of Ir(C{sub 2}H{sub 4}){sub 2}(C{sub 5}H{sub 7}O{sub 2}). The resultant structure and its treatment in He, CO, ethylene, and H2 were investigated with infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectroscopies. The IR spectra show that Ir(C{sub 2}H{sub 4}){sub 2}(C{sub 5}H{sub 7}O{sub 2}) reacted readily with surface OH groups of the zeolite, leading to the removal of C{sub 5}H{sub 7}O{sub 2} ligands and the formation of supported mononuclear iridium complexes, confirmed by the lack of Ir-Ir contributions in the EXAFS spectra. The EXAFS data show that each Ir atom was bonded to four carbon atoms at an average distance of 2.10 {angstrom}, consistent with the presence of two ethylene ligands per Ir atom and in agreement with the IR spectra indicating {pi}-bonded ethylene ligands. The EXAFS data also indicate that each Ir atom was bonded to two oxygen atoms of the zeolite at a distance of 2.15 {angstrom}. The supported iridium-ethylene complex reacted with H{sub 2} to give ethane, and it also catalyzed ethylene hydrogenation at atmospheric pressure and 294 K. Treatment of the sample in CO led to the formation of Ir(CO){sub 2} complexes bonded to the zeolite. The sharpness of the V{sub CO} bands indicates a high degree of uniformity of these complexes on the support. The iridium-ethylene complex on the crystalline zeolite support is inferred to be one of the most nearly uniform supported metal complex catalysts. The results indicate that it is isostructural with a previously reported rhodium complex on the same zeolite; thus, the results are a start to a family of analogous, structurally well-defined supported metal complex catalysts.

  3. The effect of the zeolite clinoptilolite on serum chemistry and hematopoiesis in mice.

    PubMed

    Martin-Kleiner, I; Flegar-Mestric, Z; Zadro, R; Breljak, D; Stanovic Janda, S; Stojkovic, R; Marusic, M; Radacic, M; Boranic, M

    2001-07-01

    Zeolites are natural or synthetic crystalline alumosilicates with ion exchanging properties. Supplied in fodder, they promote biomass production and animal health. Our aim was to assess the effects of the natural zeolite, clinoptilolite, on hematopoiesis, serum electrolytes and essential biochemical indicators of kidney and liver function in mice. Two preparations differing in particle size were tested: a powderized form obtained by countercurrent mechanical treatment of the clinoptilolite (MTCp) and normally ground clinoptilolite (NGCp). Young adult mice were supplied with food containing 12.5, 25 or 50% clinoptilolite powder. Control animals received the same food ration without the clinoptilolite. After 10, 20, 30 and 40 days, six animals from each group were exsanguinated to obtain blood for hematological and serum for biochemical measurements as well as to collect femoral bone marrow for determination of hematopoietic activity. Clinoptilolite ingestion was well tolerated, as judged by comparable body masses of treated and control animals. A 20% increase of the potassium level was detected in mice receiving the zeolite-rich diet, without other changes in serum chemistry. Erythrocyte, hemoglobin and platelet levels in peripheral blood were not materially affected. NGCp caused leukocytosis, with concomitant decline of the GM-CFU content in the bone marrow, which was attributed to intestinal irritation by rough zeolite particles. The mechanically treated clinoptilolite preparation caused similar, albeit less pronounced, changes. In a limited experiment, mice having transplanted mammary carcinoma in the terminal stage showed increased potassium and decreased sodium and chloride levels, severe anemia and leukocytosis, decreased bone marrow cellularity and diminished content of hematopoietic progenitor cells in the marrow. The clinoptilolite preparations ameliorated the sodium and chloride decline, whereas the effects on hematopoiesis were erratic.

  4. Effect of aluminosilicates and bentonite on aflatoxin-induced developmental toxicity in rat.

    PubMed

    Abdel-Wahhab, M A; Nada, S A; Amra, H A

    1999-01-01

    Numerous studies have established that aflatoxin is a potent developmental toxin in animals. Previous research has demonstrated that a phyllosilicate clay, hydrated sodium calcium aluminosilicate (HSCAS or Novasil), tightly binds and immobilizes aflatoxins in the gastrointestinal tract of animals and markedly reduces the bioavailability and toxicity of aflatoxin. Our objective in this study was to utilize the pregnant rat as an in vivo model to compare the potential of HSCAS and bentonite to prevent the developmental toxicity of aflatoxin. Aluminosilicates (HSCAS) and bentonite were added to the diet at a level of 0.5% (w/w) and fed to the pregnant rat throughout pregnancy (i.e. days 0-20). Test animals were fed an aflatoxin-contaminated diet (2.5 mg kg(-1) diet) with or without sorbents during gestation days 6-15. Evaluations of toxicity were performed on day 20. These included maternal (mortality, body weights, feed intake and litter weights), developmental (embryonic resorptions and fetal body weights) and biochemical (ALT, AST and AP) evaluations. Sorbents alone were not toxic and aflatoxin alone resulted in significant maternal and developmental toxicity. Animals treated with phyllosilicate (plus aflatoxin) were comparable to controls following evaluations for resorptions, live fetuses and fetal body weights, as well as biochemical parameters. While bentonite plus aflatoxin resulted in significant reduction in fetal body weight, none of the fetuses from HSCAS or bentonite plus aflatoxin-treated groups had any gross, internal soft tissue or major skeletal malformations.

  5. Fate of Uranium during Sodium Aluminosilicate Formation under Waste Tank Conditions

    SciTech Connect

    Wilmarth, B

    2005-06-22

    Experiments have been conducted to examine the fate of uranium during the formation of sodium aluminosilicate (NAS) when wastes containing high aluminate concentrations are mixed with wastes of high silicate concentration. Testing was conducted at varying degrees of uranium saturation. Testing examined typical tank conditions, e.g., stagnant, slightly elevated temperature (50 C). The results showed that under sub-saturated conditions uranium is not removed from solution to any large extent in both simulant testing and actual tank waste testing. There are data supporting a small removal due to sorption of uranium on sites in the NAS. Above the solubility limit the data are clear that a reduction in uranium concentration occurs with the formation of aluminosilicate. This uranium precipitation is fairly rapid and ceases when uranium reaches its solubility limit. At the solubility limit, it appears that uranium is not affected, but further testing might be warranted. Lastly, analysis of the uranium speciation in a Tank 49H set of samples showed the uranium to be soluble. Analysis of the solution composition and subsequent use of the Hobb's uranium solubility model indicated a uranium solubility limit of 32 mg/L. The measured value of uranium in the Tank 49H matched the model prediction.

  6. Cellular morphology of organic-inorganic hybrid foams based on alkali alumino-silicate matrix

    NASA Astrophysics Data System (ADS)

    Verdolotti, Letizia; Liguori, Barbara; Capasso, Ilaria; Caputo, Domenico; Lavorgna, Marino; Iannace, Salvatore

    2014-05-01

    Organic-inorganic hybrid foams based on an alkali alumino-silicate matrix were prepared by using different foaming methods. Initially, the synthesis of an inorganic matrix by using aluminosilicate particles, activated through a sodium silicate solution, was performed at room temperature. Subsequently the viscous paste was foamed by using three different methods. In the first method, gaseous hydrogen produced by the oxidization of Si powder in an alkaline media, was used as blowing agent to generate gas bubbles in the paste. In the second method, the porous structure was generated by mixing the paste with a "meringue" type of foam previously prepared by whipping, under vigorous stirring, a water solution containing vegetal proteins as surfactants. In the third method, a combination of these two methods was employed. The foamed systems were consolidated for 24 hours at 40°C and then characterized by FTIR, X-Ray diffraction, scanning electron microscopy (SEM) and compression tests. Low density foams (˜500 Kg/m3) with good cellular structure and mechanical properties were obtained by combining the "meringue" approach with the use of the chemical blowing agent based on Si.

  7. Aqueous dissolution, solubilities and thermodynamic stabilities of common aluminosilicate clay minerals: Kaolinite and smectites

    USGS Publications Warehouse

    May, Howard M.; Klnniburgh, D.G.; Helmke, P.A.; Jackson, M.L.

    1986-01-01

    Determinations of the aqueous solubilities of kaolinite at pH 4, and of five smectite minerals in suspensions set between pH 5 and 8, were undertaken with mineral suspensions adjusted to approach equilibrium from over- and undersaturation. After 1,237 days, Dry Branch, Georgia kaolinite suspensions attained equilibrium solubility with respect to the kaolinite, for which Keq = (2.72 ?? 0.35) ?? 107. The experimentally determined Gibbs free energy of formation (??Gf,2980) for the kaolinite is -3,789.51 ?? 6.60 kj mol-1. Equilibrium solubilities could not be determined for the smectites because the composition of the solution phase in the smectite suspensions appeared to be controlled by the formation of gibbsite or amorphous aluminum hydroxide and not by the smectites, preventing attempts to determine valid ??Gf0 values for these complex aluminosilicate clay minerals. Reported solubility-based ??Gf0 determinations for smectites and other variable composition aluminosilicate clay minerals are shown to be invalid because of experimental deficiencies and of conceptual flaws arising from the nature of the minerals themselves. Because of the variable composition of smectites and similar minerals, it is concluded that reliable equilibrium solubilities and solubility-derived ??Gf0 values can neither be rigorously determined by conventional experimental procedures, nor applied in equilibriabased models of smectite-water interactions. ?? 1986.

  8. White light emission from Sm3+/Tb3+ codoped oxyfluoride aluminosilicate glasses under UV light excitation

    NASA Astrophysics Data System (ADS)

    Lakshminarayana, G.; Yang, R.; Qiu, J. R.; Brik, M. G.; Kumar, G. A.; Kityk, I. V.

    2009-01-01

    In this paper, we report on the absorption and photoluminescence properties of oxyfluoride aluminosilicate and boro-aluminosilicate glasses codoped with Sm3+ and Tb3+ ions. The differential thermal analysis profiles of these glasses have been obtained to confirm their thermal stability. From the measured absorption spectrum, Judd-Ofelt (J-O) intensity parameters (Ω2, Ω4 and Ω6) have been evaluated for the Sm3+ ion. When excited by ultraviolet light these glasses emit a combination of blue, green and orange-red wavelengths forming white light. The ratio of the intensities of orange-red to green emissions can be tuned by varying both the concentration of the Sm3+ ion and the composition of the glass matrix. The excitation and emission spectra have shown a self-quenching effect for the Sm3+ ions and an efficient energy transfer from Tb3+ : 5D4 → Sm3+ : 4G5/2 was observed which was also confirmed by the decay lifetime measurements.

  9. 29Si NMR study of structural ordering in aluminosilicate geopolymer gels.

    PubMed

    Duxson, Peter; Provis, John L; Lukey, Grant C; Separovic, Frances; van Deventer, Jannie S J

    2005-03-29

    A systematic series of aluminosilicate geopolymer gels was synthesized and then analyzed using 29Si magic-angle spinning nuclear magnetic resonance (MAS NMR) in combination with Gaussian peak deconvolution to characterize the short-range ordering in terms of T-O-T bonds (where T is Al or Si). The effect of nominal Na2O/(Na2O + K2O) and Si/Al ratios on short-range network ordering was quantified by deconvolution of the 29Si MAS NMR spectra into individual Gaussian peaks representing different Q4(mAl) silicon centers. The deconvolution procedure developed in this work is applicable to other aluminosilicate gel systems. The short-range ordering observed here indicates that Loewenstein's Rule of perfect aluminum avoidance may not apply strictly to geopolymeric gels, although further analyses are required to quantify the degree of aluminum avoidance. Potassium geopolymers appeared to exhibit a more random Si/Al distribution compared to that of mixed-alkali and sodium systems. This work provides a quantitative account of the silicon and aluminum ordering in geopolymers, which is essential for extending our understanding of the mechanical strength, chemical and thermal stability, and fundamental structure of these systems.

  10. Amorphous and Ultradisperse Crystalline Materials,

    DTIC Science & Technology

    The book sums up experimental and theoretical findings on amorphous and ultradisperse crystalline materials , massive and film types. Present-day... crystalline materials of metallic systems are presented. Emphasis is placed on inorganic film materials.

  11. Catalytic reforming with improved zeolite catalysts

    SciTech Connect

    Chu, Y.F.

    1990-05-22

    This patent describes a method for reforming a naphtha. It comprises contacting the naphtha with a noble metal/alkali metal-containing zeolite naphtha reforming catalyst the catalyst containing from about 0.1--1.0 wt % of the noble metal and an amount of the alkali metal which exceeds the cationic exchange capacity of the zeolite, a pressure of from about 0 to about 2000 psig, a temperature of about 750{degrees} F. to about 1200{degrees} F., a hydrogen to hydrocarbon molar ratio of about 0.1 to 1 to about 15 to 1 and a weight hourly spaced velocity of about 0.5 to about 20, whereby naphtha reforming activity of the catalyst is enhanced by the zeolite resulting in significantly improved C{sub 4}{sup +} gasoline yields.

  12. Hydrogen Purification Using Natural Zeolite Membranes

    NASA Technical Reports Server (NTRS)

    DelValle, William

    2003-01-01

    The School of Science at Universidad del Turabo (UT) have a long-lasting investigation plan to study the hydrogen cleaning and purification technologies. We proposed a research project for the synthesis, phase analysis and porosity characterization of zeolite based ceramic perm-selective membranes for hydrogen cleaning to support NASA's commitment to achieving a broad-based research capability focusing on aerospace-related issues. The present study will focus on technology transfer by utilizing inorganic membranes for production of ultra-clean hydrogen for application in combustion. We tested three different natural zeolite membranes (different particle size at different temperatures and time of exposure). Our results show that the membranes exposured at 900 C for 1Hr has the most higher permeation capacity, indicated that our zeolite membranes has the capacity to permeate hydrogen.

  13. Synthesis of silver nanoclusters on zeolite substrates

    NASA Astrophysics Data System (ADS)

    Posada, Y.

    2009-06-01

    Silver nanoclusters were synthesized by reducing silver nitrate with ethylene glycol at 160 °C in the presence of zeolite. A one-pot procedure has rendered uniform size distributions of quasispherical silver clusters of average sizes of 100-200 nm synthesized on the surfaces of cubiclike zeolite substrates of ˜1 μm side. Bulk material microanalysis measurements showed samples with silver mass percentages of 20%-38%. Surface atomic composition analysis found silver concentrations of 3.1%-5.7%, zeolite compounds and nontraces of nitrogen were measured. The binding energy for the Ag 3d5/2 core electrons was shifted to higher energies at 368.6 eV compared to that of metallic silver. Herein, is presented a cost-effective technique for producing a narrow size distribution of silver nanocomposites with great potential for optoelectronics, catalysis, and nanobiotechnological applications.

  14. Photocatalytic activity of undoped and Ag-doped TiO{sub 2}-supported zeolite for humic acid degradation and mineralization

    SciTech Connect

    Lazau, C.; Ratiu, C.; Orha, C.; Pode, R.; Manea, F.

    2011-11-15

    Highlights: {yields} Hybrid materials based on natural zeolite and TiO{sub 2} obtained by solid-state reaction. {yields} XRD proved the presence of anatase form of undoped and Ag-doped TiO{sub 2} onto zeolite. {yields} FT-IR spectra evidenced the presence on TiO{sub 2} bounded at the zeolite network. {yields} Ag-doped TiO{sub 2} onto zeolitic matrix exhibited an enhanced photocatalytic activity. -- Abstract: The hybrid materials based on natural zeolite and undoped and Ag-doped TiO{sub 2}, i.e., Z-Na-TiO{sub 2} and Z-Na-TiO{sub 2}-Ag, were successfully synthesized by solid-state reaction in microwave-assisted hydrothermal conditions. Undoped TiO{sub 2} and Ag-doped TiO{sub 2} nanocrystals were previously synthesized by sol-gel method. The surface characterization of undoped TiO{sub 2}/Ag-doped TiO{sub 2} and natural zeolite hybrid materials has been investigated by X-ray diffraction, DRUV-VIS spectroscopy, FT-IR spectroscopy, BET analysis, SEM microscopy and EDX analysis. The results indicated that anatase TiO{sub 2} is the dominant crystalline type as spherical form onto zeolitic matrix. The presence of Ag into Z-Na-TiO{sub 2}-Ag was confirmed by EDX analysis. The DRUV-VIS spectra showed that Z-Na-TiO{sub 2}-Ag exhibited absorption within the range of 400-500 nm in comparison with Z-Na-TiO{sub 2} catalyst. The enhanced photocatalytic activity of Z-Na-TiO{sub 2}-Ag catalyst is proved through the degradation and mineralization of humic acid under ultraviolet and visible irradiation.

  15. Liquid crystalline composites containing phyllosilicates

    DOEpatents

    Chaiko; David J.

    2007-05-08

    The present invention provides barrier films having reduced gas permeability for use in packaging and coating applications. The barrier films comprise an anisotropic liquid crystalline composite layer formed from phyllosilicate-polymer compositions. Phyllosilicate-polymer liquid crystalline compositions of the present invention can contain a high percentage of phyllosilicate while remaining transparent. Because of the ordering of the particles in the liquid crystalline composite, barrier films comprising liquid crystalline composites are particularly useful as barriers to gas transport.

  16. Binding and catalytic reduction of NO by transition metal aluminosilicates. Technical progress report, March 1992--May 1992

    SciTech Connect

    Klier, K.; Herman, R.G.; Hou, S.

    1992-06-01

    Na, Co{sup 2+}, Ce{sup 3+}, and Co{sup 2+}Ce{sup 3+} exchanged A type zeolite have been tested for NO and N{sub 2}O adsorption and decomposition at room temperature. Dynamic temperature programmed desorption (TPD) studies were also carried out with these four zeolites, as well as with CeO{sub 2} and CoA zeolite mixed with CeO{sub 2}. It was demonstrated that NO was especially decomposed into N{sub 2}, with some N{sub 2}, with some N{sub 2}O, over the doubly ion exchanged CoCeA zeolite that contained 1.77 Co and 2 Ce per unit cell. Some segregation of CeO{sub 2} occurred during these experiments, and a lower content of Ce in the CoCeA zeolite might be utilizable.

  17. Adsorption of CO2 by alginate immobilized zeolite beads

    NASA Astrophysics Data System (ADS)

    Suratman, A.; Kunarti, E. S.; Aprilita, N. H.; Pamurtya, I. C.

    2017-03-01

    Immobilized zeolit in alginate beads for adsorption of CO2 was developed. Alginate immobilized zeolit beads was generated by dropping the mixture of Na-alginate and zeolite solution into Ca2+ solution. The adsorption efficacy such as the influence of contact time, mass of zeolite, flowrate of CO2, and mass of adsorbent was evaluated. The adsorption of CO2 onto alginate immobilized zeolit beads was investigated by performing both equilibrium and kinetic batch test. Bead was characterized by FTIR and SEM. Alginate immobilized zeolit beads demonstrated significantly higher sorption efficacy compared to plain alginate beads and zeolite with 0.25 mmol CO2 adsorbed /g adsorbent. Optimum condition was achieved with mass composition of alginate:zeolite (3:1), flowrate 50 mL/min for 20 minutes. The alginate immobilized zeolit beads showed that adsorption of CO2 followed Freundlich isotherm and pseudo second order kinetic model. Adsorption of CO2 onto alginate immobilized zeolite beads is a physisorption with adsorption energy of 6.37 kJ/mol. This results indicates that the alginate immobilized zeolit beads can be used as promising adsorbents for CO2.

  18. Natural zeolite reactivity towards ozone: the role of compensating cations.

    PubMed

    Valdés, Héctor; Alejandro, Serguei; Zaror, Claudio A

    2012-08-15

    Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L(-1)). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH(3)-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal.

  19. Crystalline oxides on silicon.

    PubMed

    Reiner, James W; Kolpak, Alexie M; Segal, Yaron; Garrity, Kevin F; Ismail-Beigi, Sohrab; Ahn, Charles H; Walker, Fred J

    2010-07-20

    This review outlines developments in the growth of crystalline oxides on the ubiquitous silicon semiconductor platform. The overall goal of this endeavor is the integration of multifunctional complex oxides with advanced semiconductor technology. Oxide epitaxy in materials systems achieved through conventional deposition techniques is described first, followed by a description of the science and technology of using atomic layer-by-layer deposition with molecular beam epitaxy (MBE) to systematically construct the oxide-silicon interface. An interdisciplinary approach involving MBE, advanced real-space structural characterization, and first-principles theory has led to a detailed understanding of the process by which the interface between crystalline oxides and silicon forms, the resulting structure of the interface, and the link between structure and functionality. Potential applications in electronics and photonics are also discussed.

  20. Early age hydration and pozzolanic reaction in natural zeolite blended cements: Reaction kinetics and products by in situ synchrotron X-ray powder diffraction

    SciTech Connect

    Snellings, R.; Mertens, G.; Cizer, O.; Elsen, J.

    2010-12-15

    The in situ early-age hydration and pozzolanic reaction in cements blended with natural zeolites were investigated by time-resolved synchrotron X-ray powder diffraction with Rietveld quantitative phase analysis. Chabazite and Na-, K-, and Ca-exchanged clinoptilolite materials were mixed with Portland cement in a 3:7 weight ratio and hydrated in situ at 40 {sup o}C. The evolution of phase contents showed that the addition of natural zeolites accelerates the onset of C{sub 3}S hydration and precipitation of CH and AFt. Kinetic analysis of the consumption of C{sub 3}S indicates that the enveloping C-S-H layer is thinner and/or less dense in the presence of alkali-exchanged clinoptilolite pozzolans. The zeolite pozzolanic activity is interpreted to depend on the zeolite exchangeable cation content and on the crystallinity. The addition of natural zeolites alters the structural evolution of the C-S-H product. Longer silicate chains and a lower C/S ratio are deduced from the evolution of the C-S-H b-cell parameter.

  1. Studies of anions sorption on natural zeolites.

    PubMed

    Barczyk, K; Mozgawa, W; Król, M

    2014-12-10

    This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method.

  2. Crystalline titanate catalyst supports

    DOEpatents

    Anthony, Rayford G.; Dosch, Robert G.

    1993-01-01

    A series of new crystalline titanates (CT) are shown to have considerable potential as catalyst supports. For Pd supported catalyst, the catalytic activity for pyrene hydrogenation was substantially different depending on the type of CT, and one was substantially more active than Pd on hydrous titanium oxide (HTO). For 1-hexene hydrogenation the activities of the new CTs were approximately the same as for the hydrous metal oxide supports.

  3. Liquid Crystalline Polymers

    DTIC Science & Technology

    1990-02-28

    Liquid crystalline polymers (LCPs); fibers ; thermotropic; lyotropic; processing; rheology; nonlinear optical (4L-" properties* blends* Q2 P- USTRACT...CowMnue on reverse if , cevwy and identify by block number) The remarkable mechanical properties and thermal stability of fibers fabricated from liquid...control of orientation falls short of allowing manipula- tion of macroscopic orientation (except for the case of uniaxial fibers ). This report

  4. Crystalline titanate catalyst supports

    DOEpatents

    Anthony, R.G.; Dosch, R.G.

    1993-01-05

    A series of new crystalline titanates (CT) are shown to have considerable potential as catalyst supports. For Pd supported catalyst, the catalytic activity for pyrene hydrogenation was substantially different depending on the type of CT, and one was substantially more active than Pd on hydrous titanium oxide (HTO). For 1-hexene hydrogenation the activities of the new CTs were approximately the same as for the hydrous metal oxide supports.

  5. CRYSTALLINE SOYBEAN TRYPSIN INHIBITOR

    PubMed Central

    Kunitz, M.

    1947-01-01

    A study has been made of the general properties of crystalline soybean trypsin inhibitor. The soy inhibitor is a stable protein of the globulin type of a molecular weight of about 24,000. Its isoelectric point is at pH 4.5. It inhibits the proteolytic action approximately of an equal weight of crystalline trypsin by combining with trypsin to form a stable compound. Chymotrypsin is only slightly inhibited by soy inhibitor. The reaction between chymotrypsin and the soy inhibitor consists in the formation of a reversibly dissociable compound. The inhibitor has no effect on pepsin. The inhibiting action of the soybean inhibitor is associated with the native state of the protein molecule. Denaturation of the soy protein by heat or acid or alkali brings about a proportional decrease in its inhibiting action on trypsin. Reversal of denaturation results in a proportional gain in the inhibiting activity. Crystalline soy protein when denatured is readily digestible by pepsin, and less readily by chymotrypsin and by trypsin. Methods are given for measuring trypsin and inhibitor activity and also protein concentration with the aid of spectrophotometric density measurements at 280 mµ. PMID:19873496

  6. One-pot synthesis of MWW zeolite nanosheets using a rationally designed organic structure-directing agent

    PubMed Central

    Luo, Helen Y.; Michaelis, Vladimir K.; Hodges, Sydney; Griffin, Robert G.

    2015-01-01

    A new material MIT-1 comprised of delaminated MWW zeolite nanosheets is synthesized in one-pot using a rationally designed organic structure-directing agent (OSDA). The OSDA is comprised of a hydrophilic head segment that resembles the OSDA used to synthesize the zeolite precursor MCM22(P), a hydrophobic tail segment that resembles the swelling agent used to swell MCM22(P), and a di-quaternary ammonium linker that connects both segments. MIT-1 features high crystallinity and surface areas exceeding 500 m2g−1, and can be synthesized over a wide synthesis window that includes Si/Al ratios ranging from 13 to 67. Characterization data reveal high mesoporosity and acid strength with no detectable amorphous silica phases. Compared to MCM-22 and MCM-56, MIT-1 shows a three-fold increase in catalytic activity for the Friedel-Crafts alkylation of benzene with benzyl alcohol. PMID:26478803

  7. One-pot synthesis of MWW zeolite nanosheets using a rationally designed organic structure-directing agent

    SciTech Connect

    Luo, Helen Y.; Michaelis, Vladimir K.; Hodges, Sydney; Griffin, Robert G.; Roman-Leshkov, Yuriy

    2015-07-22

    A new material MIT-1 comprised of delaminated MWW zeolite nanosheets is synthesized in one-pot using a rationally designed organic structure-directing agent (OSDA). The OSDA is comprised of a hydrophilic head segment that resembles the OSDA used to synthesize the zeolite precursor MCM22(P), a hydrophobic tail segment that resembles the swelling agent used to swell MCM22(P), and a di-quaternary ammonium linker that connects both segments. MIT-1 features high crystallinity and surface areas exceeding 500 m2g-1, and can be synthesized over a wide synthesis window that includes Si/Al ratios ranging from 13 to 67. Characterization data reveal high mesoporosity and acid strength with no detectable amorphous silica phases. In conclusion, compared to MCM-22 and MCM-56, MIT-1 shows a three-fold increase in catalytic activity for the Friedel-Crafts alkylation of benzene with benzyl alcohol.

  8. One-pot synthesis of MWW zeolite nanosheets using a rationally designed organic structure-directing agent

    DOE PAGES

    Luo, Helen Y.; Michaelis, Vladimir K.; Hodges, Sydney; ...

    2015-07-22

    A new material MIT-1 comprised of delaminated MWW zeolite nanosheets is synthesized in one-pot using a rationally designed organic structure-directing agent (OSDA). The OSDA is comprised of a hydrophilic head segment that resembles the OSDA used to synthesize the zeolite precursor MCM22(P), a hydrophobic tail segment that resembles the swelling agent used to swell MCM22(P), and a di-quaternary ammonium linker that connects both segments. MIT-1 features high crystallinity and surface areas exceeding 500 m2g-1, and can be synthesized over a wide synthesis window that includes Si/Al ratios ranging from 13 to 67. Characterization data reveal high mesoporosity and acid strengthmore » with no detectable amorphous silica phases. In conclusion, compared to MCM-22 and MCM-56, MIT-1 shows a three-fold increase in catalytic activity for the Friedel-Crafts alkylation of benzene with benzyl alcohol.« less

  9. Catalytic Fast Pyrolysis of Cellulose Using Nano Zeolite and Zeolite/Matrix Catalysts in a GC/Micro-Pyrolyzer.

    PubMed

    Lee, Kyong-Hwan

    2016-05-01

    Cellulose, as a model compound of biomass, was catalyzed over zeolite (HY,.HZSM-5) and zeolite/matrix (HY/Clay, HM/Clay) in a GC/micro-pyrolyzer at 500 degrees C, to produce the valuable products. The catalysts used were pure zeolite and zeolite/matrix including 20 wt% matrix content, which were prepared into different particle sizes (average size; 0.1 mm, 1.6 mm) to study the effect of the particle size of the catalyst for the distribution of product yields. Catalytic pyrolysis had much more volatile products as light components and less content of sugars than pyrolysis only. This phenomenon was strongly influenced by the particle size of the catalyst in catalytic fast pyrolysis. Also, in zeolite and zeolite/matrix catalysts the zeolite type gave the dominant impact on the distribution of product yields.

  10. Preparation and characterization of cesium-137 aluminosilicate pellets for radioactive source applications

    SciTech Connect

    Schultz, F.J.; Tompkins, J.A.; Haff, K.W.; Case, F.N.

    1981-07-01

    Twenty-seven fully loaded /sup 137/Cs aluminosilicate pellets were fabricated in a hot cell by the vacuum hot pressing of a cesium carbonate/montmorillonite clay mixture at 1500/sup 0/C and 570 psig. Four pellets were selected for characterization studies which included calorimetric measurements, metallography, scanning electron microscope and electron backscattering (SEM-BSE), electron microprobe, x-ray diffraction, and cesium ion leachability measurements. Each test pellet contained 437 to 450 curies of /sup 137/Cs as determined by calorimetric measurements. Metallographic examinations revealed a two-phase system: a primary, granular, gray matrix phase containing large and small pores and small pore agglomerations, and a secondary fused phase interspersed throughout the gray matrix. SEM-BSE analyses showed that cesium and silicon were uniformly distributed throughout both phases of the pellet. This indicated that the cesium-silicon-clay reaction went to completion. Aluminum homogeneity was unconfirmed due to the high background noise associated with the inherent radioactivity of the test specimens. X-ray diffraction analyses of both radioactive and non-radioactive aluminosilicate pellets confirmed the crystal lattice structure to be pollucite. Cesium ion quasistatic leachability measurements determined the leach rates of fully loaded /sup 137/Cs sectioned pollucite pellets to date to be 4.61 to 34.4 x 10/sup -10/ kg m/sup -2/s/sup -1/, while static leach tests performed on unsectioned fully loaded pellets showed the leach rates of the cesium ion to date to be 2.25 to 3.41 x 10/sup -12/ kg m/sup -2/s/sup -1/. The cesium ion diffusion coefficients through the pollucite pellet were calculated using Fick's first and second laws of diffusion. The diffusion coefficients calculated for three tracer level /sup 137/Cs aluminosilicate pellets were 1.29 x 10/sup -16/m/sup 2/s/sup -1/, 6.88 x 10/sup -17/m/sup 2/s/sup -1/, and 1.35 x 10/sup -17/m/sup 2/s/sup -1/, respectively.

  11. Characteristic of fly ash derived-zeolite and its catalytic performance for fast pyrolysis of Jatropha waste.

    PubMed

    Vichaphund, S; Aht-Ong, D; Sricharoenchaikul, V; Atong, D

    2014-01-01

    Fly ash from pulp and paper industries was used as a raw material for synthesizing zeolite catalyst. Main compositions of fly ash consisted of 41 wt%SiO2, 20 wt%Al2O3, 14 wt%CaO, and 8 wt% Fe2O3. High content of silica and alumina indicated that this fly ash has potential uses for zeolite synthesis. Fly ash was mixed with 1-3 M NaOH solution. Sodium silicate acting as silica source was added into the solution to obtain the initial SiO2/Al2O3 molar ratio of 23.9. The mixtures were then crystallized at 160 degrees C for 24 and 72 h. Zeolites synthesized after a long synthesis time of 72 h showed superior properties in terms of high crystallinity, less impurity, and small particle size. The catalytic activities of fly ash-derived zeolites were investigated via fast pyrolysis of Jatropha wastes using analytical pyrolysis-gas chromatograph/mass spectrometer (GC/MS). Pyrolysis temperature was set at 500 degrees C with Jatropha wastes to catalyst ratio of 1:1, 1:5, and 1:10. Results showed that higher amounts of catalyst have a positive effect on enhancing aromatic hydrocarbons as well as decreasing in the oxygenated and N-containing compounds. Zeolite Socony Mobil-5 (ZSM-5) treated with 3 M NaOH at 72 h showed the highest hydrocarbon yield of 97.4%. The formation of hydrocarbon led to the high heating value of bio-oils. In addition, the presence of ZSM-5 derived from fly ash contributed to reduce the undesirable oxygenated compounds such as aldehydes, acids, and ketones which cause poor quality of bio-oil to only 0.8% while suppressed N-compounds to 1.7%. Overall, the ZSM-5 synthesized from fly ash proved to be an effective catalyst for catalytic fast pyrolysis application.

  12. Reduction of nitrogen oxides with catalytic acid resistant aluminosilicate molecular sieves and ammonia

    DOEpatents

    Pence, Dallas T.; Thomas, Thomas R.

    1980-01-01

    Noxious nitrogen oxides in a waste gas stream such as the stack gas from a fossil-fuel-fired power generation plant or other industrial plant off-gas stream is catalytically reduced to elemental nitrogen and/or innocuous nitrogen oxides employing ammonia as reductant in the presence of a zeolite catalyst in the hydrogen or sodium form having pore openings of about 3 to 10 A.

  13. Zeolite 5A Catalyzed Etherification of Diphenylmethanol

    ERIC Educational Resources Information Center

    Cooke, Jason; Henderson, Eric J.; Lightbody, Owen C.

    2009-01-01

    An experiment for the synthetic undergraduate laboratory is described in which zeolite 5A catalyzes the room temperature dehydration of diphenylmethanol, (C[subscript 6]H[subscript 5])[subscript 2]CHOH, producing 1,1,1',1'-tetraphenyldimethyl ether, (C[subscript 6]H[subscript 5])[subscript 2]CHOCH(C[subscript 6]H[subscript 5])[subscript 2]. The…

  14. MERCURY SEPARATION FROM POLLUTANT WATER USING ZEOLITES

    EPA Science Inventory

    Arsenic is known to be a hazardous contaminant in drinking water that causes arsenical dermatitis and skin cancer. In the present work, the potential use of a variety of synthetic zeolites for removal of arsenic from water has been examined at room temperature. Experiments have...

  15. ARSENIC SEPARATION FROM WATER USING ZEOLITES

    EPA Science Inventory

    Arsenic is known to be a hazardous contaminant in drinking water. The presence of arsenic in water supplies has been linked to arsenical dermatosis and skin cancer . Zeolites are well known for their ion exchange capacities. In the present work, the potential use of a variety of ...

  16. Multicomponent liquid ion exchange with chabazite zeolites

    SciTech Connect

    Robinson, S.M.; Arnold, W.D. Jr.; Byers, C.W.

    1993-10-01

    In spite of the increasing commercial use of zeolites for binary and multicomponent sorption, the understanding of the basic mass-transfer processes associated with multicomponent zeolite ion-exchange systems is quite limited. This study was undertaken to evaluate Na-Ca-Mg-Cs-Sr ion exchange from an aqueous solution using a chabazite zeolite. Mass-transfer coefficients and equilibrium equations were determined from experimental batch-reactor data for single and multicomponent systems. The Langmuir isotherm was used to represent the equilibrium relationship for binary systems, and a modified Dubinin-Polyani model was used for the multicomponent systems. The experimental data indicate that diffusion through the microporous zeolite crystals is the primary diffusional resistance. Macropore diffusion also significantly contributes to the mass-transfer resistance. Various mass-transfer models were compared to the experimental data to determine mass-transfer coefficients. Effective diffusivities were obtained which accurately predicted experimental data using a variety of models. Only the model which accounts for micropore and macropore diffusion occurring in series accurately predicted multicomponent data using single-component diffusivities. Liquid and surface diffusion both contribute to macropore diffusion. Surface and micropore diffusivities were determined to be concentration dependent.

  17. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, W.M.H.; Tzou, M.S.; Jiang, H.J.

    1987-03-31

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  18. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, Wolfgang M. H.; Tzou, Ming-Shin; Jiang, Hui-Jong

    1987-01-01

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  19. Framework Al zoning in zeolite ECR-1.

    PubMed

    Shin, Jiho; Ahn, Nak Ho; Cho, Sung June; Ren, Limin; Xiao, Feng-Shou; Hong, Suk Bong

    2014-02-25

    Rietveld analyses of the synchrotron X-ray diffraction data for various cation forms of zeolite ECR-1 have demonstrated framework Al zoning, which parallels the alternation of Al-rich maz and Al-poor mor layers. This can be further supported by notable differences in the average bond valence of its 10 crystallographically distinct tetrahedral sites.

  20. The Determination of Zeolite Sorption Properties

    NASA Astrophysics Data System (ADS)

    Tishin, A. A.; Laguntsov, N. I.; Kurchatov, I. M.

    The installation and the measurement data procedure were established for the sorbent characteristics determination. Sorption isotherms of the three gases (nitrogen, oxygen and carbon dioxide) are obtained on the industrial zeolites NaX, NaX-BKO and NaA in a pressure range (0;7) bar.

  1. Silver clusters and chemistry in zeolites

    SciTech Connect

    Sun, T.; Seff, K. . Dept. of Chemistry)

    1994-06-01

    The spectroscopic work done on silver clusters trapped in solid noble gas matrices at low temperature has been extensively reviewed by Ozin, and Henglein has done the same for photochemical studies of colloidal silver particles in solution. This article will review the chemistry of silver in zeolite hosts, including the synthesis and structures of silver clusters. 127 refs.

  2. Enhanced chromium adsorption capacity via plasma modification of natural zeolites

    NASA Astrophysics Data System (ADS)

    Cagomoc, Charisse Marie D.; Vasquez, Magdaleno R., Jr.

    2017-01-01

    Natural zeolites such as mordenite are excellent adsorbents for heavy metals. To enhance the adsorption capacity of zeolite, sodium-exchanged samples were irradiated with 13.56 MHz capacitively coupled radio frequency (RF) argon gas discharge. Hexavalent chromium [Cr(VI)] was used as the test heavy metal. Pristine and plasma-treated zeolite samples were soaked in 50 mg/L Cr solution and the amount of adsorbed Cr(VI) on the zeolites was calculated at predetermined time intervals. Compared with untreated zeolite samples, initial Cr(VI) uptake was 70% higher for plasma-treated zeolite granules (50 W 30 min) after 1 h of soaking. After 24 h, all plasma-treated zeolites showed increased Cr(VI) uptake. For a 2- to 4-month period, Cr(VI) uptake increased about 130% compared with untreated zeolite granules. X-ray diffraction analyses between untreated and treated zeolite samples revealed no major difference in terms of its crystal structure. However, for plasma-treated samples, an increase in the number of surface defects was observed from scanning electron microscopy images. This increase in the number of surface defects induced by plasma exposure played a crucial role in increasing the number of active sorption sites on the zeolite surface.

  3. Conversion of Ethanol to Hydrocarbons on Hierarchical HZSM-5 Zeolites

    SciTech Connect

    Ramasamy, Karthikeyan K.; Zhang, He; Sun, Junming; Wang, Yong

    2014-02-22

    This study reports synthesis, characterization, and catalytic activity of the nano-size hierarchical HZSM-5 zeolite with high mesoporosity produced via a solvent evaporation procedure. Further, this study compares hierarchical zeolites with conventional HZSM-5 zeolite with similar Si/Al ratios for the ethanol-to-hydrocarbon conversion process. The catalytic performance of the hierarchical and conventional zeolites was evaluated using a fixed-bed reactor at 360 °C, 300 psig, and a weight hourly space velocity of 7.9 h-1. For the low Si/Al ratio zeolite (~40), the catalytic life-time for the hierarchical HZSM-5 was approximately 2 times greater than the conventional HZSM-5 despite its coking amount deposited 1.6 times higher than conventional HZSM-5. For the high Si/Al ratio zeolite (~140), the catalytic life-time for the hierarchical zeolite was approximately 5 times greater than the conventional zeolite and the amount of coking deposited was 2.1 times higher. Correlation was observed between catalyst life time, porosity, and the crystal size of the zeolite. The nano-size hierarchical HZSM-5 zeolites containing mesoporosity demonstrated improved catalyst life-time compared to the conventional catalyst due to faster removal of products, shorter diffusion path length, and the migration of the coke deposits to the external surface from the pore structure.

  4. Energetics of sodium-calcium exchanged zeolite A.

    PubMed

    Sun, H; Wu, D; Guo, X; Shen, B; Navrotsky, A

    2015-05-07

    A series of calcium-exchanged zeolite A samples with different degrees of exchange were prepared. They were characterized by powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC). High temperature oxide melt drop solution calorimetry measured the formation enthalpies of hydrated zeolites CaNa-A from constituent oxides. The water content is a linear function of the degree of exchange, ranging from 20.54% for Na-A to 23.77% for 97.9% CaNa-A. The enthalpies of formation (from oxides) at 25 °C are -74.50 ± 1.21 kJ mol(-1) TO2 for hydrated zeolite Na-A and -30.79 ± 1.64 kJ mol(-1) TO2 for hydrated zeolite 97.9% CaNa-A. Dehydration enthalpies obtained from differential scanning calorimetry are 32.0 kJ mol(-1) H2O for hydrated zeolite Na-A and 20.5 kJ mol(-1) H2O for hydrated zeolite 97.9% CaNa-A. Enthalpies of formation of Ca-exchanged zeolites A are less exothermic than for zeolite Na-A. A linear relationship between the formation enthalpy and the extent of calcium substitution was observed. The energetic effect of Ca-exchange on zeolite A is discussed with an emphasis on the complex interactions between the zeolite framework, cations, and water.

  5. Zeolite Nanoparticles for Selective Sorption of Plasma Proteins

    PubMed Central

    Rahimi, M.; Ng, E.-P.; Bakhtiari, K.; Vinciguerra, M.; Ahmad, H. Ali; Awala, H.; Mintova, S.; Daghighi, M.; Bakhshandeh Rostami, F.; de Vries, M.; Motazacker, M. M.; Peppelenbosch, M. P.; Mahmoudi, M.; Rezaee, F.

    2015-01-01

    The affinity of zeolite nanoparticles (diameter of 8–12 nm) possessing high surface area and high pore volume towards human plasma proteins has been investigated. The protein composition (corona) of zeolite nanoparticles has been shown to be more dependent on the plasma protein concentrations and the type of zeolites than zeolite nanoparticles concentration. The number of proteins present in the corona of zeolite nanoparticles at 100% plasma (in vivo state) is less than with 10% plasma exposure. This could be due to a competition between the proteins to occupy the corona of the zeolite nanoparticles. Moreover, a high selective adsorption for apolipoprotein C-III (APOC-III) and fibrinogen on the zeolite nanoparticles at high plasma concentration (100%) was observed. While the zeolite nanoparticles exposed to low plasma concentration (10%) exhibited a high selective adsorption for immunoglobulin gamma (i.e. IGHG1, IGHG2 and IGHG4) proteins. The zeolite nanoparticles can potentially be used for selectively capture of APOC-III in order to reduce the activation of lipoprotein lipase inhibition during hypertriglyceridemia treatment. The zeolite nanoparticles can be adapted to hemophilic patients (hemophilia A (F-VIII deficient) and hemophilia B (F-IX deficient)) with a risk of bleeding, and thus might be potentially used in combination with the existing therapy. PMID:26616161

  6. Zeolite Nanoparticles for Selective Sorption of Plasma Proteins.

    PubMed

    Rahimi, M; Ng, E-P; Bakhtiari, K; Vinciguerra, M; Ali Ahmad, H; Awala, H; Mintova, S; Daghighi, M; Bakhshandeh Rostami, F; de Vries, M; Motazacker, M M; Peppelenbosch, M P; Mahmoudi, M; Rezaee, F

    2015-11-30

    The affinity of zeolite nanoparticles (diameter of 8-12 nm) possessing high surface area and high pore volume towards human plasma proteins has been investigated. The protein composition (corona) of zeolite nanoparticles has been shown to be more dependent on the plasma protein concentrations and the type of zeolites than zeolite nanoparticles concentration. The number of proteins present in the corona of zeolite nanoparticles at 100% plasma (in vivo state) is less than with 10% plasma exposure. This could be due to a competition between the proteins to occupy the corona of the zeolite nanoparticles. Moreover, a high selective adsorption for apolipoprotein C-III (APOC-III) and fibrinogen on the zeolite nanoparticles at high plasma concentration (100%) was observed. While the zeolite nanoparticles exposed to low plasma concentration (10%) exhibited a high selective adsorption for immunoglobulin gamma (i.e. IGHG1, IGHG2 and IGHG4) proteins. The zeolite nanoparticles can potentially be used for selectively capture of APOC-III in order to reduce the activation of lipoprotein lipase inhibition during hypertriglyceridemia treatment. The zeolite nanoparticles can be adapted to hemophilic patients (hemophilia A (F-VIII deficient) and hemophilia B (F-IX deficient)) with a risk of bleeding, and thus might be potentially used in combination with the existing therapy.

  7. Zeolite Nanoparticles for Selective Sorption of Plasma Proteins

    NASA Astrophysics Data System (ADS)

    Rahimi, M.; Ng, E.-P.; Bakhtiari, K.; Vinciguerra, M.; Ahmad, H. Ali; Awala, H.; Mintova, S.; Daghighi, M.; Bakhshandeh Rostami, F.; de Vries, M.; Motazacker, M. M.; Peppelenbosch, M. P.; Mahmoudi, M.; Rezaee, F.

    2015-11-01

    The affinity of zeolite nanoparticles (diameter of 8-12 nm) possessing high surface area and high pore volume towards human plasma proteins has been investigated. The protein composition (corona) of zeolite nanoparticles has been shown to be more dependent on the plasma protein concentrations and the type of zeolites than zeolite nanoparticles concentration. The number of proteins present in the corona of zeolite nanoparticles at 100% plasma (in vivo state) is less than with 10% plasma exposure. This could be due to a competition between the proteins to occupy the corona of the zeolite nanoparticles. Moreover, a high selective adsorption for apolipoprotein C-III (APOC-III) and fibrinogen on the zeolite nanoparticles at high plasma concentration (100%) was observed. While the zeolite nanoparticles exposed to low plasma concentration (10%) exhibited a high selective adsorption for immunoglobulin gamma (i.e. IGHG1, IGHG2 and IGHG4) proteins. The zeolite nanoparticles can potentially be used for selectively capture of APOC-III in order to reduce the activation of lipoprotein lipase inhibition during hypertriglyceridemia treatment. The zeolite nanoparticles can be adapted to hemophilic patients (hemophilia A (F-VIII deficient) and hemophilia B (F-IX deficient)) with a risk of bleeding, and thus might be potentially used in combination with the existing therapy.

  8. UTILITY OF ZEOLITES IN REMOVAL OF INORGANIC AND ORGANIC WATER POLLUTANTS

    EPA Science Inventory

    Zeolites are well known for their ion exchange, adsorption and acid catalysis properties. Different inorganic and organic pollutants have been removed from water at room temperature using various zeolites. Synthetic zeolite Faujasite Y has been used to remove inorganic pollutants...

  9. Composites of Polyindole nanowires within Silicate and Aluminosilicate hosts with distinct conductive properties

    NASA Astrophysics Data System (ADS)

    Juárez, J. M.; Gómez Costa, M. B.; Anunziata, O. A.

    2016-07-01

    Nanostructured silicate SBA-15 and aluminosilicate AlSBA-15 were synthesized in order to prepare polyindole composites. The Silica mesoporous materials were prepared by sol- gel method and alumination using post-synthesis technique and analysed by different methods (XRD, BET, TEM, and FTIR). Polyindole/host composites were prepared by in situ oxidative polymerization of pre-adsorbed indole, employing Cl3Fe as oxidant. TG, FTIR, BET, XRD, SEM and TEM were used to characterize the resulting composites. These studies show that the porous structures of the materials are preserved after polymerization, and polyindole is found within the porous channels. The composites have an electrical conductivity range between values higher than those of the pure chemically synthesized polyindole, close to those of the pure electrochemically synthesized polymer and lower than those of the pure chemically synthesized polymer, in the order of 10-8 S/cm.

  10. Synthesis and characterization of inorganic polymers from the alkali activation of an aluminosilicate

    NASA Astrophysics Data System (ADS)

    González, C. P.; Montaño, A. M.; González, A. K.; Ríos, C. A.

    2014-06-01

    This paper presents the results of the synthesis and characterization of inorganic polymers (IP) from aluminosilicates: bentonite (BT) and pumice (PP). The synthesis of IP, was carried out by two methods involving alkaline activation, at room temperature and 80 ± 5 °C, using as activating agent sodium silicate both commercial and analytical (Na2SiO3). Sodium hydroxide (NaOH) at 3 M, 7 M and 12 M was added. A lower degree of polymerization was obtained by using analytical precursors subjected to room temperature and 80 ± 5°C. Replacement of heating by the use of the commercial activating agent with greater alkalinity allows the formation of a 3D network. The materials were structurally characterized by FTIR spectroscopy with Attenuated Reflectance (ATR), Scanning Electron Microscope (SEM) and X -ray diffraction (DRX).

  11. Tailoring of Boehmite-Derived Aluminosilicate Aerogel Structure and Properties: Influence of Ti Addition

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.; Guo, Haiquan; Sheets, Erik J.; Miller, Derek R.; Newlin, Katy N.

    2010-01-01

    Aluminosilicate aerogels offer potential for extremely low thermal conductivities at temperatures greater than 900 C, beyond where silica aerogels reach their upper temperature limits. Aerogels have been synthesized at various Al:Si ratios, including mullite compositions, using Boehmite (AlOOH) as the Al source, and tetraethoxy orthosilicate as the Si precursor. The Boehmite-derived aerogels are found to form by a self-assembly process of AlOOH crystallites, with Si-O groups on the surface of an alumina skeleton. Morphology, surface area and pore size varies with the crystallite size of the starting Boehmite powder, as well as with synthesis parameters. Ternary systems, including Al-Si-Ti aerogels incorporating a soluble Ti precursor, are possible with careful control of pH. The addition of Ti influences sol viscosity, gelation time pore structure and pore size distribution, as well as phase formation on heat treatment.

  12. Room temperature tensile and fatigue properties of silicon carbide fiber-reinforced aluminosilicate glass

    SciTech Connect

    Zawada, L.P.; Butkus, L.M.; Hartman, G.A.

    1990-10-01

    Matrix-microcracking has been identified as an indicator of the onset of damage accumulation in ceramic matrix composites. Stress levels required to produce microcracking in unidirectional and cross-ply laminates of Nicalon-reinforced aluminosilicate glass were determined during monotonic tension testing. Specimens were then tested in tension-tension fatigue (R = 0.1) at stress levels ranging up to 250 percent of the matrix microcracking stress level. At high stress levels, the unidirectional specimens exhibited a sharp decrease in elastic modulus during the first 10,000 cycles, after which the modulus remained relatively constant until run-out occurred at a million cycles. Similar results were obtained from tests conducted on the cross-ply specimens. It is shown that for this material the fatigue life-limiting stress can be associated with the inelastic stress-strain behavior of those plies having fibers running parallel with the loading axis. 6 refs.

  13. Fictive temperature-independent density and minimum indentation size effect in calcium aluminosilicate glass

    SciTech Connect

    Gross, T. M.; Tomozawa, M.

    2008-09-15

    Using the calcium aluminosilicate system a glass was developed that exhibits fictive temperature-independent density by creating an intermediate glass between normal and anomalous glasses. Normal glass, such as soda-lime silicate glass, exhibits decreasing density with increasing fictive temperature while anomalous glass, such as silica glass, exhibits increasing density with increasing fictive temperature. This intermediate glass composition was found to exhibit the minimum indentation size effect during indentation hardness testing. It appears that the indentation size effect is correlated with a deformation-induced fictive temperature increase, which is accompanied by a density change and hardness change in the vicinity of the indentation. It is suggested from these observations that indentation size effect originates from the energy required to create interfaces and defects such as shear bands, subsurface cracks, and point defects near the indenter-specimen boundary, which accompany the volume change.

  14. Structural and dynamic properties of calcium aluminosilicate melts: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Bouhadja, M.; Jakse, N.; Pasturel, A.

    2013-06-01

    The structural and dynamic properties of calcium aluminosilicate (CaO-Al2O3)1-x(SiO2)x melts with low silica content, namely, along the concentration ratio R = 1 are studied by classical molecular dynamics. An empirical potential has been developed here on the basis of our previous ab initio molecular dynamics. The new potential gives a description of the structural as well as the dynamics with a good accuracy. The self-intermediate scattering function and associated α-relaxation times are analyzed within the mode-coupling theory. Our results indicate a decrease of the fragility whose structural origin is a reduction of the number of fivefold coordinated Al atoms and non-bridging oxygen.

  15. Crystallization, Microstructure, and Viscosity Evolutions in Lithium Aluminosilicate Glass-Ceramics

    NASA Astrophysics Data System (ADS)

    Fu, Qiang; Wheaton, Bryan; Geisinger, Karen; Credle, Allen; Wang, Jie

    2016-11-01

    Lithium aluminosilicate glass-ceramics have found widespread commercial success in areas such as consumer products, telescope mirrors, fireplace windows, etc. However, there is still much to learn regarding the fundamental mechanisms of crystallization, especially related to the evolution of viscosity as a function of the crystallization (ceramming) process. In this study, the impact of phase assemblage and microstructure on the viscosity was investigated using high temperature X-ray diffraction (HTXRD), beam bending viscometry (BBV), and transmission electron microscopy (TEM). Results from this study provide a first direct observation of viscosity evolution as a function of ceramming time and temperature. Sharp viscosity increases due to phase separation, nucleation and phase transformation are noticed through BBV measurement. A near-net shape ceramming can be achieved in TiO2-containing compositions by keeping the glass at a high viscosity (> 109 Pa.s) throughout the whole thermal treatment.

  16. A facile strategy to recycle template P123 from mesoporous aluminosilicates by ultrasonic extraction.

    PubMed

    Jin, Jun-su; Cao, Li; Su, Guang-xun; Xu, Chun-yan; Zhang, Ze-ting; Gao, Xiong-hou; Liu, Hong-hai; Liu, Hong-tao

    2014-09-01

    High synthesis cost of mesoporous aluminosilicates (MA) limits their practical application. Recycling of copolymer template employed in preparation of MA is an effective way to reduce the synthesis cost. An ultrasonic extraction strategy for recycling of organic template P123 in MAs is reported. Effects of different extraction parameters on P123 recovery are investigated and the optimum conditions are obtained. 75.0% P123 is recovered from MAs within 10 min by one-step ultrasonication. Characterizations indicated that the resulting P123-free MA (MA-U) exhibits excellent properties compared with that of calcined products. Moreover, recovered P123 can be employed to synthesize high hydrothermally stable MA. This investigation provides a facile strategy to recycle P123 from MA.

  17. Impact of ZnO on the structure of aluminosilicate glazes

    NASA Astrophysics Data System (ADS)

    Leśniak, M.; Partyka, J.; Sitarz, M.

    2016-12-01

    This paper focuses on the effect of the ZnO content on the microstructure and structure of the internal aluminosilicooxygen network of the glazes from the SiO2-Al2O3-Na2O-K2O-CaO system. In order to examine the real composition of the obtained samples, a chemical analysis was performed. In order to determine the microstructure, research using the scanning electron microscope (SEM) with EDS was done. For the inner structural study, X-ray diffraction (XRD), Raman spectroscopy as well as MIR, FIR spectroscopy and 29Si, 27Al MAS NMR were performed. The study has shown that the experimental glazes are amorphous material. The studies showed that, zinc ions in the structure of the aluminosilicate glazes cause depolymerization of silicon-oxygen network. This means that, the zinc ions Zn2+ in the tested glazes are in octahedral coordination.

  18. Effect of additions of aluminosilicate and silicate materials on the softening temperature of chromite ore

    NASA Astrophysics Data System (ADS)

    Zhdanov, A. V.; Nurmaganbetova, B. N.; Pavlov, V. A.

    2015-07-01

    The temperatures of the beginning and end of softening and the temperature range of softening of the fines of the rich chromite ore of the Donskoy Ore Mining & Processing Plant in Kazakhstan are experimentally determined. The following natural and technical silica-containing materials, which are considered as fluxing additions to decrease the melting temperature of the chromite ore, are investigated: aluminosilicate clays, microsilica, and quartzite of various fractions. The effect of additions of the natural and technical silica-containing materials on the temperatures of the beginning and end of softening and the temperature range of softening of the chromite ore of DODPE is analyzed. The influences of various materials and their fraction compositions on the temperature of softening of the chromite ores are compared.

  19. Investigating the Potential of Single-Walled Aluminosilicate Nanotubes in Water Desalination.

    PubMed

    Liou, Kai-Hsin; Kang, Dun-Yen; Lin, Li-Chiang

    2017-01-18

    Water shortage has become a critical issue. To facilitate the large-scale deployment of reverse-osmosis water desalination to produce fresh water, discovering novel membranes is essential. Here, we computationally demonstrate the great potential of single-walled aluminosilicate nanotubes (AlSiNTs), materials that can be synthesized through scalable methods, in desalination. State-of-the-art molecular dynamics simulations were employed to investigate the desalination performance and structure-performance relationship of AlSiNTs. Free energy profiles, passage time distribution, and water density map were also analyzed to further understand the dependence of transport properties on diameter and water dynamics in the nanotubes. AlSiNTs with an inner diameter of 0.86 nm were found to fully reject NaCl ions while allowing orders of magnitude higher water fluxes compared to currently available reverse osmosis membranes, providing opportunities in water desalination.

  20. Calcium-magnesium Aluminosilicate (CMAS) Interactions with Advanced Environmental Barrier Coating Material

    NASA Technical Reports Server (NTRS)

    Wiesner, Valerie L.; Bansal, Narottam P.

    2015-01-01

    Particulates, like sand and volcanic ash, threaten the development of robust environmental barrier coatings (EBCs) that protect next-generation silicon-based ceramic matrix composite (CMC) turbine engine components from harsh combustion environments during service. The siliceous particulates transform into molten glassy deposits of calcium-magnesium aluminosilicate (CMAS) when ingested by an aircraft engine operating at temperatures above 1200C. In this study, a sample of desert sand was melted into CMAS glass to evaluate high-temperature interactions between the sand glass and an advanced EBC material. Desert sand glass was added to the surface of hot-pressed EBC substrates, which were then heated in air at temperatures ranging from 1200C to 1500C. Scanning electron microscopy and X-ray energy-dispersive spectroscopy were used to evaluate microstructure and phase compositions of specimens and the CMASEBC interface after heat treatments.

  1. Structure and properties of sodium aluminosilicate glasses from molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Xiang, Ye; Du, Jincheng; Smedskjaer, Morten M.; Mauro, John C.

    2013-07-01

    Addition of alumina to sodium silicate glasses considerably improves the mechanical properties and chemical durability and changes other properties such as ionic conductivity and melt viscosity. As a result, aluminosilicate glasses find wide industrial and technological applications including the recent Corning® Gorilla® Glass. In this paper, the structures of sodium aluminosilicate glasses with a wide range of Al/Na ratios (from 1.5 to 0.6) have been studied using classical molecular dynamics simulations in a system containing around 3000 atoms, with the aim to understand the structural role of aluminum as a function of chemical composition in these glasses. The short- and medium-range structures such as aluminum coordination, bond angle distribution around cations, Qn distribution (n bridging oxygen per network forming tetrahedron), and ring size distribution have been systematically studied. In addition, the mechanical properties including bulk, shear, and Young's moduli have been calculated and compared with experimental data. It is found that aluminum ions are mainly four-fold coordinated in peralkaline compositions (Al/Na < 1) and form an integral part of the rigid silicon-oxygen glass network. In peraluminous compositions (Al/Na > 1), small amounts of five-fold coordinated aluminum ions are present while the concentration of six-fold coordinated aluminum is negligible. Oxygen triclusters are also found to be present in peraluminous compositions, and their concentration increases with increasing Al/Na ratio. The calculated bulk, shear, and Young's moduli were found to increase with increasing Al/Na ratio, in good agreement with experimental data.

  2. CO2 SEPARATIONS USING ZEOLITE MEMBRANES

    SciTech Connect

    Richard D. Noble; John L. Falconer

    2001-06-30

    Zeolite and other inorganic molecular sieve membranes have shown potential for separations based on molecular size and shape because of their small pore sized, typically less than 1 nm, and their narrow pore size distribution. The high thermal and chemical stability of these inorganic crystals make them ideal materials for use in high temperature applications such as catalytic membrane reactors. Most of the progress with zeolite membranes has been with MFI zeolites prepared on porous disks and tubes. The MFI zeolite is a medium pore size structure having nearly circular pores with diameters between .53 and .56 nm. Separation experiments through MFI membranes indicate that competitive adsorption separates light gas mixtures. Light gas selectivities are typically small, however, owing to small differences in adsorption strengths and their small sizes relative to the MFI pore opening. Furthermore, competitive adsorption does not work well at high temperature where zeolite membranes are stable and have potential application. Separation by differences in size has a greater potential to work at high temperature than competitive adsorption, but pores smaller than those in MFI zeolites are required. Therefore, some studies focused on the synthesis of a small, 8-membered-pore structures such as zeolite A (0.41-nm pore diameter) and SAPO-34, a chabazite (about .4-nm pore diameter with about 1.4 nm cages) analog. The small pore size of the zeolite A and SAPO-34 structures made the separation of smaller molecules by differences in size possible. Zeolite MFI and SAPO-34 membranes were prepared on the inside surface of porous alumina tubes by hydrothermal synthesis, and single gas and binary mixture permeances were measured to characterize the membrane's performance. A mathematical diffusion model was developed to determine the relative quantities of zeolite and non-zeolite pores in different membranes by modeling the permeation date of CO{sub 2}. This model expresses the total

  3. Efficiency of basalt zeolite and Cuban zeolite to adsorb ammonia released from poultry litter.

    PubMed

    Nuernberg, Giselle B; Moreira, Marcelo A; Ernani, Paulo R; Almeida, Jaime A; Maciel, Tais M

    2016-12-01

    Confined poultry production is an important livestock activity, which generates large amounts of waste associated with the potential for environmental pollution and ammonia (NH3) emissions. The release of ammonia negatively affects poultry production and decreases the N content of wastes that could be used as soil fertilizers. The objective of this study was to evaluate a low-cost, simple and rapid method to simulate ammonia emissions from poultry litter as well as to quantify the reduction in the ammonia emissions to the environment employing two adsorbent zeolites, a commercial Cuban zeolite (CZ) and a ground basalt Brazilian rock containing zeolite (BZ). The experiments were conducted in a laboratory, in 2012-2013. The zeolites were characterized by X-ray diffraction (XRD), X-ray fluorescence spectrometry (XRF), physical adsorption of N2 (BET) and scanning electron microscopy (SEM). Ammonia released from poultry litter and its simulation from NH4OH solution presented similar capture rates of 7.99 × 10(-5) and 7.35 × 10(-5) mg/h, respectively. Both zeolites contain SiO2 and Al2O3 as major constituents, with contents of 84% and 12% in the CZ, and 51% and 12% in the BZ, respectively, besides heulandite groups. Their BET surface areas were 89.4 and 11.3 m(2) g(-1), respectively, and the two zeolites had similar surface morphologies. The zeolites successfully adsorbed the ammonia released, but CZ was more efficient than BZ, since to capture all of the ammonia 5 g of CZ and 20 g of BZ were required. This difference is due to higher values for the superficial area, porosity, CEC and acid site strength of CZ relatively to BZ. The proposed methodology was shown to be an efficient method to simulate and quantify the ammonia released from poultry litter.

  4. Spectroscopic and XRD characterisation of zeolite catalysts active for the oxidative methylation of benzene with methane.

    PubMed

    Adebajo, Moses O; Long, Mervyn A; Frost, Ray L

    2004-03-01

    The benzene methylation with methane over zeolite catalysts was previously shown in our laboratory to require the presence of oxygen. Thus, a two-step mechanism involving the intermediate formation of methanol by partial oxidation of methane followed by the methylation of benzene with methanol in the second step, was postulated. This paper now reports the results of the characterisation of the zeolite catalysts used for the oxidative benzene methylation reaction in order to provide some information about their composition, structure, properties and their behaviour before and after the reaction. The catalysts were characterised by X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray fluorescence (XRF), FT-IR and solid state NMR. XRD results indicate that the crystalline structures of all the ZSM-5 and H-beta catalysts remained unchanged after batch reaction of benzene with methane over the catalysts in agreement with the observation that the catalysts recovered from the reactor could be reused without loss of activity. Elemental analyses and FT-IR data show that as the level of metal ion exchange increases, the Brönsted acid concentration decreases but this metal ion exchange does not totally remove Brönsted acidity. FT-IR results further show that only a small amount of acid sites is actually necessary for a catalyst to be active since used catalysts containing highly reduced Brönsted acidity are found to be reusable without any loss of their activity. 29Si and 27Al magic angle spinning (MAS) NMR together with FT-IR spectra also show that all the active zeolites catalysts contain some extra-framework octahedral aluminium in addition to the normal tetrahedral framework aluminium. The presence of this extra-lattice aluminium does not, however, have any adverse effect on the crystallinity of the catalysts both before and after oxidative benzene methylation reaction. There appears also to be no significant dealumination

  5. Spectroscopic and XRD characterisation of zeolite catalysts active for the oxidative methylation of benzene with methane

    NASA Astrophysics Data System (ADS)

    Adebajo, Moses O.; Long, Mervyn A.; Frost, Ray L.

    2004-03-01

    The benzene methylation with methane over zeolite catalysts was previously shown in our laboratory to require the presence of oxygen. Thus, a two-step mechanism involving the intermediate formation of methanol by partial oxidation of methane followed by the methylation of benzene with methanol in the second step, was postulated. This paper now reports the results of the characterisation of the zeolite catalysts used for the oxidative benzene methylation reaction in order to provide some information about their composition, structure, properties and their behaviour before and after the reaction. The catalysts were characterised by X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray fluorescence (XRF), FT-IR and solid state NMR. XRD results indicate that the crystalline structures of all the ZSM-5 and H-beta catalysts remained unchanged after batch reaction of benzene with methane over the catalysts in agreement with the observation that the catalysts recovered from the reactor could be reused without loss of activity. Elemental analyses and FT-IR data show that as the level of metal ion exchange increases, the Brönsted acid concentration decreases but this metal ion exchange does not totally remove Brönsted acidity. FT-IR results further show that only a small amount of acid sites is actually necessary for a catalyst to be active since used catalysts containing highly reduced Brönsted acidity are found to be reusable without any loss of their activity. 29Si and 27Al magic angle spinning (MAS) NMR together with FT-IR spectra also show that all the active zeolites catalysts contain some extra-framework octahedral aluminium in addition to the normal tetrahedral framework aluminium. The presence of this extra-lattice aluminium does not, however, have any adverse effect on the crystallinity of the catalysts both before and after oxidative benzene methylation reaction. There appears also to be no significant dealumination

  6. Zeolite catalysis in conversion of cellulosics. Annual report

    SciTech Connect

    Tsao, G.T.

    1994-02-01

    The authors have studied the kinetics of oxylose/xylulose isomerization in significant detail over a variety of zeolites and obtained the pseudo-first order reaction rate constants. The authors have found that HY zeolite is still the best material and zeolites are more selective than homogeneous acid catalysts where decomposition of the sugar compounds is much faster. They have completed, as described in the Year 2 Work Plan, the study of cellobiose hydrolysis with an ion exchange resin. The kinetics of the solid-catalyzed reaction is qualitatively similar to that for catalysis by homogeneous acids. The planned program of NMR studies has revealed the dynamics of sugar molecules within the zeolite cavities. Two chemisorbed and a physisorbed state have been identified in HY zeolite. A new state, accounting for as much as a half of the sugar, has been found in ZSM-5 zeolite.

  7. Atomic sites and stability of Cs+ captured within zeolitic nanocavities

    NASA Astrophysics Data System (ADS)

    Yoshida, Kaname; Toyoura, Kazuaki; Matsunaga, Katsuyuki; Nakahira, Atsushi; Kurata, Hiroki; Ikuhara, Yumi H.; Sasaki, Yukichi

    2013-08-01

    Zeolites have potential application as ion-exchangers, catalysts and molecular sieves. Zeolites are once again drawing attention in Japan as stable adsorbents and solidification materials of fission products, such as 137Cs+ from damaged nuclear-power plants. Although there is a long history of scientific studies on the crystal structures and ion-exchange properties of zeolites for practical application, there are still open questions, at the atomic-level, on the physical and chemical origins of selective ion-exchange abilities of different cations and detailed atomic structures of exchanged cations inside the nanoscale cavities of zeolites. Here, the precise locations of Cs+ ions captured within A-type zeolite were analyzed using high-resolution electron microscopy. Together with theoretical calculations, the stable positions of absorbed Cs+ ions in the nanocavities are identified, and the bonding environment within the zeolitic framework is revealed to be a key factor that influences the locations of absorbed cations.

  8. Zeolite and swine inoculum effect on poultry manure biomethanation

    NASA Astrophysics Data System (ADS)

    Kougias, P. G.; Fotidis, I. A.; Zaganas, I. D.; Kotsopoulos, T. A.; Martzopoulos, G. G.

    2013-03-01

    Poultry manure is an ammonia-rich substrate that inhibits methanogenesis, causing severe problems to the anaerobic digestion process. In this study, the effect of different natural zeolite concentrations on the mesophilic anaerobic digestion of poultry waste inoculated with well-digested swine manure was investigated. A significant increase in methane production was observed in treatments where zeolite was added, compared to the treatment without zeolite.Methane production in the treatment with 10 g dm-3 of natural zeolite was found to be 109.75% higher compared to the treatment without zeolite addition. The results appear to be influenced by the addition of zeolite, which reduces ammonia toxicity in anaerobic digestion and by the ammonia-tolerant swine inoculum.

  9. Large zeolites - Why and how to grow in space

    NASA Technical Reports Server (NTRS)

    Sacco, Albert, Jr.

    1991-01-01

    The growth of zeolite crystals which are considered to be the most valuable catalytic and adsorbent materials of the chemical processing industry are discussed. It is proposed to use triethanolamine as a nucleation control agent to control the time release of Al in a zeolite A solution and to increase the average and maximum crystal size by 25-50 times. Large zeolites could be utilized to make membranes for reactors/separators which will substantially increase their efficiency.

  10. Microwave assisted crystallization of zeolite A from dense gels

    NASA Astrophysics Data System (ADS)

    Bonaccorsi, Lucio; Proverbio, Edoardo

    2003-01-01

    Pure zeolite NaA has been obtained, in a total processing time of 1 h, by exposing the reaction mixture to a microwave electromagnetic field under atmospheric pressure. The strong effect of microwave radiation has been used to progressively reduce the water content in the formulation, up to 86.9 mol%, with a 30% (in weight) yield in dried product. SEM images of microwave-produced zeolite have shown peculiar morphological differences from the zeolite obtained by conventional synthesis.

  11. Zeolite (clinoptilolite) as feed additive to reduce manure mineral content.

    PubMed

    Leung, S; Barrington, S; Wan, Y; Zhao, X; El-Husseini, B

    2007-12-01

    Clinoptilolite (a species of zeolite) as grower hog feed additive can potentially improve nutrient ingestion and lower manure nutrient levels. A first objective was to establish the optimal particle size of the zeolite powder, as a fine size increases the adsorption surface while a coarse size can facilitate handling. The second objective tested the effect of feeding zeolite on manure nutrient levels. For the first objective, three zeolite powders (250-500 microm; 50-250 microm, and 50-500 microm) were exposed to an NH(4)(+) solution under a pH of either 7.0 or 2.0. The resulting solutions were tested for cation exchange. A commercial zeolite was also tested for the pH of 2.0 to evaluate zeolite stability. At 0%, 5% and 10% humidity, the same three particle size powders were subjected to shear tests to determine the zeolite's angle of friction. For the second objective using metabolic cages, female hogs were subjected to one of four rations (a control and three with zeolite) while collecting and analyzing their manures. For the first objective, the coarse particle zeolite performed best, adsorbing 158 and 123 Cmol(+)/kg of NH(4)(+) under neutral and acid pH, respectively, and releasing an equivalent amount of minerals only under neutral pH. The commercial zeolite with less clinoptilolite released more Al, Fe, Cu and Pb, showing less stability. The high internal angle of friction of zeolite did not vary with particle size and moisture, indicating funnel flow under gravity. For the second objective, hogs fed a zeolite diet produced manure with 15% and 22% less N and P, respectively, and demonstrated a better feed conversion, although not statistically significant (P>0.05). These results show that there is some potential in using high quality clinoptilolite in the ration of grower hogs.

  12. Fluoride-assisted synthesis of bimodal microporous SSZ-13 zeolite.

    PubMed

    Zhu, Xiaochun; Kosinov, Nikolay; Hofmann, Jan P; Mezari, Brahim; Qian, Qingyun; Rohling, Roderigh; Weckhuysen, Bert M; Ruiz-Martínez, Javier; Hensen, Emiel J M

    2016-02-21

    The presence of small amount of fluoride in alkaline hydrothermal synthesis of SSZ-13 zeolite yields bimodal microporous particles with substantially improved performance in the methanol-to-olefins (MTO) reaction. Hydrocarbon uptake measurements and fluorescence microspectroscopy of spent catalysts demonstrate enhanced diffusion through micropores at the grain boundaries of nanocrystals running through the zeolite particles. Fluoride-assisted SSZ-13 synthesis is a cheap and scalable approach to optimize the performance of MTO zeolite catalysts.

  13. Catalytic Oxidation by Transition Metal Ions in Zeolites.

    DTIC Science & Technology

    1984-09-28

    nmber) Zeolite, Oxidation Catalysis, Molybdenum Zeolite, Cobalt Zeolite, Oxygen Adduct, Cobalt-Oxygen Complexes, Epoxidation _j-J AVIATRACr .1kisa...and substrate ligands. Molybdenum-Y seolites were effective catalysts for the epoxidation of propylene using tert-butyl hydroperoxide as the source...of oxygen. They exhibited high selectivity to the epoxide , and initially were quite active. The activity, *I 0 OF, , , , , ,, , , UNCLASSIFIED -4 1 0 1

  14. Single crystalline magnetite nanotubes.

    PubMed

    Liu, Zuqin; Zhang, Daihua; Han, Song; Li, Chao; Lei, Bo; Lu, Weigang; Fang, Jiye; Zhou, Chongwu

    2005-01-12

    We descried a method to synthesize single crystalline Fe3O4 nanotubes by wet-etching the MgO inner cores of MgO/Fe3O4 core-shell nanowires. Homogeneous Fe3O4 nanotubes with controllable length, diameter, and wall thickness have been obtained. Resistivity of the Fe3O4 nanotubes was estimated to be approximately 4 x 10-2 Omega cm at room temperature. Magnetoresistance of approximately 1% was observed at T = 77 K when a magnetic field of B = 0.7 T was applied. The synthetic strategy presented here may be extended to a variety of materials such as YBCO, PZT, and LCMO which should provide ideal candidates for fundamental studies of superconductivity, piezoelectricity, and ferromagnetism in nanoscale structures.

  15. Liquid crystalline polymers

    NASA Technical Reports Server (NTRS)

    1990-01-01

    The remarkable mechanical properties and thermal stability of fibers fabricated from liquid crystalline polymers (LCPs) have led to the use of these materials in structural applications where weight savings are critical. Advances in processing of LCPs could permit the incorporation of these polymers into other than uniaxial designs and extend their utility into new areas such as nonlinear optical devices. However, the unique feature of LCPs (intrinsic orientation order) is itself problematic, and current understanding of processing with control of orientation falls short of allowing manipulation of macroscopic orientation (except for the case of uniaxial fibers). The current and desirable characteristics of LCPs are reviewed and specific problems are identified along with issues that must be addressed so that advances in the use of these unique polymers can be expedited.

  16. A Novel Conversion Process for Waste Slag: The Preparation of Aluminosilicate Glass with Evaluation of the Dielectric Properties from Blast Furnace Slag

    NASA Astrophysics Data System (ADS)

    Li, Sheng; Huang, Sanxi; Liu, Hongting; Wu, Fengnian; Chang, Ziyuan; Yue, Yunlong

    2015-11-01

    In this paper, aluminosilicate glass was prepared from blast furnace slag and quartz sand. Fourier transform infrared, differential scanning calorimetry and density measurements were carried out to investigate the effects of SiO2 on the aluminosilicate glass network rigidity. The results indicate that glass structure would be enhanced if more SiO2 was introduced into the glass system. Meanwhile, both the glass transition temperature ( T g) and the glass crystallization temperature ( T c) increase slightly; the increase in density of the glass being further evidence of the enhancement in glass network rigidity. Dielectric measurements show that the dielectric constant and dielectric loss decrease with more SiO2. The properties of the prepared aluminosilicate glasses are comparable to those of E glass, indicating that blast furnace slags are suitable for producing aluminosilicate glass with low dielectric constant and dielectric loss.

  17. Cation locations and dislocations in zeolites

    NASA Astrophysics Data System (ADS)

    Smith, Luis James

    The focus of this dissertation is the extra-framework cation sites in a particular structural family of zeolites, chabazite. Cation sites play a particularly important role in the application of these sieves for ion exchange, gas separation, catalysis, and, when the cation is a proton, acid catalysis. Structural characterization is commonly performed through the use of powder diffraction and Rietveld analysis of powder diffraction data. Use of high-resolution nuclear magnetic resonance, in the study of the local order of the various constituent nuclei of zeolites, complements well the long-range order information produced by diffraction. Recent developments in solid state NMR techniques allow for increased study of disorder in zeolites particularly when such phenomena test the detection limits of diffraction. These two powerful characterization techniques, powder diffraction and NMR, offer many insights into the complex interaction of cations with the zeolite framework. The acids site locations in SSZ-13, a high silica chabazite, and SAPO-34, a silicoaluminophosphate with the chabazite structure, were determined. The structure of SAPO-34 upon selective hydration was also determined. The insensitivity of X-rays to hydrogen was avoided through deuteration of the acid zeolites and neutron powder diffraction methods. Protons at inequivalent positions were found to have different acid strengths in both SSZ-13 and SAPO-34. Other light elements are incorporated into zeolites in the form of extra-framework cations, among these are lithium, sodium, and calcium. Not amenable by X-ray powder diffraction methods, the positions of such light cations in fully ion-exchanged versions of synthetic chabazite were determined through neutron powder diffraction methods. The study of more complex binary cation systems were conducted. Powder diffraction and solid state NMR methods (MAS, MQMAS) were used to examine cation site preferences and dislocations in these mixed-akali chabazites

  18. Peculiarities of the dielectric response of natural zeolite composites prepared by using zeolite and silicon powders

    NASA Astrophysics Data System (ADS)

    Ozturk Koc, S.; Orbukh, V. I.; Eyvazova, G. M.; Lebedeva, N. N.; Salamov, B. G.

    2016-03-01

    We present the real and imaginary part of the dielectric permittivity of natural zeolite composites prepared by using zeolite and silicon powders. The dielectric response (DR) dependences on the frequency (3-300 GHz) of electric field and different Si concentrations (5-33%) are non-monotonic and a maximum peak is observed. This peak position is practically independent on the frequency and its maximum is observed in zeolite composites which included 9% of the Si-powder. Also the maximum peak is decreased by about an order of magnitude when frequency increases from 500 Hz to 5 kHz. Addition of the conductive Si-particles to zeolite-powder leads to two opposite effects. Firstly, the movement of electrons in the Si-particles provides increase of DR. Secondly, cations which leaving from zeolite pores can be neutralized by the particles of Si in the intercrystalline-space. Such a peculiar mechanism for recombination of Si electrons and cations from pores leads to a reduction of DR for large silicon concentrations. Due to the fact that the contribution of free carriers in the decreasing of the DR as the frequency increases, it is consistent with the suggestion that the maximum peak decreases with increasing frequency.

  19. Zeolites are effective ROS-scavengers in vitro.

    PubMed

    Pellegrino, Perrine; Mallet, Bernard; Delliaux, Stéphane; Jammes, Yves; Guieu, Regis; Schäf, Oliver

    2011-07-08

    We report on the use of zeolites to limit the effects of reactive oxygen species (ROS) on human albumin under in vitro conditions. Zeolites of different structure type, channel size, channel polarity, and charge-compensating cation were screened for the elimination of ROS, notably HO(·), resulting from the Fenton reaction. A test based on ischemia-modified albumin (IMA) was used as a marker to monitor the activity of HO(·) after co-exposure of human serum to these zeolites. Two commercial zeolites, faujasite (FAU 13×, channel opening 0.74×0.74 nm with Na(+) as charge-compensating cation) and ferrierite (FER, channel opening 0.54×0.42 nm with H(+) as charge-compensating cation), were found to reduce IMA formation by more than 65% due to removal of HO(·) relative to reference values. It was established that partial ion exchange of the zeolites' respective charge-compensating cation vs. Fe(3+) implicated in the Fenton reaction plays a major role in HO(·) deactivation process. Moreover, our results show that no saturation of the respective zeolite active sites occurred. This is possible only when ROS are actively converted to water molecules within the zeolite void system, which generates H(+) ion transport. Because zeolites cannot be administered in blood, their use in medicine should be limited to extra corporeal circuits. Zeolites could be of use during cardiopulmonary bypass or hemodialysis procedures.

  20. Method for the recovery of silver from silver zeolite

    DOEpatents

    Reimann, George A.

    1986-01-01

    High purity silver is recovered from silver exchanged zeolite used to capture radioactive iodine from nuclear reactor and nuclear fuel reprocessing environments. The silver exchanged zeolite is heated with slag formers to melt and fluidize the zeolite and release the silver, the radioactivity removing with the slag. The silver containing metallic impurities is remelted and treated with oxygen and a flux to remove the metal impurities. About 98% of the silver in the silver exchanged zeolite having a purity of 99% or better is recoverable by the method.

  1. Method for the recovery of silver from silver zeolite

    DOEpatents

    Reimann, G.A.

    1985-03-05

    High purity silver is recovered from silver exchanged zeolite used to capture radioactive iodine from nuclear reactor and nuclear fuel reprocessing environments. The silver exchanged zeolite is heated with slag formers to melt and fluidize the zeolite and release the silver, the radioactivity removing with the slag. The silver containing metallic impurities is remelted and treated with oxygen and a flux to remove the metal impurities. About 98% of the silver in the silver exchanged zeolite having a purity of 99% or better is recoverable by the method.

  2. Natural zeolites in diet or litter of broilers.

    PubMed

    Schneider, A F; Almeida, D S De; Yuri, F M; Zimmermann, O F; Gerber, M W; Gewehr, C E

    2016-04-01

    This study aims to analyse the influence of adding natural zeolites (clinoptilolite) to the diet or litter of broilers and their effects on growth performance, carcass yield and litter quality. Three consecutive flocks of broilers were raised on the same sawdust litter, from d 1 to d 42 of age, and distributed in three treatments (control with no added zeolites, addition of 5 g/kg zeolite to diet and addition of 100 g/kg zeolites to litter). The addition of zeolites to the diet or litter did not affect growth performance or carcass yield. The addition of zeolites to the diet did not influence moisture content of the litter, ammonia volatilisation was reduced only in the first flock and pH of litter was reduced in the second and third flock. However, the addition of zeolites to the litter reduced moisture content, litter pH and ammonia volatilisation in all flocks analysed. The addition of 5 g/kg zeolite to the diet in three consecutive flocks was not effective in maintaining litter quality, whereas the addition of 100 g/kg natural zeolites to sawdust litter reduced litter moisture and ammonia volatilisation in three consecutive flocks raised on the same litter.

  3. Zeolite Crystal Growth in Microgravity and on Earth

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The Center for Advanced Microgravity Materials Processing (CAMMP), a NASA-sponsored Research Partnership Center, is working to improve zeolite materials for storing hydrogen fuel. CAMMP is also applying zeolites to detergents, optical cables, gas and vapor detection for environmental monitoring and control, and chemical production techniques that significantly reduce by-products that are hazardous to the environment. Shown here are zeolite crystals (top) grown in a ground control experiment and grown in microgravity on the USML-2 mission (bottom). Zeolite experiments have also been conducted aboard the International Space Station.

  4. Dry method for recycling iodine-loaded silver zeolite

    DOEpatents

    Thomas, Thomas R.; Staples, Bruce A.; Murphy, Llewellyn P.

    1978-05-09

    Fission product iodine is removed from a waste gas stream and stored by passing the gas stream through a bed of silver-exchanged zeolite until the zeolite is loaded with iodine, passing dry hydrogen gas through the bed to remove the iodine and regenerate the bed, and passing the hydrogen stream containing the hydrogen iodide thus formed through a lead-exchanged zeolite which adsorbs the radioactive iodine from the gas stream and permanently storing the lead-exchanged zeolite loaded with radioactive iodine.

  5. Electrical Response of PEDOT-PSS/FAU Zeolite Composites toward SO2: Controlling the Adsorption Properties of FAU Zeolite

    NASA Astrophysics Data System (ADS)

    Chanthaanont, Pojjawan; Sirivat, Anuvat

    2012-02-01

    In our work, we propose to combine a conductive polymer, Poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonic acid) (PEDOT-PSS), with FAU zeolites to investigate the potential of the composites for use as SO2 sensing materials.Composites with PEDOT-PSS as a matrix containing faujasite zeolites of various cation types (divalent transition metal ions: Fe^2+, Co^2+, Ni^2+ and Cu^2+), were fabricated to investigate the effect of the cation type of the faujasite zeolites on the electrical conductivity response when exposed to SO2. The composite was tested through repeated sensing and recovery processes to investigate the reversibility and reproducibility. During the recovery process, the electrical conductivity of the composites were recovered, which proves that the sensing characteristics are repeatable. Responses and the interaction mechanism of the conductive polymer/zeolite composites were investigated. The composite with 20% (v/v) of zeolite content gives the highest sensitivity. The electrical conductivity responses of PEDOT-PSS/Zeolite composites can be altered due to the available adsorption sites for gas molecules. The addition of zeolites to the pristine PEDOT-PSS improved the electrical conductivity sensitivity of the composites by enhancing the interaction between PEDOT-PSS and SO2. The type of cation in the zeolite pores effected the sensitivity of the composites, depending on the acidity of the ion-exchanged zeolites.

  6. Preparation of zeolite ANA crystal from zeolite Y by in situ solid phase iso-structure transformation.

    PubMed

    Wang, Yi; Li, Xuguang; Xue, Zhiyuan; Dai, Linsen; Xie, Songhai; Li, Quanzhi

    2010-05-06

    A new method has been explored to synthesize zeolite ANA crystals with regular icositetrahedron in aqueous media via transformation of zeolite Y under the conditions of low temperature, short reaction time, and without organic template. The products are perfect, almost 100% crystals. The samples prepared at different crystallization stages are measured by XRD, TEM, and SEM to investigate the transformation mechanism from zeolite Y to zeolite ANA. It has been demonstrated for the first time that the mechanism of forming a zeolite ANA polycrystal with sphere or shell morphologies is the in situ solid phase iso-structure transformation (Is-SPIST) of zeolite Y. The Is-SPIST mechanism is also supported by the results of steam-induced crystallization experiments and other assistant means, including the same Si/Al ratio, the same weight, the same particle size, and the same morphology before and after transformation of zeolite Y to zeolite ANA. It is also observed that a spherical or shell ANA polycrystal is constructed via the reconstruction from its exterior to interior, to form an ANA single crystal with a solid or hollow icositetrahedron. The main driving force of the reconstruction is considered to be the grain boundary energy existing between polycrystalline grains. This process also obeys the mechanism of in situ solid phase reconstruction (Is-SPR). Furthermore, the size and morphology of the zeolite ANA single crystal can be modified by surfactants.

  7. Pf/Zeolite Catalyst for Tritium Stripping

    SciTech Connect

    Hsu, R.H.

    2001-03-26

    This report described promising hydrogen (protium and tritium) stripping results obtained with a Pd/zeolite catalyst at ambient temperature. Preliminary results show 90-99+ percent tritium stripping efficiency may be obtained, with even better performance expected as bed configuration and operating conditions are optimized. These results suggest that portable units with single beds of the Pd/zeolite catalyst may be utilized as ''catalytic absorbers'' to clean up both tritium gas and tritiated water. A cart-mounted prototype stripper utilizing this catalyst has been constructed for testing. This portable stripper has potential applications in maintenance-type jobs such as tritium line breaks. This catalyst can also potentially be utilized in an emergency stripper for the Replacement Tritium Facility.

  8. Olefins from methanol by modified zeolites

    SciTech Connect

    Inui, T.; Takegami, Y.

    1982-11-01

    Compares the effects of modified catalysts (ZSM-34 and ZSM-5 class zeolites) on methanol conversion to olefins (MTO) with regard to olefin selectivity and cost. Presents tables with prices of olefins in the US and Japan; comparison of methanol-cracking with naphtha cracking; methanol conversion data for Type-1, Type-II and reference catalysts; hydrocarbon distribution from MTO processes; and speculative economics for MTO processes of Concept-1 and 2. Diagrams the proposed MTO process scheme. Scanning electron micrographs of the zeolite catalysts are shown. Graphs indicate the change of ethylene prices in the US since 1978 and forecast ethylene prices in several countries. Concludes that the prices of ethylene for both MTO processes examined compare favorably with products of conventional processes.

  9. COLD DRAWING IN CRYSTALLINE POLYMERS

    DTIC Science & Technology

    alcohols, phenol) in Nylon 6 produced changes in the crystalline structure as well as plasticizer action; these two effects must therefore be carefully...distinguished. Changes in the crystalline structure were followed by changes in the infrared spectrum. Dynamic mechanical and thermogravimetric analysis

  10. Charge-transfer state excitation as the main mechanism of the photodarkening process in ytterbium-doped aluminosilicate fibres

    SciTech Connect

    Bobkov, K K; Rybaltovsky, A A; Vel'miskin, V V; Likhachev, M E; Bubnov, M M; Dianov, E M; Umnikov, A A; Gur'yanov, A N; Vechkanov, N N; Shestakova, I A

    2014-12-31

    We have studied photodarkening in ytterbium-doped fibre preforms with an aluminosilicate glass core. Analysis of their absorption and luminescence spectra indicates the formation of stable Yb{sup 2+} ions in the glass network under IR laser pumping at a wavelength λ = 915 nm and under UV irradiation with an excimer laser (λ = 193 nm). We have performed comparative studies of the luminescence spectra of the preforms and crystals under excitation at a wavelength of 193 nm. The mechanism behind the formation of Yb{sup 2+} ions and aluminium – oxygen hole centres (Al-OHCs), common to ytterbium-doped YAG crystals and aluminosilicate glass, has been identified: photoinduced Yb{sup 3+} charge-transfer state excitation. (optical fibres)

  11. Flux Decoupling and Chemical Diffusion in Redox Dynamics in Aluminosilicate Melts and Glasses (Invited)

    NASA Astrophysics Data System (ADS)

    Cooper, R. F.

    2010-12-01

    Measurements of redox dynamics in silicate melts and glasses suggest that, for many compositions and for many external environments, the reaction proceeds and is rate-limited by the diffusive flux of divalent-cation network modifiers. Application of ion-backscattering spectrometry either (i) on oxidized or reduced melts (subsequently quenched before analysis) or (ii) on similarly reacted glasses, both of basalt-composition polymerization, demonstrates that the network modifiers move relative to the (first-order-rigid) aluminosilicate network. Thus, the textures associated with such reactions are often surprising, and frequently include metastable or unstable phases and/or spatial compositional differences. This response is only possible if the motion of cations can be decoupled from that of anions. In many cases, decoupling is accomplished by the presence in the melt/glass of transition-metal cations, whose heterovalency creates distortions in the electronic band structure resulting in electronic defects: electron “holes” in the valence band or electrons in the conduction band. (The prevalence of holes or electrons being a function of bulk chemistry and oxygen activity.) These electronic species make the melt/glass a “defect semiconductor.” Because (a) the critical issue in reaction dynamics is the transport coefficient (the product of species mobility and species concentration) and (b) the electronic species are many orders of magnitude more mobile than are the ions, very low concentrations of transition-metal ions are required for flux decoupling. For example, 0.04 at% Fe keeps a magnesium aluminosilicate melt/glass a defect semiconductor down to 800°C [Cook & Cooper, 2000]. Depending on composition, high-temperature melts can see ion species having a high-enough transport coefficient to allow decoupling, e.g., alkali cations in a basaltic melt [e.g., Pommier et al., 2010]. In this presentation, these ideas will be illustrated by examining redox dynamics

  12. Corrosion of MgO-MgAl{sub 2}O{sub 4} spinel refractory bricks by calcium aluminosilicate slag

    SciTech Connect

    Goto, Kiyoshi; Argent, B.B.; Lee, W.E.

    1997-02-01

    Microstructural analysis of MgO-MgAl{sub 2}O{sub 4} refractory bricks corroded at 1,400--1,500 C by calcium aluminosilicate slag reveals secondary spinel, monticellite, merwinite, and MgO as microscopic corrosion products, generally forming in this sequence as the brick is penetrated. The secondary spinel forms an incomplete layer close to (but not at) the MgO grain. Thermodynamic calculations are used to support a detailed model of the corrosion mechanism.

  13. Preparation and screening of crystalline zeolite and hydrothermally-synthesized materials

    DOEpatents

    Schultz, Peter G.; Xiang, Xiaodong; Goldwasser, Isy; Briceno, Gabriel; Sun, Xiao-Dong; Wang, Kai-An

    2005-03-08

    Methods and apparatus for the preparation and use of a substrate having an array of diverse materials in predefined regions thereon. A substrate having an array of diverse materials thereon is generally prepared by delivering components of materials to predefined regions on a substrate, and simultaneously reacting the components to form at least two materials. Materials which can be prepared using the methods and apparatus of the present invention include, for example, covalent network solids, ionic solids and molecular solids. More particularly, materials which can be prepared using the methods and apparatus of the present invention include, for example, inorganic materials, intermetallic materials, metal alloys, ceramic materials, organic materials, organometallic materials, non-biological organic polymers, composite materials (e.g., inorganic composites, organic composites, or combinations thereof), etc. Once prepared, these materials can be screened for useful properties including, for example, electrical, thermal, mechanical, morphological, optical, magnetic, chemical, or other properties. Thus, the present invention provides methods for the parallel synthesis and analysis of novel materials having useful properties.

  14. Organosilane with Gemini-Type Structure as the Mesoporogen for the Synthesis of the Hierarchical Porous ZSM-5 Zeolite.

    PubMed

    Zhu, Haibo; Abou-Hamad, Edy; Chen, Yin; Saih, Youssef; Liu, Weibing; Samal, Akshaya Kumar; Basset, Jean-Marie

    2016-03-01

    A new kind of organosilane (1,6-bis(diethyl(3-trimethoxysilylpropyl)ammonium) hexane bromide) with a gemini-type structure was prepared and used as a mesoporogen for the synthesis of hierarchical porous ZSM-5 zeolite. There are two quaternary ammonium centers along with double-hydrolyzable -RSi(OMe)3 fragments in the organosilane, which results in a strong interaction between this mesoporogen and silica-alumina gel. The organosilane can be easily incorporated into the ZSM-5 zeolite structure during the crystallization process, and it was finally removed by calcination, leading to secondary pores in ZSM-5. The synthesized ZSM-5 has been systematically studied by XRD, nitrogen adsorption, SEM, TEM, TG, and solid-state one-dimensional (1D) and two-dimensional (2D) NMR, which reveal information on its detailed structure. It has a hierarchical porosity system, which combines the intrinsic micropores coming from the crystalline structure and irregular mesopores created by the organosilane template. Moreover, the mesoposity including pore size and volume within ZSM-5 can be systematically tuned by changing the organosilane/TEOS ratio, which confirms that this organosilane has high flexibility of use as a template for the synthesis of hierarchical porous zeolite.

  15. New antiaxillary odour deodorant made with antimicrobial Ag-zeolite (silver-exchanged zeolite).

    PubMed

    Nakane, T; Gomyo, H; Sasaki, I; Kimoto, Y; Hanzawa, N; Teshima, Y; Namba, T

    2006-08-01

    The causative substances for axillary osmidrosis, which are often found in apocrine sweat, are the decomposed/denatured products of short-chain fatty acid and other biological metabolite compounds produced by axillary-resident bacteria. Conventional underarm deodorants suppress the process of odour production mostly by the following mechanism: (1) suppression of perspiration, (2) reduction in numbers of resident bacteria, (3) deodorization and (4) masking. The most important and effective method to reduce odour is to suppress the growth of resident bacteria with antimicrobials, which have several drawbacks, especially in their safety aspect. To solve these problems, we focused on Ag-zeolite (silver-exchanged zeolite) that hold stable Ag, an inorganic bactericidal agent, in its structure, and therefore, poses less risk in safety. Its bactericidal effect on skin-resident bacteria was found to be excellent and comparable with that of triclosan, a most frequently used organic antimicrobial in this product category. The dose-response study of Ag-zeolite powder spray (0-40 w/w%) using 39 volunteers revealed that 5-40 w/w% Ag-zeolite could show a sufficient antimicrobial effect against skin-resident bacteria. The comparison study using 0.2 w/w% triclosan as the control and 10 w/w% Ag-zeolite indicated that: (1) one application of the powder spray containing 10 w/w% Ag-zeolite could show a sufficient antimicrobial effect against the resident bacteria and its effect continued for 24 h, (2) a powder spray containing 0.2 w/w% triclosan was unable to show a sufficient antimicrobial effect, and (3) no adverse event was observed. These studies show that Ag-zeolite has a superior antimicrobial ability that is rarely found in conventional antimicrobials used in deodorant products and a strong antiaxillary odour deodorant ability because of its long-lasting effect. During clinical study, patch tests with humans and other clinical studies of this product showed no adverse events

  16. Source fabrication and lifetime for Li+ ion beams extracted from alumino-silicate sources

    SciTech Connect

    Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W

    2012-03-05

    A space-charge-limited beam with current densities (J) exceeding 1 mA/cm2 have been measured from lithium alumino-silicate ion sources at a temperature of ~1275 °C. At higher extraction voltages, the source appears to become emission limited with J ≥ 1.5 mA/cm2, and J increases weakly with the applied voltage. A 6.35 mm diameter source with an alumino-silicate coating, ≤0.25 mm thick, has a measured lifetime of ~40 h at ~1275 °C, when pulsed at 0.05 Hz and with pulse length of ~6 μs each. At this rate, the source lifetime was independent of the actual beam charge extracted due to the loss of neutral atoms at high temperature. Finally, the source lifetime increases with the amount of alumino-silicate coated on the emitting surface, and may also be further extended if the temperature is reduced between pulses.

  17. Source fabrication and lifetime for Li+ ion beams extracted from alumino-silicate sources

    SciTech Connect

    Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W.

    2012-04-01

    A space-charge-limited beam with current densities (J) exceeding 1 mA/cm2 have been measured from lithium alumino-silicate ion sources at a temperature of ~1275 °C. At higher extraction voltages, the source appears to become emission limited with J ≥ 1.5 mA/cm2, and J increases weakly with the applied voltage. A 6.35 mm diameter source with an alumino-silicate coating, ≤0.25 mm thick, has a measured lifetime of ~40 h at ~1275 °C, when pulsed at 0.05 Hz and with pulse length of ~6 μs each. At this rate, the source lifetime was independent of the actual beam charge extracted due to the loss of neutral atoms at high temperature. Finally, the source lifetime increases with the amount of alumino-silicate coated on the emitting surface, and may also be further extended if the temperature is reduced between pulses.

  18. Chlorine, in the Presence of Iron, Does Indeed Decrease the Viscosity of Aluminosilicate Melts

    NASA Astrophysics Data System (ADS)

    Webb, S. L.

    2012-12-01

    The effect of volatiles on melt rheology is investigated here, as the degassing of magma before an eruption usually leads to an increase in magma viscosity; and therefore increases the probability of an explosive eruption. There is not a large amount of data on the effect of chlorine on viscosity. It would appear, however, that chlorine increases the viscosity of peralkaline sodium-aluminosilicate melts, and decreases the viscosity of peraluminous sodium-aluminosilicate melts. These different effects of chlorine on viscosity indicate that the chlorine sits in different structural sites in peraluminous and peralkaline melts. In previous studies of rheology in this laboratory, we have shown that chlorine does indeed increase the viscosity of a phonolite analog Na2O-CaO-Al2O3-SiO2 melt. In this study, we have extended our investigation of the rheology of chlorine-bearing melts to basaltic compositions. The melt composition used here is that of a basaltic glass taken from the mid-Atlantic Ridge at 3000 m depth during the Venture Cruise (Ireland) of 2011. The viscosities were determined using the micropenetration technique in the 109-1012 Pa s range at temperatures 600-800 C. It was found that the addition of 0.6 wt% Cl resulted in a 0.5 log unit decrease in viscosity. A synthetic haplo-basaltic melt with the iron replaced by Mg and the Al was also synthesized. The addition of 0.3 wt% chlorine to this melt resulted in a 0.3 log unit increase in viscosity; as observed previously for Fe-free peralkaline melts. Based on these viscosity data it would appear that the effect of chlorine on rheology is a function of the composition of the melt, and that the structural site taken by chlorine varies as a function of the presence or absence of iron. The addition of chlorine to the iron-bearing melt, increased the Fe2+/Fetot from 0.30 to 0.45. This indicates that the presence of chlorine results in an energetic preference for Fe2+ in the melt structure. Thus, it is not so much the

  19. Alkali aluminosilicate melts and glasses: structuring at the middle range order of amorphous matter

    NASA Astrophysics Data System (ADS)

    Le Losq, C.; neuville, D. R.

    2012-12-01

    Rheological properties of silicate melts govern both magma ascension from the mantle to the surface of the earth and volcanological eruptions styles and behaviours. It is well known that several parameters impact strongly these properties, such as for instance the temperature, pressure, chemical composition and volatiles concentration, finally influencing eruptive behaviour of volcanoes. In this work, we will focus on the Na2O-K2O-Al2O3-SiO2 system, which is of a prime importance because it deals with a non-negligible part of natural melts, like for instance the Vesuvius (Italy) or Erebus (Antartica) magmas. In an oncoming paper in Chemical Geology (Le Losq and Neuville, 2012), we have communicated results of the study of mixing Na-K in tectosilicate melts containing a high concentration of silica (≥75mol%). In the present communication, we will enlarge this first point of view to tectosilicate melts presenting a lower silica concentration. We will first present our viscosity data, and then the Adam and Gibbs theory that allows theoretically modelling Na-K mixing in aluminosilicate melts by using the so-called "mixed alkali effect". On the basis of the rheological results, the Na-K mixing cannot be explained with the ideal "mixed alkali effect", which involves random exchange of Na-K cationic pairs. To go further and as rheological properties are directly linked with structural properties, we will present our first results obtained by Raman and NMR spectroscopy. These last ones provide important structural pieces of information on the polymerization state of glasses and melts, and also on the environment of tetrahedrally coordinated cations. Rheological and structural results all highlight that Na and K are not randomly distributed in aluminosilicate glasses and melts networks. Na melts present a network with some channels and a non-random distribution of Al and Si. K networks are different. They also present a non-random distribution of Al and Si, but in two sub

  20. In Situ SAXS/WAXS of Zeolite Microwave Synthesis: NaY, NaA, and Beta Zeolites

    SciTech Connect

    Panzarella,B.; Tompsett, G.; Conner, W.; Jones, K.

    2007-01-01

    A custom waveguide apparatus is constructed to study the microwave synthesis of zeolites by in situ small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). The WR-284 waveguide is used to heat precursor solutions using microwaves at a frequency of 2.45 GHz. The reaction vessels are designed to include sections of thin-walled glass, which permit X-rays to pass through the precursor solutions with minimal attenuation. Slots were machined into the waveguide to provide windows for X-ray energy to enter and scatter from solutions during microwave heating. The synthesis of zeolites with conventional heating is also studied using X-ray scattering in the same reactor. SAXS studies show that the crystallization of beta zeolite and NaY zeolite is preceded by a reorganization of nanosized particles in their precursor solutions or gels. The evolution of these particles during the nucleation and crystallization stages of zeolite formation depends on the properties of the precursor solution. The synthesis of NaA and NaX zeolites and sodalite from a single zeolite precursor is studied by microwave and conventional heating. Microwave heating shifts the selectivity of this synthesis in favor of NaA and NaX over sodalite; conventional heating leads to the formation of sodalite for synthesis from the same precursor. The use of microwave heating also led to a more rapid onset of NaA zeolite product crystallization compared to conventional heating. Pulsed and continuous microwave heating are compared for zeolite synthesis. The resulting rates of formation of the zeolite products, and the relative amounts of the products determined from the WAXS spectra, are similar when either pulsed or continuous microwave heating is applied in the reactor while maintaining the same synthesis temperature. The consequences of these results in terms of zeolite synthesis are discussed.

  1. In situ SAXS/WAXS of zeolite microwave synthesis: NaY, NaA, and beta zeolites.

    PubMed

    Panzarella, Bernard; Tompsett, Geoffrey; Conner, William C; Jones, Keith

    2007-02-19

    A custom waveguide apparatus is constructed to study the microwave synthesis of zeolites by in situ small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). The WR-284 waveguide is used to heat precursor solutions using microwaves at a frequency of 2.45 GHz. The reaction vessels are designed to include sections of thin-walled glass, which permit X-rays to pass through the precursor solutions with minimal attenuation. Slots were machined into the waveguide to provide windows for X-ray energy to enter and scatter from solutions during microwave heating. The synthesis of zeolites with conventional heating is also studied using X-ray scattering in the same reactor. SAXS studies show that the crystallization of beta zeolite and NaY zeolite is preceded by a reorganization of nanosized particles in their precursor solutions or gels. The evolution of these particles during the nucleation and crystallization stages of zeolite formation depends on the properties of the precursor solution. The synthesis of NaA and NaX zeolites and sodalite from a single zeolite precursor is studied by microwave and conventional heating. Microwave heating shifts the selectivity of this synthesis in favor of NaA and NaX over sodalite; conventional heating leads to the formation of sodalite for synthesis from the same precursor. The use of microwave heating also led to a more rapid onset of NaA zeolite product crystallization compared to conventional heating. Pulsed and continuous microwave heating are compared for zeolite synthesis. The resulting rates of formation of the zeolite products, and the relative amounts of the products determined from the WAXS spectra, are similar when either pulsed or continuous microwave heating is applied in the reactor while maintaining the same synthesis temperature. The consequences of these results in terms of zeolite synthesis are discussed.

  2. Characterization and antibacterial activity of silver exchanged regenerated NaY zeolite from surfactant-modified NaY zeolite.

    PubMed

    Salim, Mashitah Mad; Malek, Nik Ahmad Nizam Nik

    2016-02-01

    The antibacterial activity of regenerated NaY zeolite (thermal treatment from cetyltrimethyl ammonium bromide (CTAB)-modified NaY zeolite and pretreatment with Na ions) loaded with silver ions were examined using the broth dilution minimum inhibitory concentration (MIC) method against Escherichia coli (E. coli ATCC 11229) and Staphylococcus aureus (S. aureus ATCC 6538). X-ray diffraction (XRD), attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) and chemical elemental analyses were used to characterize the regenerated NaY and AgY zeolites. The XRD patterns indicated that the calcination and addition of silver ions on regenerated NaY zeolite did not affect the structure of the regenerated NaY zeolite as the characteristic peaks of the NaY zeolite were retained, and no new peaks were observed. The regenerated AgY zeolite showed good antibacterial activity against both bacteria strains in distilled water, and the antibacterial activity of the samples increased with increasing Ag loaded on the regenerated AgY zeolite; the regenerated AgY zeolite was more effective against E. coli than S. aureus. However, the antibacterial activity of the regenerated AgY was not effective in saline solution for both bacteria. The study showed that CTAB-modified NaY zeolite materials could be regenerated to NaY zeolite using thermal treatment (550°C, 5h) and this material has excellent performance as an antibacterial agent after silver ions loading.

  3. Design of composite photocatalyst of TiO2 and Y-zeolite for degradation of 2-propanol in the gas phase under UV and visible light irradiation.

    PubMed

    Kamegawa, Takashi; Ishiguro, Yasushi; Kido, Ryota; Yamashita, Hiromi

    2014-10-13

    Hydrophobic Y-zeolite (SiO2/Al2O3 = 810) and TiO2 composite photocatalysts were designed by using two different types of TiO2 precursors, i.e., titanium ammonium oxalate and ammonium hexafluorotitanate. The porous structure, surface property and state of TiO2 were investigated by various characterization techniques. By using an ammonium hexafluorotitanate as a precursor, hydrophobic modification of the Y-zeolite surface and realizing visible light sensitivity was successfully achieved at the same time after calcination at 773 K in the air. The prepared sample still maintained the porous structure of Y-zeolite and a large surface area. Highly crystalline anatase TiO2 was also formed on the Y-zeolite surface by the role of fluorine in the precursor. The usages of ammonium hexafluorotitanate were effective for the improvement of the photocatalytic performance of the composite in the degradation of 2-propanol in the gas phase under UV and visible light (λ > 420 nm) irradiation.

  4. Monoethanol amine modified zeolite 13X for CO{sub 2} adsorption at different temperatures

    SciTech Connect

    P.D. Jadhav; R.V. Chatti; R.B. Biniwale; N.K. Labhsetwar; S. Devotta; S.S. Rayalu . s_rayalu@neeri.res.in

    2007-12-15

    Zeolite 13X has been modified with monoethanol amine (MEA). MEA loadings of 0.5-25 wt % have been achieved using the impregnation method in different solvents. The mode of incorporation based on methanol with stirring at room temperature appears to be the most feasible. The adsorbent has been characterized for crystallinity, surface area, pore volume, and pore size. The thermal stability of the adsorbent is studied using a thermal analyzer. The CO{sub 2} adsorption capacity of adsorbents is evaluated using the breakthrough adsorption method with a packed column on a 10 g scale. The adsorption capacities of adsorbents are estimated in the temperature range 30-120{sup o}C. The adsorbents show improvement in CO{sub 2} adsorption capacity over the unmodified zeolite by a factor of ca. 1.6 at 30{sup o}C, whereas at 120{sup o}C the efficiency improved by a factor of 3.5. For adsorption at these temperatures, different MEA loading levels were found to be suitable as per the governing adsorption phenomena, that is, physical or chemical. The adsorbent is also studied for CO{sub 2} selectivity over N{sub 2} at 75{sup o}C. The MEA-modified adsorbent shows better CO{sub 2} selectivity, which was improved further in the presence of moisture. 25 refs., 6 figs., 3t abs.

  5. Intrusion-extrusion spring performance of -COK-14 zeolite enhanced by structural changes.

    PubMed

    Kirschhock, Christine E A; De Prins, Michiel; Verheijen, Elke; Ryzhikov, Andrey; Jean Daou, T; Nouali, Habiba; Taulelle, Francis; Martens, Johan A; Patarin, Joël

    2016-07-28

    -COK-14 zeolite, the variant of COK-14 (OKO topology) with a systematically interrupted framework, exhibits unusual behaviour in high pressure intrusion-extrusion cycles of 20 M LiCl solution. After the first cycle with deviating behaviour and partially irreversible intrusion, subsequent cycles show stable reversible behaviour. The system behaves like a spring with unique progressive intrusion in the range of 10-120 MPa followed by enhanced uptake before saturation. While the intrusion-extrusion cycling leads to fragmented crystals, powder diffraction reveals high crystallinity of the fragments. Based on the detailed characterisation of the zeolite samples with XRD, Rietveld refinement, N2 adsorption, TGA and (29)Si MAS NMR before and after intrusion-extrusion experiments, a model of the structure of the intruded -COK-14 samples is proposed. Intrusion-extrusion of LiCl solution systematically breaks the most strained bonds in the structure which results in a new framework connectivity with enhanced stability, which persists during the harsh intrusion-extrusion conditions.

  6. Zeolites in Eocene basaltic pillow lavas of the Siletz River Volcanics, Central Coast Range, Oregon.

    USGS Publications Warehouse

    Keith, T.E.C.; Staples, L.W.

    1985-01-01

    Zeolites and associated minerals occur in a tholeiitic basaltic pillow lava sequence. Although the zeolite assemblages are similar to those found in other major zeolite occurrences in basaltic pillow lavas, regional zoning of the zeolite assemblages is not apparent. The formation of the different assemblages is discussed.-D.F.B.

  7. Zeolites in the Pine Ridge Indian Reservation, South Dakota

    USGS Publications Warehouse

    Raymond, William H.; Bush, Alfred L.; Gude, Arthur J.

    1982-01-01

    Zeolites of possible commercial value occur in the Brule Formation of Oligocene age and the Sharps Formation (Harksen, 1961) of Miocene age which crop out in a wide area in the northern part of the Pine Ridge Indian Reservation. The thickness of the zeolite-bearing Interval and the extent of areas within the Interval which contain significant amounts of zeolites are far greater than was expected prior to this investigation. The shape of the zeolite-bearing Interval is tabular and the dimensions of Its exposure are roughly 10 ml x 200 mi x 150 ft (16 km x 160 km x 45 m) thick. Within the study area, there are tracts in which the zeolite resource potential is significant (see pl. 2). This report is intended to inform the Oglala Sioux Tribe of some of the most promising zeolite occurrences. Initial steps can then be taken by the Tribe toward possible development of the resources, should they wish to do so. The data contained herein identify areas of high zeolite potential, but are not adequate to establish economic value for the deposits. If development is recommended by the tribal government, we suggest that the tribal government contact companies involved in research and production of natural zeolites and provide them with the data in this report.

  8. Crewmember working on the mid deck Zeolite Crystal Growth experiment.

    NASA Technical Reports Server (NTRS)

    1992-01-01

    View showing Payload Specialist Bonnie Dunbar, in the mid deck, conducting the Zeolite Crystal Growth (ZCG) Experiment in the mid deck stowage locker work area. View shows assembly of zeolite sample in the metal autoclave cylinders prior to insertion into the furnace.

  9. Selective thermal oxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    2000-01-01

    A process for selective thermal oxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls is carried out in solvent free zeolites under dark thermal conditions. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

  10. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, H.; Blatter, F.; Sun, H.

    1999-06-22

    A process is described for selective thermal oxidation or photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts. 19 figs.

  11. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    2001-01-01

    A process for a combined selective thermal oxidation and photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly combined selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

  12. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    1999-01-01

    A process for selective thermal oxidation or photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

  13. Antibacterial activity of heavy metal-loaded natural zeolite.

    PubMed

    Hrenovic, Jasna; Milenkovic, Jelena; Ivankovic, Tomislav; Rajic, Nevenka

    2012-01-30

    The antibacterial activity of natural zeolitized tuffs containing 2.60wt.% Cu(2+), 1.47 Zn(2+) or 0.52 Ni(2+) were tested. Antibacterial activities of the zeolites against Escherichia coli and Staphylococcus aureus were tested after 1h and 24h of exposure to 1g of the zeolite in 100mL of three different media, namely Luria Bertani, synthetic wastewater and secondary effluent wastewater. The antibacterial activities of the zeolites in Luria Bertani medium were significantly lower than those in the other media and negatively correlated with the chemical oxygen demand of the media. The Ni-loaded zeolite showed high leaching of Ni(2+) (3.44-9.13wt.% of the Ni(2+) loaded) and weak antibacterial activity in the effluent water. Since Cu-loaded zeolite did not leach Cu(2+) and the leaching of Zn(2+) from Zn-loaded zeolite was low (1.07-1.61wt.% of the Zn(2+) loaded), the strong antibacterial activity classified the Cu- and Zn-loaded zeolite as promising antibacterial materials for disinfection of secondary effluent water.

  14. Preferential orientations of structure directing agents in zeolites.

    PubMed

    Dib, Eddy; Gimenez, Antoine; Mineva, Tzonka; Alonso, Bruno

    2015-10-14

    The local structure of as-synthesised silicalite-1 zeolites is modified using asymmetric R(Pr)3N(+) structure directing agents. Using multi-nuclear NMR ((1)H, (13)C, (14)N, (19)F, (29)Si), we show for the first time the ability of these cations to adopt preferential orientations at the zeolite channels' crossing.

  15. FUNDAMENTALS AND APPLICATIONS OF PERVAPORATION THROUGH ZEOLITE MEMBRANES

    EPA Science Inventory

    Zeolite membranes are well suited for separating liquid-phase mixtures by pervaporation because of their molecular-sized pores and their hydrophilic/hydrophobic nature, and the first commercial application of zeolite membranes has been for dehydrating organics [1]. Because of ...

  16. Protein adsorption to hydrophobic Zeolite Y: salt effects and application to protein fractionation.

    PubMed

    Ghose, S; Mattiasson, B

    1993-12-01

    The binding equilibria of proteins with a hydrophobic variety of crystalline Zeolite Y is affected by salt and is a function of the type of salt and its concentration. The behaviour does not always follow the conventional pattern of increased binding at high salt concentrations and varies also for the different proteins involved. The overall process may be looked upon as a salting-in/salting-out mechanism. This material can be used as a surface for the selective adsorption of proteins and has been applied for the fractionation of ox heart homogenate in multi-stage operations. The presence of NaCl influences the protein binding, and this can be seen by monitoring the activity profile of lactate dehydrogenase. The bound protein can be reversed by treating the equilibrium mixture with low-molecular-mass poly(ethylene glycol)s.

  17. Aluminosilicate melts and glasses at 1 to 3 GPa: temperature and pressure effects on recovered structural and density changes

    NASA Astrophysics Data System (ADS)

    Bista, S.; Stebbins, J. F.; Hankins, B.; Sisson, T. W.

    2013-12-01

    The effects of pressure on aluminosilicate melt and glass structure have been studied by both in-situ methods and by quenching and recovering glasses from high pressure and temperature. Significant increases in the coordination number of Al are now well known from the pressure range of 6-10 GPa. New results show that even at shallower mantle pressures of 1-3 GPa, typical aluminosilicate melts have significant concentrations of aluminum cations with coordination numbers greater than 4, with up to 10's of percents of AlO5 and AlO6. Here, we compare the densities and Al coordinations of glass samples recovered from piston-cylinder experiments carried out at 1 to 3 GPa and different temperatures. Samples of two different compositions (Ca3Al2Si6O18 and Na2Si3O7 with 0.5% Al2O3) were compressed and held at temperatures ranging from near to their ambient glass transitions (Tg) up to temperatures above the liquidus. Our 2 GPa sodium aluminosilicate and calcium aluminosilicate glasses quenched from near to Tg show about 5 and 6 percent recovered densification, respectively. In both compositions, samples that were quenched from above the melting point showed substantially lower recovered density and lower Al coordination number compared to the samples that were held near to Tg. For example, sodium aluminosilicate glass quenched from 510°C (near to Tg) had 70% more AlO5 than samples from 1200°C. Based on the measurement of actual cooling rates, fictive temperature differences for the glasses from these two extreme temperatures are not large enough to account for this apparent loss in density and Al-coordination during quench. The most likely cause for these differences is therefore probably the pressure drop during cooling from temperatures above liquidus, as the pressure medium does not respond quickly enough to the thermal contraction of the liquid and furnace parts to remain isobaric. Results from previous high T and P quenching studies thus give only minimum estimates

  18. Non-bridging Oxygen and Five-coordinated Aluminum in Aluminosilicate Glasses: A Cation Field Strength Study

    NASA Astrophysics Data System (ADS)

    Thompson, L. M.; Stebbins, J. F.

    2011-12-01

    Linda M. Thompson Jonathan F. Stebbins Dept. of Geological and Environmental Sciences, Stanford University, Stanford CA 94305 Although it is understood in aluminosilicate melts and glasses that non-bridging oxygens (NBO) have significant influence on thermodynamic and transport properties, questions remain about its role and the extent of its influence, particularly in metaluminous and peraluminous compositions. One major question persists regarding whether the formation of NBO is in any way coupled with the formation of VAl (AlO5), which is significantly impacted by cation field strength (defined as the cation charge divided by the square of the distance between the cation and oxygen atoms) (Kelsey et al., 2009). Previous work on calcium and potassium aluminosilicate glasses has shown the presence of NBO on the metaluminous join and persisting into the peraluminous region, with significantly more NBO present in Ca glasses compared to K glasses of similar composition (Thompson and Stebbins, 2011). However, it is unclear if there is any systematic impact on NBO content by cation field strength similar to the impact on VAl. Expanding on the previous study, barium aluminosilicate glasses were synthesized covering a range of compositions crossing the metaluminous (e.g. BaAl2O4-SiO2) join to observe changes in the NBO for comparison against the calcium aluminosilicate glasses, thus looking at the impact of cation size on NBO versus cation charge. In the barium glasses on the 30 mol% SiO2 isopleth, the highest NBO content was 6.9% for the barium rich glass (R = 0.51, where R is Ba2+ / (Ba2+ + 2Al3+)) while the most peraluminous glass (R = 0.45) had an NBO content of 1.9%. Comparison of these results to earlier data shows these numbers are similar to what is observed in the Ca glasses, indicating cation size alone does not have a significant impact on NBO content. However the VAl content does show a decrease (compared to calcium aluminosilicate glasses at similar R values

  19. Fly ash based zeolitic pigments for application in anticorrosive paints

    NASA Astrophysics Data System (ADS)

    Shaw, Ruchi; Tiwari, Sangeeta

    2016-04-01

    The purpose of this work is to evaluate the utilization of waste fly ash in anticorrosive paints. Zeolite NaY was synthesized from waste fly ash and subsequently modified by exchanging its nominal cation Na+ with Mg2+ and Ca2+ ions. The metal ion exchanged zeolite was then used as anticorrosive zeolitic pigments in paints. The prepared zeolite NaY was characterized using X-Ray diffraction technique and Scanning electron microscopy. The size, shape and density of the prepared fly ash based pigments were determined by various techniques. The paints were prepared by using fly ash based zeolitic pigments in epoxy resin and the percentages of pigments used in paints were 2% and 5%. These paints were applied to the mild steel panels and the anticorrosive properties of the pigments were assessed by the electrochemical spectroscopy technique (EIS).

  20. Potential and actual uses of zeolites in crop protection.

    PubMed

    De Smedt, Caroline; Someus, Edward; Spanoghe, Pieter

    2015-10-01

    In this review, it is demonstrated that zeolites have a potential to be used as crop protection agents. Similarly to kaolin, zeolites can be applied as particle films against pests and diseases. Their honeycomb framework, together with their carbon dioxide sorption capacity and their heat stress reduction capacity, makes them suitable as a leaf coating product. Furthermore, their water sorption capacity and their smaller particle sizes make them effective against fungal diseases and insect pests. Finally, these properties also ensure that zeolites can act as carriers of different active substances, which makes it possible to use zeolites for slow-release applications. Based on the literature, a general overview is provided of the different basic properties of zeolites as promising products in crop protection.

  1. Modified zeolite-based catalyst for effective extinction hydrocracking

    SciTech Connect

    Yan, T.Y. )

    1989-10-01

    The shape selectivity of zeolites makes them generally ineffective for extinction hydrocracking of polycyclic aromatic feeds. To overcome this problem, the zeolite can be modified with an amorphous cracking component to form a composite catalyst. This composite catalyst will be effective for extinction hydrocracking and retain the superior performance characteristics of a zeolite catalyst at the same time because the zeolite and the amorphous components of the catalyst operate complementarily. To illustrate this principle, NiW/REX-NiW/SiO/sub 2/Al/sub 2/O/sub 3/ composite catalyst was tested in the pilot plant. It was active, low in aging rate, resistant to nitrogen poisoning and high in selectivities for naphthas. The aged catalyst could be oxidatively regenerated to fully recover the activity and the product selectivities. This composite catalyst was superior to both individual (zeolite and amorphous) components for extinction hydrocracking. Catalysts similar to this have been used commercially for many years.

  2. Synthesis and catalytic applications of combined zeolitic/mesoporous materials

    PubMed Central

    Vernimmen, Jarian; Cool, Pegie

    2011-01-01

    Summary In the last decade, research concerning nanoporous siliceous materials has been focused on mesoporous materials with intrinsic zeolitic features. These materials are thought to be superior, because they are able to combine (i) the enhanced diffusion and accessibility for larger molecules and viscous fluids typical of mesoporous materials with (ii) the remarkable stability, catalytic activity and selectivity of zeolites. This review gives an overview of the state of the art concerning combined zeolitic/mesoporous materials. Focus is put on the synthesis and the applications of the combined zeolitic/mesoporous materials. The different synthesis approaches and formation mechanisms leading to these materials are comprehensively discussed and compared. Moreover, Ti-containing nanoporous materials as redox catalysts are discussed to illustrate a potential implementation of combined zeolitic/mesoporous materials. PMID:22259762

  3. Preparation of a Versatile Bifunctional Zeolite for Targeted Imaging Applications

    PubMed Central

    Ndiege, Nicholas; Raidoo, Renugan; Schultz, Michael K.; Larsen, Sarah

    2011-01-01

    Bifunctional zeolite Y was prepared for use in targeted in vivo molecular imaging applications. The strategy involved functionalization of the external surface of zeolite Y with chloropropyltriethoxysilane followed by reaction with sodium azide to form azide-functionalized NaY, which is amenable to copper(1) catalyzed click chemistry. In this study, a model alkyne (4-pentyn-1-ol) was attached to the azide-terminated surface via click chemistry to demonstrate feasibility for attachment of molecular targeting vectors (e.g., peptides, aptamers) to the zeolite surface. The modified particle efficiently incorporates the imaging radioisotope gallium-68 (68Ga) into the pores of the azide-functionalized NaY zeolite to form a stable bifunctional molecular targeting vector. The result is a versatile “clickable” zeolite platform that can be tailored for future in vivo molecular targeting and imaging modalities. PMID:21306141

  4. Preparation of a versatile bifunctional zeolite for targeted imaging applications.

    PubMed

    Ndiege, Nicholas; Raidoo, Renugan; Schultz, Michael K; Larsen, Sarah

    2011-03-15

    Bifunctional zeolite Y was prepared for use in targeted in vivo molecular imaging applications. The strategy involved functionalization of the external surface of zeolite Y with chloropropyltriethoxysilane followed by reaction with sodium azide to form azide-functionalized NaY, which is amenable to copper(1)-catalyzed click chemistry. In this study, a model alkyne (4-pentyn-1-ol) was attached to the azide-terminated surface via click chemistry to demonstrate feasibility for attachment of molecular targeting vectors (e.g., peptides, aptamers) to the zeolite surface. The modified particle efficiently incorporates the imaging radioisotope gallium-68 ((68)Ga) into the pores of the azide-functionalized NaY zeolite to form a stable bifunctional molecular targeting vector. The result is a versatile "clickable" zeolite platform that can be tailored for future in vivo molecular targeting and imaging modalities.

  5. Relationships among the structural topology, bond strength, and mechanical properties of single-walled aluminosilicate nanotubes.

    PubMed

    Liou, Kai-Hsin; Tsou, Nien-Ti; Kang, Dun-Yen

    2015-10-21

    Carbon nanotubes (CNTs) are regarded as small but strong due to their nanoscale microstructure and high mechanical strength (Young's modulus exceeds 1000 GPa). A longstanding question has been whether there exist other nanotube materials with mechanical properties as good as those of CNTs. In this study, we investigated the mechanical properties of single-walled aluminosilicate nanotubes (AlSiNTs) using a multiscale computational method and then conducted a comparison with single-walled carbon nanotubes (SWCNTs). By comparing the potential energy estimated from molecular and macroscopic material mechanics, we were able to model the chemical bonds as beam elements for the nanoscale continuum modeling. This method allowed for simulated mechanical tests (tensile, bending, and torsion) with minimum computational resources for deducing their Young's modulus and shear modulus. The proposed approach also enabled the creation of hypothetical nanotubes to elucidate the relative contributions of bond strength and nanotube structural topology to overall nanotube mechanical strength. Our results indicated that it is the structural topology rather than bond strength that dominates the mechanical properties of the nanotubes. Finally, we investigated the relationship between the structural topology and the mechanical properties by analyzing the von Mises stress distribution in the nanotubes. The proposed methodology proved effective in rationalizing differences in the mechanical properties of AlSiNTs and SWCNTs. Furthermore, this approach could be applied to the exploration of new high-strength nanotube materials.

  6. First Principles Studies of Fe-Containing Aluminosilicate and Aluminogermanate Nanotubes.

    PubMed

    Alvarez-Ramírez, Fernando

    2009-12-08

    A theoretical study of the electronic effects of the inclusion of iron on aluminosilicates and aluminogermanates nanotubes with imogolite-like structure was carried out by unrestricted all-electron density functional theory calculations of periodic boundary models. The iron ion was incorporated to the imogolitic models by an isomorphic substitution of Al by Fe and by the adsorption of the Fe ion in the inner and outer nanotube structure in the octahedral hydrated configuration. Additionally, the effects of the Fe concentration in the interval 0.05 ≤ x ≤ 0.1 were analyzed. We observe a drastic reduction of the bandgap value from 4.6 to 2.6 eV and from 4.2 to 1.0 eV for the silicon and germanium respectively. Finally, in all the models there is a shift of the Fermi energy toward the gap region as a result of the inclusion of iron electronic states in the bandgap region.

  7. Pressure induced elastic softening in framework aluminosilicate- albite (NaAlSi3O8)

    DOE PAGES

    Mookherjee, Mainak; Mainprice, David; Maheshwari, Ketan; ...

    2016-10-13

    Albite (NaAlSi3O8) is an aluminosilicate mineral. Its crystal structure consists of 3-D framework of Al and Si tetrahedral units. We have used Density Functional Theory to investigate the high-pressure behavior of the crystal structure and how it affects the elasticity of albite. Our results indicate elastic softening between 6–8 GPa. This is observed in all the individual elastic stiffness components. Our analysis indicates that the softening is due to the response of the three-dimensional tetrahedral framework, in particular by the pressure dependent changes in the tetrahedral tilts. At pressure <6 GPa, the PAW-GGA can be described by a Birch-Murnaghan equationmore » of state with VGGA0 = 687.4Å3, KGGA0 = 51.7 GPa, and GGGA0 = 4.7. The shear modulus and its pressure derivative are K⊕GGA0 = 33.7 GPa, and G⊕GGA0 = 2.9. At 1 bar, the azimuthal compressional and shear wave anisotropy AVGGAP = 42.8%, and AVGGAS = 50.1%. We also investigate the densification of albite to a mixture of jadeite and quartz. The transformation is likely to cause a discontinuity in density, compressional, and shear wave velocity across the crust and mantle. Furthermore, this could partially account for the Mohorovicic discontinuity in thickened continental crustal regions.« less

  8. Effects of Thermal and Pressure Histories on the Chemical Strengthening of Sodium Aluminosilicate Glass

    NASA Astrophysics Data System (ADS)

    Svenson, Mouritz; Thirion, Lynn; Youngman, Randall; Mauro, John; Bauchy, Mathieu; Rzoska, Sylwester; Bockowski, Michal; Smedskjaer, Morten

    2016-03-01

    Glasses can be chemically strengthened through the ion exchange process, wherein smaller ions in the glass (e.g., Na+) are replaced by larger ions from a salt bath (e.g., K+). This develops a compressive stress (CS) on the glass surface, which, in turn, improves the damage resistance of the glass. The magnitude and depth of the generated CS depends on the thermal and pressure histories of the glass prior to ion exchange. In this study, we investigate the ion exchange-related properties (mutual diffusivity, CS, and hardness) of a sodium aluminosilicate glass, which has been densified through annealing below the initial fictive temperature of the glass or through pressure-quenching from the glass transition temperature at 1 GPa prior to ion exchange. We show that the rate of alkali interdiffusivity depends only on the density of the glass, rather than on the applied densification method. However, we also demonstrate that for a given density, the increase in CS and increase in hardness induced by ion exchange strongly depends on the densification method. Specifically, at constant density, the CS and hardness values achieved through thermal annealing are larger than those achieved through pressure-quenching. These results are discussed in relation to the structural changes in the environment of the network-modifier and the overall network densification.

  9. Molecular dynamics simulations of uranyl and uranyl carbonate adsorption at aluminosilicate surfaces.

    PubMed

    Kerisit, Sebastien; Liu, Chongxuan

    2014-04-01

    Adsorption at mineral surfaces is a critical factor controlling the mobility of uranium(VI) in aqueous environments. Therefore, molecular dynamics (MD) simulations were performed to investigate uranyl(VI) adsorption onto two neutral aluminosilicate surfaces, namely, the orthoclase (001) surface and the octahedral aluminum sheet of the kaolinite (001) surface. Although uranyl preferentially adsorbs as a bidentate inner-sphere complex on both surfaces, the free energy of adsorption on the orthoclase surface (-15 kcal mol(-1)) is significantly more favorable than that at the kaolinite surface (-3 kcal mol(-1)), which is attributed to differences in surface functional groups and the ability of the orthoclase surface to release a surface potassium ion upon uranyl adsorption. The structures of the adsorbed complexes compare favorably with X-ray absorption spectroscopy results. Simulations of the adsorption of uranyl complexes with up to three carbonate ligands revealed that uranyl complexes coordinated to up to two carbonate ions are stable on the orthoclase surface whereas uranyl carbonate surface complexes are unfavored at the kaolinite surface. Combining the MD-derived equilibrium adsorption constants for orthoclase with aqueous equilibrium constants for uranyl carbonate species indicates the presence of adsorbed uranium complexes with one or two carbonates under alkaline conditions, in support of current uranium(VI) surface complexation models.

  10. Single-Walled Aluminosilicate Nanotube/Poly(vinyl alcohol) Nanocomposite Membranes

    SciTech Connect

    Kang, Dun-Yen; Tong, Ho Ming; Zang, Ji; Choudhury, Rudra Prosad; Sholl, David S.; Beckham, Haskell W.; Jones, Christopher W.; Nair, Sankar

    2012-05-29

    The fabrication, detailed characterization, and molecular transport properties of nanocomposite membranes containing high fractions (up to 40 vol %) of individually-dispersed aluminosilicate single-walled nanotubes (SWNTs) in poly(vinyl alcohol) (PVA), are reported. The microstructure, SWNT dispersion, SWNT dimensions, and intertubular distances within the composite membranes are characterized by scanning and transmission electron microscopy (SEM and TEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), XRD rocking curve analysis, small-angle X-ray scattering (SAXS), and solid-state NMR. PVA/SWNT nanocomposite membranes prepared from SWNT gels allow uniform dispersion of individual SWNTs in the PVA matrix with a random distribution of orientations. SAXS analysis reveals the length ({approx}500 nm) and outer diameter ({approx}2.2 nm) of the dispersed SWNTs. Electron microscopy indicates good adhesion between the SWNTs and the PVA matrix without the occurrence of defects such as voids and pinholes. The transport properties of the PVA/SWNT membranes are investigated experimentally by ethanol/water mixture pervaporation measurements, computationally by grand canonical Monte Carlo and molecular dynamics, and by a macroscopic transport model for anisotropic permeation through nanotube-polymer composite membranes. The nanocomposite membranes substantially enhance the water throughput with increasing SWNT volume fraction, which leads to a moderate reduction of the water/ethanol selectivity. The model is parameterized purely from molecular simulation data with no fitted parameters, and shows reasonably good agreement with the experimental water permeability data.

  11. Molecular Dynamics Simulations of Uranyl and Uranyl Carbonate Adsorption at Alumino-silicate Surfaces

    SciTech Connect

    Kerisit, Sebastien N.; Liu, Chongxuan

    2014-03-03

    Adsorption at mineral surfaces is a critical factor controlling the mobility of uranium(VI) in aqueous environments. Therefore, molecular dynamics (MD) simulations were performed to investigate uranyl(VI) adsorption onto two neutral alumino-silicate surfaces, namely the orthoclase (001) surface and the octahedral aluminum sheet of the kaolinite (001) surface. Although uranyl preferentially adsorbed as a bi-dentate innersphere complex on both surfaces, the free energy of adsorption at the orthoclase surface (-15 kcal mol-1) was significantly more favorable than that at the kaolinite surface (-3 kcal mol-1), which was attributed to differences in surface functional groups and to the ability of the orthoclase surface to dissolve a surface potassium ion upon uranyl adsorption. The structures of the adsorbed complexes compared favorably with X-ray absorption spectroscopy results. Simulations of the adsorption of uranyl complexes with up to three carbonate ligands revealed that uranyl complexes coordinated to up to 2 carbonate ions are stable on the orthoclase surface whereas uranyl carbonate surface complexes are unfavored at the kaolinite surface. Combining the MD-derived equilibrium adsorption constants for orthoclase with aqueous equilibrium constants for uranyl carbonate species indicates the presence of adsorbed uranium complexes with one or two carbonates in alkaline conditions, in support of current uranium(VI) surface complexation models.

  12. Lithium aluminosilicate reinforced with carbon nanofiber and alumina for controlled-thermal-expansion materials

    NASA Astrophysics Data System (ADS)

    Borrell, Amparo; García-Moreno, Olga; Torrecillas, Ramón; García-Rocha, Victoria; Fernández, Adolfo

    2012-02-01

    Materials with a very low or tailored thermal expansion have many applications ranging from cookware to the aerospace industry. Among others, lithium aluminosilicates (LAS) are the most studied family with low and negative thermal expansion coefficients. However, LAS materials are electrical insulators and have poor mechanical properties. Nanocomposites using LAS as a matrix are promising in many applications where special properties are achieved by the addition of one or two more phases. The main scope of this work is to study the sinterability of carbon nanofiber (CNFs)/LAS and CNFs/alumina/LAS nanocomposites, and to adjust the ratio among components for obtaining a near-zero or tailored thermal expansion. Spark plasma sintering of nanocomposites, consisting of commercial CNFs and alumina powders and an ad hoc synthesized β-eucryptite phase, is proposed as a solution to improving mechanical and electrical properties compared with the LAS ceramics obtained under the same conditions. X-ray diffraction results on phase compositions and microstructure are discussed together with dilatometry data obtained in a wide temperature range (-150 to 450 °C). The use of a ceramic LAS phase makes it possible to design a nanocomposite with a very low or tailored thermal expansion coefficient and exceptional electrical and mechanical properties.

  13. Lithium aluminosilicate reinforced with carbon nanofiber and alumina for controlled-thermal-expansion materials.

    PubMed

    Borrell, Amparo; García-Moreno, Olga; Torrecillas, Ramón; García-Rocha, Victoria; Fernández, Adolfo

    2012-02-01

    Materials with a very low or tailored thermal expansion have many applications ranging from cookware to the aerospace industry. Among others, lithium aluminosilicates (LAS) are the most studied family with low and negative thermal expansion coefficients. However, LAS materials are electrical insulators and have poor mechanical properties. Nanocomposites using LAS as a matrix are promising in many applications where special properties are achieved by the addition of one or two more phases. The main scope of this work is to study the sinterability of carbon nanofiber (CNFs)/LAS and CNFs/alumina/LAS nanocomposites, and to adjust the ratio among components for obtaining a near-zero or tailored thermal expansion. Spark plasma sintering of nanocomposites, consisting of commercial CNFs and alumina powders and an ad hoc synthesized β-eucryptite phase, is proposed as a solution to improving mechanical and electrical properties compared with the LAS ceramics obtained under the same conditions. X-ray diffraction results on phase compositions and microstructure are discussed together with dilatometry data obtained in a wide temperature range (-150 to 450 °C). The use of a ceramic LAS phase makes it possible to design a nanocomposite with a very low or tailored thermal expansion coefficient and exceptional electrical and mechanical properties.

  14. Chemical and mechanical consequences of environmental barrier coating exposure to calcium-magnesium-aluminosilicate.

    SciTech Connect

    Harder, B.; Ramirez-Rico, J.; Almer, J. D.; Kang, L.; Faber, K.

    2011-06-01

    The success of Si-based ceramics as high-temperature structural materials for gas turbine applications relies on the use of environmental barrier coatings (EBCs) with low silica activity, such as Ba{sub 1-x}Sr{sub x}Al{sub 2}Si{sub 2}O{sub 8} (BSAS), which protect the underlying components from oxidation and corrosion in combustion environments containing water vapor. One of the current challenges concerning EBC lifetime is the effect of sandy deposits of calcium-magnesium-aluminosilicate (CMAS) glass that melt during engine operation and react with the EBC, changing both its composition and stress state. In this work, we study the effect of CMAS exposure at 1300 C on the residual stress state and composition in BSAS-mullite-Si-SiC multilayers. Residual stresses were measured in BSAS multilayers exposed to CMAS for different times using high-energy X-ray diffraction. Their microstructure was studied using a combination of scanning electron microscopy and transmission electron microscopy techniques. Our results show that CMAS dissolves the BSAS topcoat preferentially through the grain boundaries, dislodging the grains and changing the residual stress state in the topcoat to a nonuniform and increasingly compressive stress state with increasing exposure time. The presence of CMAS accelerates the hexacelsian-to-celsian phase transformation kinetics in BSAS, which reacts with the glass by a solution-reprecipitation mechanism. Precipitates have crystallographic structures consistent with Ca-doped celsian and Ba-doped anorthite.

  15. Pressure induced elastic softening in framework aluminosilicate- albite (NaAlSi3O8)

    PubMed Central

    Mookherjee, Mainak; Mainprice, David; Maheshwari, Ketan; Heinonen, Olle; Patel, Dhenu; Hariharan, Anant

    2016-01-01

    Albite (NaAlSi3O8) is an aluminosilicate mineral. Its crystal structure consists of 3-D framework of Al and Si tetrahedral units. We have used Density Functional Theory to investigate the high-pressure behavior of the crystal structure and how it affects the elasticity of albite. Our results indicate elastic softening between 6–8 GPa. This is observed in all the individual elastic stiffness components. Our analysis indicates that the softening is due to the response of the three-dimensional tetrahedral framework, in particular by the pressure dependent changes in the tetrahedral tilts. At pressure <6 GPa, the PAW-GGA can be described by a Birch-Murnaghan equation of state with  = 687.4 Å3,  = 51.7 GPa, and  = 4.7. The shear modulus and its pressure derivative are  = 33.7 GPa, and  = 2.9. At 1 bar, the azimuthal compressional and shear wave anisotropy  = 42.8%, and  = 50.1%. We also investigate the densification of albite to a mixture of jadeite and quartz. The transformation is likely to cause a discontinuity in density, compressional, and shear wave velocity across the crust and mantle. This could partially account for the Mohorovicic discontinuity in thickened continental crustal regions. PMID:27734903

  16. Atomic mobility in calcium and sodium aluminosilicate melts at 1200 °C

    NASA Astrophysics Data System (ADS)

    Claireaux, Corinne; Chopinet, Marie-Hélène; Burov, Ekaterina; Gouillart, Emmanuelle; Roskosz, Mathieu; Toplis, Michael J.

    2016-11-01

    Multicomponent chemical diffusion in liquids of the quaternary system CaO-Na2O-Al2O3-SiO2 has been studied. Diffusion-couple experiments were performed at 1200 °C and for different durations around a central composition of 64.5 wt%SiO2, 13.3 wt%Na2O, 10.8 wt%CaO, 11.4 wt%Al2O3, leading to an overconstrained system of equations that was used to determine the diffusion matrix of the system. The dominant eigenvector of the diffusion matrix was found to correspond to the exchange between sodium and calcium, consistent with the results of the ternary soda-lime silica system. On the other hand, neither of the other two eigenvectors of the diffusion matrix of the quaternary system involve sodium. Given a factor of 50 between the dominant and second eigenvalue, diffusion couples involving the exchange of sodium oxide and a network-forming oxide result in strong uphill diffusion of calcium. The second eigenvector, corresponding to the exchange of calcium with silicon and aluminum, is close to the dominant eigenvector found in previous studies of ternary alkaline-earth aluminosilicate systems. Our results therefore suggest that simple systems may be used to understand diffusive mechanisms in more complex systems.

  17. Lithium aluminosilicate reinforced with carbon nanofiber and alumina for controlled-thermal-expansion materials

    PubMed Central

    Borrell, Amparo; García-Moreno, Olga; Torrecillas, Ramón; García-Rocha, Victoria; Fernández, Adolfo

    2012-01-01

    Materials with a very low or tailored thermal expansion have many applications ranging from cookware to the aerospace industry. Among others, lithium aluminosilicates (LAS) are the most studied family with low and negative thermal expansion coefficients. However, LAS materials are electrical insulators and have poor mechanical properties. Nanocomposites using LAS as a matrix are promising in many applications where special properties are achieved by the addition of one or two more phases. The main scope of this work is to study the sinterability of carbon nanofiber (CNFs)/LAS and CNFs/alumina/LAS nanocomposites, and to adjust the ratio among components for obtaining a near-zero or tailored thermal expansion. Spark plasma sintering of nanocomposites, consisting of commercial CNFs and alumina powders and an ad hoc synthesized β-eucryptite phase, is proposed as a solution to improving mechanical and electrical properties compared with the LAS ceramics obtained under the same conditions. X-ray diffraction results on phase compositions and microstructure are discussed together with dilatometry data obtained in a wide temperature range (−150 to 450 °C). The use of a ceramic LAS phase makes it possible to design a nanocomposite with a very low or tailored thermal expansion coefficient and exceptional electrical and mechanical properties. PMID:27877474

  18. Synthesis of hydrothermally stable, hierarchically mesoporous aluminosilicate Al-SBA-1 and their catalytic properties

    NASA Astrophysics Data System (ADS)

    Li, Na; Wang, Jin-Gui; Xu, Jian-Xiong; Liu, Jin-Yu; Zhou, Hui-Jing; Sun, Ping-Chuan; Chen, Tie-Hong

    2012-03-01

    Hydrothermally stable mesoporous aluminosilicates Al-SBA-1 with hierarchical pore structure have been successfully synthesized under alkaline condition at 120 °C by employing organic mesomorphous complexes of polyelectrolyte (poly(acrylic acid) (PAA)) and cationic surfactant (hexadecyl pyridinium chloride (CPC)) as template. The Si/Al ratio could be as high as 5 and the incorporation of Al into the silica framework did not disturb the well-ordered cubic Pm3&cmb.macr;n mesostructure. Meanwhile, the incorporation of Al could greatly increase the specific surface area and pore volume of the samples. The Al-SBA-1 materials exhibited a high hydrothermal stability and remained stable even after being treated in boiling water for 10 days. The catalytic activity of the Al-SBA-1 materials was investigated by employing the Friedel-Crafts alkylation of toluene with benzyl alcohol as a model reaction and they exhibited excellent catalytic property due to the incorporated acid sites and the hierarchically mesoporous structure.

  19. Surface structure and structural point defects of liquid and amorphous aluminosilicate nanoparticles

    NASA Astrophysics Data System (ADS)

    Linh, Nguyen Ngoc; Van Hoang, Vo

    2008-07-01

    The surface structure of liquid and amorphous aluminosilicate nanoparticles of composition Al2O3·2SiO2 has been investigated in a model of different sizes ranging from 2.0 to 5.0 nm with the Born-Mayer type pair potential under non-periodic boundary conditions. Models have been obtained by cooling from the melts at a constant density of 2.6 g cm-3 via molecular dynamics (MD) simulation. The surface structure has been investigated via the coordination number, bond-angle distributions and structural point defects. Calculations show that surface effects on surface static and thermodynamic properties of models are significant according to the change in the number of Al atoms in the surface layers. Evolution of the local environment of oxygen in the surface shell of nanoparticles upon cooling from the melt toward the glassy state was also found and discussed. In addition, the nanosize dependence of the glass transition temperature was presented.

  20. Fabrication of large diameter alumino-silicate K{sup +} sources

    SciTech Connect

    Baca, D.; Chacon-Golcher, E.; Kwan, J.W.; Wu, J.K.

    2003-02-20

    Alumino-silicate K{sup +} sources have been used in HIF experiments for many years. For example the Neutralized Transport Expt. (NTX) and the High Current Transport Expt. (HCX) are now using this type of ion source with diameters of 2.54 cm and 10 cm respectively. These sources have demonstrated ion currents of 80 mA and 700 mA, for typical HIF pulse lengths of 5-10 {micro}s. The corresponding current density is {approx} 10-15 mA/cm{sup 2}, but much higher current density has been observed using smaller size sources. Recently we have improved our fabrication techniques and, therefore, are able to reliably produce large diameter ion sources with high quality emitter surface without defects. This note provides a detailed description of the procedures employed in the fabrication process. The variables in the processing steps affecting surface quality, such as substrate porosity, powder size distribution, coating technique on large area concave surfaces, drying, and heat firing temperature have been investigated.