Sample records for solid silicate matrix

  1. Calcined sodium silicate as solid base catalyst for biodiesel production

    Guo, Feng; Peng, Zhen-Gang; Dai, Jian-Ying; Xiu, Zhi-Long [Department of Bioscience and Biotechnology, School of Environmental and Biological Science and Technology, Dalian University of Technology, Dalian 116024 (China)


    This paper examined the use of calcined sodium silicate as a novel solid base catalyst in the transesterification of soybean oil with methanol. The calcined sodium silicate was characterized by DTA-TG, Hammett indicator method, XRD, SEM, BET, IR and FT-IR. It catalyzed the transesterification of soybean oil to biodiesel with a yield of almost 100% under the following conditions: sodium silicate of 3.0 wt.%, a molar ratio of methanol/oil of 7.5:1, reaction time of 60 min, reaction temperature of 60 C, and stirring rate of 250 rpm. The oil containing 4.0 wt.% water or 2.5 wt.% FFA could also be transesterified by using this catalyst. The catalyst can be reused for at least 5 cycles without loss of activity. (author)

  2. Photostable Solid Dispersion of Nifedipine by Porous Calcium Silicate.

    Fujimoto, Yumi; Hirai, Nobuaki; Takatani-Nakase, Tomoka; Takahashi, Koichi


    Nifedipine (NIF) is a typical light-sensitive drug requiring protection from light during manufacture, storage, and handling of its dosage forms. The purpose of this study was to evaluate the utility of porous calcium silicate (PCS) for maintaining the photostability of NIF in a solid dispersion formulation. Adsorption solid dispersion (ASD) prepared using NIF and PCS as an amorphous formulation was more stable to light irradiation than a physical mixture of NIF and microcrystalline cellulose (a control physical mixture) as a crystalline formulation. In addition, PCS in physical mixtures with NIF adequately protected NIF from photodegradation, suggesting that this protective effect could be because of some screening effect by the porous structure of PCS blocking the passage of light reaching NIF in pores of PCS. These findings suggest that PCS is useful for improving the solubility and photostability of NIF in solid dispersion formulation.

  3. Solid-matrix luminescence analysis

    Hurtubise, R.J.


    Several interactions with lumiphors adsorbed on filter paper were elucidated from experiments with moisture, modulus and heavy-atom salts. The data were interpreted using static and dynamic quenching models, heavy-atom theory, and a theory related to the modulus of paper. With cyclodextrin-salt matrices, it was shown that 10% [alpha]-cyclodextrin/NaCl was very effective for obtaining strong room-temperature fluorescence and moderate room-temperature phosphorescence from adsorbed stereoisomeric tetrols. Extensive photophysical information was obtained for the four tetrols on 10% [alpha]-cyclodextrin/NaCl. The photophysical information acquired was used to develop a method for characterizing two of the tetrols. Work with model compounds adsorbed on deuterated sodium acetate showed that C-H vibrations in the undeuterated sodium acetate were not responsible for the deactivation of the excited triplet state in the model phosphors investigated. A considerable amount of solution luminescence and solid-matrix luminescence data were compared. The most important finding was that in several cases the room-temperature solid-matrix luminescence quantum yields were greater than the solution low-temperature quantum yield values.

  4. Evaluation of apatite silicates as solid oxide fuel cell electrolytes

    Marrero-Lopez, D. [Dpto. de Fisica Aplicada I, Laboratorio de Materiales y Superficies (Unidad Asociada al C.S.I.C.), Universidad de Malaga, 29071 Malaga (Spain); Dpto. de Quimica Inorganica, Universidad de La Laguna, 38200 La Laguna, Tenerife (Spain); Martin-Sedeno, M.C.; Aranda, M.A.G. [Dpto. de Quimica Inorganica, Universidad Malaga, 29071 Malaga (Spain); Pena-Martinez, J. [Dpto. de Quimica Inorganica, Universidad de La Laguna, 38200 La Laguna, Tenerife (Spain); Instituto de Energias Renovables, Parque Tecnologico, Universidad de Castilla La Mancha, 02006 Albacete (Spain); Ruiz-Morales, J.C.; Nunez, P. [Dpto. de Quimica Inorganica, Universidad de La Laguna, 38200 La Laguna, Tenerife (Spain); Ramos-Barrado, J.R. [Dpto. de Fisica Aplicada I, Laboratorio de Materiales y Superficies (Unidad Asociada al C.S.I.C.), Universidad de Malaga, 29071 Malaga (Spain)


    Apatite-type silicates have been considered as promising electrolytes for Solid Oxide Fuel Cells (SOFC); however studies on the potential use of these materials in SOFC devices have received relatively little attention. The lanthanum silicate with composition La{sub 10}Si{sub 5.5}Al{sub 0.5}O{sub 26.75} has been evaluated as electrolyte with the electrode materials commonly used in SOFC, i.e. manganite, ferrite and cobaltite as cathode materials and NiO-CGO composite, chromium-manganite and Sr{sub 2}MgMoO{sub 6} as anode materials. Chemical compatibility, area-specific resistance and fuel cell studies have been performed. X-ray powder diffraction (XRPD) analysis did not reveal any trace of reaction products between the apatite electrolyte and most of the aforementioned electrode materials. However, the area-specific polarisation resistance (ASR) of these electrodes in contact with apatite electrolyte increased significantly with the sintering temperature, indicating reactivity at the electrolyte/electrode interface. On the other hand, the ASR values are significantly improved using a ceria buffer layer between the electrolyte and electrode materials to prevent reactivity. Maximum power densities of 195 and 65 mWcm{sup -2} were obtained at 850 and 700 C, respectively in H{sub 2} fuel, using an 1 mm-thick electrolyte, a NiO-Ce{sub 0.8}Gd{sub 0.2}O{sub 1.9} composite as anode and La{sub 0.6}Sr{sub 0.4}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} as cathode materials. This fuel cell was tested for 100 h in 5%H{sub 2}-Ar atmosphere showing stable performance. (author)

  5. Use of propranolol-magnesium aluminium silicate intercalated complexes as drug reservoirs in polymeric matrix tablets

    T Pongjanyakul


    Full Text Available The objective of the present study was to investigate the use of propranolol-magnesium aluminium silicate intercalated complexes as drug reservoirs in hydroxypropylmethylcellulose tablets. The matrix tablets containing the complexes were prepared and characterised with respect to propranolol release and were subsequently compared with those loading propranolol or a propranolol-magnesium aluminium silicate physical mixture. Additionally, the effects of varying viscosity grades of hydroxypropyl methylcellulose, compression pressures and calcium acetate incorporation on the drug release characteristics of the complex-loaded tablets were also examined. The results showed that the complex-loaded tablets have higher tablet hardness than those containing propranolol or a physical mixture. The drug release from the complex-loaded tablets followed a zero-order release kinetic, whereas an anomalous transport was found in the propranolol or physical mixture tablets. The drug release rate of the complex tablet significantly decreased with increasing hydroxypropylmethylcellulose viscosity grade. Increase in the compression pressure caused a decrease in the drug release rate of the tablets. Furthermore, the incorporation of calcium ions could accelerate propranolol release, particularly in acidic medium, because calcium ions could be exchanged with propranolol molecules intercalated in the silicate layers of magnesium aluminium silicate. These findings suggest that propranolol-magnesium aluminium silicate intercalated complexes show strong potential for use as drug reservoirs in matrix tablets intended for modifying drug release.

  6. High-resolution oxygen-17 NMR of solid silicates

    Mueller, K.T.; Wu, Y.; Chmelka, B.F. (Lawrence Berkeley Lab., CA (USA)); Stebbins, J. (Stanford Univ, CA (USA)); Pines, A. (Univ. of California, Berkeley (USA))


    Several{sup 17}O-enriched silicates were studied by use of dynamic angle spinning (DAS) and double rotation (DOR) nuclear magnetic resonance spectroscopy. These methods average away second-order quadrupolar interactions by reorienting a sample about a time-dependent axis, thereby yielding high-resolution spectra of oxygen-17 nuclei. A narrow spectral line is observed for each distinct oxygen site at the sum of the isotropic chemical shift and the field-dependent isotropic second-order quadrupolar shift. Resolution is increased by up to 2 orders of magnitude compared to conventional magic angle spinning (MAS) spectra. Crystallographically inequivalent oxygen are now observable as distinct resonances in spectra of polycrystalline silicates such as diopside (CaMgSi{sub 2}{sup 17}O{sub 6}), wollastonite (CaSi{sup 17}O{sub 3}), larnite (Ca{sub 2}Si{sup 17}O{sub 4}), and forsterite (Mg{sub 2}Si{sup 17}O{sub 4}).

  7. Cellular morphology of organic-inorganic hybrid foams based on alkali alumino-silicate matrix

    Verdolotti, Letizia; Capasso, Ilaria; Lavorgna, Marino [Institute of Composite and Biomedical Materials, National Research Council, Naples (Italy); Liguori, Barbara; Caputo, Domenico [Department of Chemical, Materials and Industrial Engineering, University of Naples Federico II, Naples (Italy); Iannace, Salvatore [Institute of Composite and Biomedical Materials, National Research Council, Naples, Italy and IMAST SCRAL, Piazza Bovio 22 Napoli 80133 (Italy)


    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/m{sup 3}) 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.

  8. The development of silicate matrix phosphors with broad excitation band for phosphor-convered white LED

    LUO XiXian; CAO WangHe; SUN Fei


    This paper briefly reviews the recent progress in alkaline earth silicate host luminescent materials with broad excitation band for phosphor-convered white LED. Among them, the Sr-rich binary phases (Sr, Ba, Ca, Mg)2SiO4: Eu2+ and (Sr, Ba, Ca, Mg)3SiO5: Eu2+ are excellent phosphors for blue LED chip white LED. They have very broad excitation bands and exhibit strong absorption of blue radiation in the range of 450-480 nm. And they exhibit green and yellow-orange emission under the InGaN blue LED chip radiation, respectively. The luminous efficiency of InGaN-based (Sr, Ba, Ca, Mg)2SiO4: Eu2+ and (Sr, Ba, Ca, Mg)3SiO5: Eu2+ is about 70-80 lm/W, about 95%-105% that of the InGaN-based YAG:Ce, while the correlated color temperature is between 4600-11000 K. Trinary alkaline earth silicate host luminescent materials MO(M=Sr, Ca, Ba)-Mg(Zn)O-SiO2 show strong absorption of deep blue/near-ultraviolet radia-tion in the range of 370-440 nm. They can convert the deep blue/near-ultraviolet radiation into blue, green, and red emissions to generate white light. The realization of high-performance white-light LEDs by this approach presents excellent chromaticity and high color rendering index, and the application disadvantages caused by the mixture of various matrixes can be avoided. Moreover, the application prospects and the trends of research and development of alkaline earth silicate phosphors are also discussed.

  9. Understanding the defect chemistry of alkali metal strontium silicate solid solutions: insights from experiment and theory

    Bayliss, Ryan D.


    © the Partner Organisations 2014. Recent reports of remarkably high oxide ion conduction in a new family of strontium silicates have been challenged. It has recently been demonstrated that, in the nominally potassium substituted strontium germanium silicate material, the dominant charge carrier was not the oxygen ion, and furthermore that the material was not single phase (R. D. Bayliss et. al., Energy Environ. Sci., 2014, DOI: 10.1039/c4ee00734d). In this work we re-investigate the sodium-doped strontium silicate material that was reported to exhibit the highest oxide ion conductivity in the solid solution, nominally Sr0.55Na0.45SiO2.775. The results show lower levels of total conductivity than previously reported and sub-micron elemental mapping demonstrates, in a similar manner to that reported for the Sr0.8K0.2Si0.5Ge0.5O2.9 composition, an inhomogeneous chemical distribution correlating with a multiphase material. It is also shown that the conductivity is not related to protonic mobility. A density functional theory computational approach provides a theoretical justification for these new results, related to the high energetic costs associated with oxygen vacancy formation. This journal is

  10. Dispersion of Silicate in Tricalcium Phosphate Elucidated by Solid-State NMR

    Rewal, A.; Wei, X.; Akinc, M.; Schmidt-Rohr, K.


    The dispersion of silicate in tricalcium phosphate, a resorbable bioceramics for bone replacement, has been investigated by various solid-state nuclear magnetic resonance (NMR) methods. In samples prepared with 5 and 10 mol% of both {sup 29}SiO{sub 2} and ZnO, three types of silicate have been detected: (i) SiO{sub 4}{sup 4-} (Q{sub 0} sites) with long longitudinal (T{sub 1,Si}) relaxation times ({approx} 10,000 s), which substitute for {approx}1% of PO{sub 4}{sup 3-}; (ii) silicate nanoinclusions containing Q{sub 2}, Q{sub 1}, and Q{sub 0} sites with T{sub 1,Si} 100 s, which account for most of the silicon; and (iii) crystalline Q{sub 4} (SiO{sub 2}) with long T{sub 1,Si}. Sensitivity was enhanced >100-fold by {sup 29}Si enrichment and refocused detection. The inclusions in both samples have a diameter of {approx}8 nm, as proved by {sup 29}Si{l_brace}{sup 31}P{r_brace} REDOR dephasing on a 30-ms time scale, which was simulated using a multispin approach specifically suited for nanoparticles. {sup 29}Si CODEX NMR with 30-s {sup 29}Si spin diffusion confirms that an inclusion contains >10 Si (consistent with the REDOR result of >100 Si per inclusion). Overlapping signals of silicate Q{sub 2}, Q{sub 1}, and Q{sub 0} sites were spectrally edited based on their J-couplings, using double-quantum filtering. The large inhomogeneous broadening of the Q{sub 2}, Q{sub 1}, and Q{sub 0} {sup 29}Si subspectra indicates that the nanoinclusions are amorphous.

  11. Low Velocity Impact and Creep-Strain Behaviour of Vinyl Ester Matrix Nanocomposites Based on Layered Silicate

    A. I. Alateyah


    Full Text Available The impact properties of neat vinyl ester and the nanocomposites were performed using a low velocity impact testing. The addition of layered silicate into the polymer matrix shows that an optimum range of nanoclay reinforcement in the vinyl ester matrix can produce enhanced load bearing and energy absorption capability compared to the neat matrix. In addition, the amount of microvoids in the nanocomposites structure influences the overall properties. Likewise, the influence of the clay addition into the neat polymer on the creep relaxation behaviour at 25°C and 60°C was studied. In both cases, the presence of the layered silicate remarkably improved the creep behaviour. The improvement of these properties can be assigned to the stiff fillers and the configurational linkage between the polymer and the layered silicate which are supported by scanning electron microscopy (SEM and transmission electron microscopy (TEM characterisations by showing a distinct change in surface morphology associated with improved impact toughness and creep response.

  12. A Solid State NMR Investigation of Recent Marine Siliceous Sponge Spicules

    Sylvie Masse


    Full Text Available The composition of four recent siliceous marine sponge spicules was studied and compared. In particular, multinuclear (29Si, 13C, 31P solid state nuclear magnetic resonance (NMR allowed the characterization of both the mineral and organic constituents in a non-destructive manner. The silica network condensation was similar for all samples. The organic matter showed a similar pattern but varied in abundance as a function of the sponge group (Hexactinellida or Demospongiae and sampling conditions (living or dead organisms. This indicates that the striking morphological differences observed at the macroscale for the various samples do not lead to significant fingerprints in the spectroscopic signatures of the mineral and organic constituents.

  13. Ultrasonic Monitoring of the Interaction between Cement Matrix and Alkaline Silicate Solution in Self-Healing Systems.

    Ait Ouarabi, Mohand; Antonaci, Paola; Boubenider, Fouad; Gliozzi, Antonio S; Scalerandi, Marco


    Alkaline solutions, such as sodium, potassium or lithium silicates, appear to be very promising as healing agents for the development of encapsulated self-healing concretes. However, the evolution of their mechanical and acoustic properties in time has not yet been completely clarified, especially regarding their behavior and related kinetics when they are used in the form of a thin layer in contact with a hardened cement matrix. This study aims to monitor, using linear and nonlinear ultrasonic methods, the evolution of a sodium silicate solution interacting with a cement matrix in the presence of localized cracks. The ultrasonic inspection via linear methods revealed that an almost complete recovery of the elastic and acoustic properties occurred within a few days of healing. The nonlinear ultrasonic measurements contributed to provide further insight into the kinetics of the recovery due to the presence of the healing agent. A good regain of mechanical performance was ascertained through flexural tests at the end of the healing process, confirming the suitability of sodium silicate as a healing agent for self-healing cementitious systems.

  14. Ultrasonic Monitoring of the Interaction between Cement Matrix and Alkaline Silicate Solution in Self-Healing Systems

    Mohand Ait Ouarabi


    Full Text Available Alkaline solutions, such as sodium, potassium or lithium silicates, appear to be very promising as healing agents for the development of encapsulated self-healing concretes. However, the evolution of their mechanical and acoustic properties in time has not yet been completely clarified, especially regarding their behavior and related kinetics when they are used in the form of a thin layer in contact with a hardened cement matrix. This study aims to monitor, using linear and nonlinear ultrasonic methods, the evolution of a sodium silicate solution interacting with a cement matrix in the presence of localized cracks. The ultrasonic inspection via linear methods revealed that an almost complete recovery of the elastic and acoustic properties occurred within a few days of healing. The nonlinear ultrasonic measurements contributed to provide further insight into the kinetics of the recovery due to the presence of the healing agent. A good regain of mechanical performance was ascertained through flexural tests at the end of the healing process, confirming the suitability of sodium silicate as a healing agent for self-healing cementitious systems.

  15. The role of an organic matrix during the formation of siliceous scales in the heliozoon Actinophrys sol (actinophryida, protista).

    Newman, P J; Patterson, D J


    Actinophrys sol is a freshwater heliozoon which has trophic and encysted body forms. During encystment, siliceous scales are laid down in silica deposition vesicles. The scales form one layer of a multi-layered cyst wall. Scale production is described using light microscopy, transmission electron microscopy, scanning electron microscopy, and X-ray microanalysis. Silica is laid down on an organic matrix which is visible prior to silicification and after removal of silica with hydrofluoric acid. Actinophrys sol can be cultured under silica impoverished conditions, with the result that the siliceous plates are absent. The cysts continue to form but are fragile. Silica is not a prerequisite for the processes of encystment and cyst formation. Copyright © 1993 Gustav Fischer Verlag · Stuttgart · Jena · New York. Published by Elsevier GmbH.. All rights reserved.

  16. Environmental Topology and Water Availability Modulates the Catalytic Activity of β-Galactosidase Entrapped in a Nanosporous Silicate Matrix

    M. Ines Burgos; Manuel I. Velasco; Acosta, Rodolfo H.; María A. Perillo


    In the present work we studied the catalytic activity of E. coli β-Gal confined in a nanoporous silicate matrix (Eβ-Gal) at different times after the beginning of the sol-gel polymerization process. Enzyme kinetic experiments with two substrates (ONPG and PNPG) that differed in the rate-limiting steps of the reaction mechanism for their β-Gal-catalyzed hydrolysis, measurements of transverse relaxation times (T 2 ) of water protons through 1H-NMR, and scanning electron microscopy analysis of t...

  17. Template-engaged solid-state synthesis of barium–strontium silicate hexagonal tubes

    Chen, Xuncai; Kim, Woo-Sik, E-mail:


    Solid materials with hollow structures are of significant interest due to their beneficial features, such as a high surface to volume ratio, high void space in the structure, and low apparent density, allowing such applications as high efficiency catalysts and drug delivery agent. This study presents a new synthetic method for generating hexagonal hollow tubes of (BaSr)SiO{sub 4} via a template-engaged solid–solid reaction. First, the composition tuneable (BaSr)CO{sub 3} hexagonal rods were prepared as the template by the co-precipitation of Ba{sup 2+}, Sr{sup 2+}, and then uniformly shelled with the silica (SiO{sub 2}) using CTAB, thereby forming (BaSr)CO{sub 3}–SiO{sub 2} core–shell rods. The SiO{sub 2} shell thickness is adjustable based on the TEOS concentration in the sol–gel process. The (BaSr)CO{sub 3}–SiO{sub 2} core–shell rods were converted to the (BaSr)SiO{sub 4} hexagonal hollow tubes by an interfacial solid–solid reaction between the (BaSr)CO{sub 3} core and SiO{sub 2} shell at 750 °C. During this interfacial solid–solid reaction, the (BaSr)CO{sub 3} hexagonal rods are the template for hexagonal tubes of (BaSr)SiO{sub 4}. Kirkendall effect contributes to the formation of hollow tube structure of (BaSr)SiO{sub 4}. The proposed synthetic method demonstrated a significant advantage for the preparation of (BaSr)SiO:Eu{sup 2+} phosphor, where the synthetic temperature was reduced from 1200 °C to 500 °C when compared with the conventional method. The photoluminescence property of the hollow tubular (BaSr)SiO:Eu{sup 2+} showed a green emission between 480 nm and 600 nm with the maximum peak intensity at 517 nm under UV excitation. This synthetic method could also be applied to the preparation of hollow-structured multi-component metal silicates.

  18. Solidification/stabilization and leaching behavior of PbCl₂ in fly-ash hydrated silicate matrix and fly-ash geopolymer matrix.

    Li, Yang; Gao, Xingbao; Wang, Qi; He, Jie; Yan, Dahai


    Fly ash (FA) for reuse as a construction material is activated using two methods, to produce hydrated silicate and geopolymer gels. We investigated the solidification/stabilization and leaching behavior of PbCl2 in a geopolymer matrix (GM) and hydrated silicate matrix (HSM), based on FA as the source material, to evaluate the environmental and health risks. The GM and HSM synthetic conditions were 60 °C, 20 % relative humidity (RH), and 12 wt% (6 mol/L) NaOH, and 20 ± 2 °C, ≥ 90 % RH, and 30 wt.%, respectively, based on their compressive strength performances. X-ray diffraction (XRD) showed that Pb participated in hydration and geopolymerization, and was incorporated in the structural components of the hydrated silicate and geopolymer. In leaching experiments, the solidification/stabilization effects of Pb and Cl in the HSM and GM improved with increasing curing time. After long-term curing (28 days), the immobility of Pb in the GM was better than that in the HSM. Sodalite improved the Cl-stabilizing ability of the GM compared with that of the HSM. In static monolithic leaching experiments, HSM and GM had the same Pb-leaching behaviors. Based on the changes in the location of the neutral sphere layer with decreasing acid-neutralizing capacity, Pb release was divided into alkaline-release, stagnation, and acid-release stages. The neutral sphere layer contained the highest Pb concentration during permeation toward the block center from the block edge. This behavior regulation could also apply to other amphoteric metals immobilized by GMs and HSMs.

  19. Preparation and characterization of high-strength calcium silicate boards from coal-fired industrial solid wastes

    Zhao Cao; Yong-dan Cao; Jin-shan Zhang; Chun-bao Sun; Xian-long Li


    To realize the comprehensive utilization of coal-fired industrial solid wastes, a novel high-strength board was prepared from cal-cium silicate slag, fly ash, and flue gas desulfurization (FGD) gypsum. The changes in mineral phases, chemical structure, and morphology during hydration were investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron mi-croscopy (SEM). A traditional board made from quartz and lime was prepared as a reference. The novel board not only consumes a lot of solid wastes, but also meets the strength requirement of the class-five calcium silicate board according to the Chinese Standard JC/T 564.2—2008. Microanalysis showed that hydrated calcium silicate gel (C−S−H(I)), ettringite, tobermorite, and xonotlite were successivelygenerated in the novel board by synergistic hydration of the mixed solid wastes. The board strength was improved by the formation of tobermorite and xonotlite but decreased by unhydrated quartz. It was demonstrated that quartz was not completely hydrated in the traditional board. As a re-sult, the flexural strength of the traditional board was much lower than that of the novel board.

  20. Carbonate Formation in Non-Aqueous Environments by Solid-Gas Carbonation of Silicates

    Day, S J; Evans, A; Parker, J E


    We have produced synthetic analogues of cosmic silicates using the Sol Gel method, producing amorphous silicates of composition Mg(x)Ca(1-x)SiO3. Using synchrotron X-ray powder diffraction on Beamline I11 at the Diamond Light Source, together with a newly-commissioned gas cell, real-time powder diffraction scans have been taken of a range of silicates exposed to CO2 under non-ambient conditions. The SXPD is complemented by other techniques including Raman and Infrared Spectroscopy and SEM imaging.

  1. Carbonate formation in non-aqueous environments by solid-gas carbonation of silicates

    Day, S. J.; Thompson, S. P.; Evans, A.; Parker, J. E.


    We have produced synthetic analogues of cosmic silicates using the Sol Gel method, producing amorphous silicates of composition Mg(x)Ca(1-x)SiO3. Using synchrotron X-ray powder diffraction on Beamline I11 at the Diamond Light Source, together with a newly-commissioned gas cell, real-time powder diffraction scans have been taken of a range of silicates exposed to CO2 under non-ambient conditions. The SXPD is complemented by other techniques including Raman and Infrared Spectroscopy and SEM imaging.

  2. Determination of several trace elements in silicate rocks by an XRF method with background and matrix corrections

    Pascual, J.


    An X-ray fluorescence method for determining trace elements in silicate rock samples was studied. The procedure focused on the application of the pertinent matrix corrections. Either the Compton peak or the reciprocal of the mass absorption coefficient of the sample was used as internal standard for this purpose. X-ray tubes with W or Cr anodes were employed, and the W L..beta.. and Cr K..cap alpha.. Compton intensities scattered by the sample were measured. The mass absorption coefficients at both sides of the absorption edge for Fe (1.658 and 1.936 A) were calculated. The elements Zr, Y, Rb, Zn, Ni, Cr and V were determined in 15 international reference rocks covering wide ranges of concentration. Relative mean errors were in many cases less than 10%.

  3. Creep Behavior of Hafnia and Ytterbium Silicate Environmental Barrier Coating Systems on SiC/SiC Ceramic Matrix Composites

    Zhu, Dongming; Fox, Dennis S.; Ghosn, Louis J.; Harder, Bryan


    Environmental barrier coatings will play a crucial role in future advanced gas turbine engines because of their ability to significantly extend the temperature capability and stability of SiC/SiC ceramic matrix composite (CMC) engine components, thus improving the engine performance. In order to develop high performance, robust coating systems for engine components, appropriate test approaches simulating operating temperature gradient and stress environments for evaluating the critical coating properties must be established. In this paper, thermal gradient mechanical testing approaches for evaluating creep and fatigue behavior of environmental barrier coated SiC/SiC CMC systems will be described. The creep and fatigue behavior of Hafnia and ytterbium silicate environmental barrier coatings on SiC/SiC CMC systems will be reported in simulated environmental exposure conditions. The coating failure mechanisms will also be discussed under the heat flux and stress conditions.

  4. Template-Engaged Solid-State Synthesis of Barium Magnesium Silicate Yolk@Shell Particles and Their High Photoluminescence Efficiency.

    Chen, Xuncai; Kim, Woo-Sik


    This study presents a new synthetic method for fabricating yolk@shell-structured barium magnesium silicate (BMS) particles through a template-engaged solid-state reaction. First, as the core template, (BaMg)CO3 spherical particles were prepared based on the coprecipitation of Ba(2+) and Mg(2+) . These core particles were then uniformly shelled with silica (SiO2 ) by using CTAB as the structure-directing template to form (BaMg)CO3 @SiO2 particles with a core@shell structure. The (BaMg)CO3 @SiO2 particles were then converted to yolk@shell barium magnesium silicate (BMS) particles by an interfacial solid-state reaction between the (BaMg)CO3 (core) and the SiO2 (shell) at 750 °C. During this interfacial solid-state reaction, Kirkendall diffusion contributed to the formation of yolk@shell BMS particles. Thus, the synthetic temperature for the (BaMg)SiO4 :Eu(3+) phosphor is significantly reduced from 1200 °C with the conventional method to 750 °C with the proposed method. In addition, the photoluminescence intensity of the yolk@shell (BaMg)SiO4 :Eu(3+) phosphor was found to be 9.8 times higher than that of the conventional (BaMg)SiO4 :Eu(3+) phosphor. The higher absorption of excitation light by the structure of the yolk@shell phosphor is induced by multiple light-reflection and -scattering events in the interstitial void between the yolk and the shell. When preparing the yolk@shell (BaMg)SiO4 :Eu(3+) phosphor, a hydrogen environment for the solid-state reaction results in higher photoluminescence efficiency than nitrogen and air environments. The proposed synthetic method can be easily extended to the synthesis of other yolk@shell multicomponent metal silicates.

  5. Determination of Iron in Layered Crystal Sodium Disilicate and Sodium Silicate by Flame Atomic Absorption Spectrometry with Boric Acid as a Matrix Modifier

    Zhi Hua WANG; Min CAI; Shu Jun WANG


    The effects of matrix silicate and experimental conditions on the determination of iron in flame atomic absorption spectrometry (FAAS) were investigated. It was found that boric acid as a matrix modifier obviously eliminated silicate interference. Under the optimum operating conditions, the determination results of iron in layered crystal sodium disilicate and sodium silicate samples by FAAS were satisfactory. The linear range of calibration curve is 0-10.5 μg.mL-1, the relative standard deviation of method is 1.2%-2.2%, the recovery of added iron is 96.0%-101%, the of iron of the standard curve method, standard addition calibration and colorimetry method was the same, but the first has the merits of rapid sample preparation, reduced contamination risks and fast analysis.


    I. A. Dyomichev


    Full Text Available We present spectra of the alkali-silicate glasses with copper ions in near-surface area, introduced by ion exchange of different temperature and duration. It is shown that the reduction of Cu2+ in the near-surface area causes existence of Cu+ and neutral atoms in glass after the ion-exchange in divalent salt. The ion-exchange itself involves only Cu+ and Na+ ions. The formation of subnanometer clusters Cun is due to neutral copper atoms staying in near-surface zone. We have shown that the waveguide layer in near-surface area, made by ion-exchange, has а visible luminescence with the excitation by UVradiation. At the same time, the contribution to luminescence is made by Cu+ ions, molecular clusters Cun and by dimers Cu+ - Cu+ . During the high-temperature ion-exchange at 600 °С the formation and destruction equilibrium shift of molecular clusters Cun can be seen. An hour ion-exchange leads to molecular clusters Cun destruction, while at time periods less than 30 min and around 18 hours it leads to the formation of Cun. The sample turns green after 18,5 hours ion-exchange showing formation of a considerable amount of divalent copper ions Cu2+ therein.

  7. Preparation and rebinding properties of protein-imprinted polysiloxane using mesoporous calcium silicate grafted non-woven polypropylene as matrix.

    Kan, Bohong; Feng, Lingzhi; Zhao, Kongyin; Wei, Junfu; Zhu, Dunwan; Zhang, Linhua; Ren, Qian


    Calcium silicate particle containing mesoporous SiO2 (CaSiO3@SiO2) was grafted on the surface of non-woven polypropylene. The PP non-woven grafted calcium silicate containing mesoporous SiO2 (PP-g-CaSiO3@SiO2) was used as the matrix to prepare bovine serum albumin (BSA) molecularly imprinted polysiloxane (MIP) by using silanes as the functional monomers and BSA as the template. PP non-woven grafted BSA-imprinted polysiloxane (PP-g-CaSiO3@SiO2 MIP) was characterized by scanning electron microscope (SEM), Fourier transform infrared spectometry (FTIR) and drilling string compensator (DSC). Influence factors on the rebinding capacity of the MIP were investigated, such as grafting degree, the pH in treating CaSiO3 and the type and proportion of silanes. The rebinding properties of BSA on PP-g-CaSiO3@SiO2 and MIP were investigated under different conditions. The results indicated that the rebinding capacity of MIP for BSA reached 56.32 mg/g, which was 2.65 times of NIP. The non-woven polypropylene grafted BSA-imprinted polysiloxane could recognize the template protein and the selectivity factor (β) was above 2.4 when using ovalbumin, hemoglobin and γ-globulin as control proteins. The PP-g-CaSiO3@SiO2 MIP has favorable reusability. Copyright © 2015 John Wiley & Sons, Ltd.

  8. Dichromatic laser photolysis of eosin in solid gelatinous matrix

    Sizykh, A. G.; Slyusareva, E. A.


    The laser irradiation of the thin films of solid solution of eosin in gelatinous matrix in the first and some upper dyes absorption bands leads to decrease of films optical density due to reaction of photoreduction. In the paper the kinetic of photoreduction of the dye eosin K in polymeric matrix in three cases of irradiation was experimentally investigated: a) irradiation by N2 laser (λ=337nm, second band of absorption, π=2 nsec, repetition rate-100 Hz, average power-2,2 mW), b) irradiation by Ar-laser (λ=488 nm, first band of absorption, 6,5-12 mW), c) under a simultaneous action of both Ar and N2-lasers. It was demonstrated that the most effective reaction of photoreduction took place in case of direct populating of upper singlet states with probable following nonradiative transition into equienergetic triplet states (energy ranges 35000-45000 sm-1).

  9. Thermal transport investigation in a CNTs/solid matrix composite

    Boulerouah, Aoumeur; Longuemart, Stéphane; Hus, Philippe; Sahraoui, Abdelhak Hadj


    The evolution of the thermal parameters of solid-solid composites based on carbon nanotubes (CNTs) (single-walled (SWNT) and multi-walled (MWNT)) were studied. A granular potassium bromide (KBr) material was chosen as a matrix. The evolutions of the dynamic thermal parameters (diffusivity, effusivity and conductivity) of the composites as a function of the weight fraction of the CNTs inclusions were obtained using the photoacoustic technique. The experimental evolution of the thermal conductivity of the composites with the CNTs loading showed two distinct behaviours, an increase up to around 2% of CNTs loading followed by a decrease. A heat transport model has been proposed to account for these two different observed trends providing a consistent explanation of the experimental data.

  10. Biological assessment of a calcium silicate incorporated hydroxyapatite-gelatin nanocomposite: a comparison to decellularized bone matrix.

    Lee, Dong Joon; Padilla, Ricardo; Zhang, He; Hu, Wei-Shou; Ko, Ching-Chang


    Our laboratory utilized biomimicry to develop a synthetic bone scaffold based on hydroxyapatite-gelatin-calcium silicate (HGCS). Here, we evaluated the potential of HGCS scaffold in bone formation in vivo using the rat calvarial critical-sized defect (CSD). Twelve Sprague-Dawley rats were randomized to four groups: control (defect only), decellularized bone matrix (DECBM), and HGCS with and without multipotent adult progenitor cells (MAPCs). DECBM was prepared by removing all the cells using SDS and NH4OH. After 12 weeks, the CSD specimens were harvested to evaluate radiographical, histological, and histomorphometrical outcomes. The in vitro osteogenic effects of the materials were studied by focal adhesion, MTS, and alizarin red. Micro-CT analysis indicated that the DECBM and the HGCS scaffold groups developed greater radiopaque areas than the other groups. Bone regeneration, assessed using histological analysis and fluorochrome labeling, was the highest in the HGCS scaffold seeded with MAPCs. The DECBM group showed limited osteoinductivity, causing a gap between the implant and host tissue. The group grafted with HGCS+MAPCs resulting in twice as much new bone formation seems to indicate a role for effective bone regeneration. In conclusion, the novel HGCS scaffold could improve bone regeneration and is a promising carrier for stem cell-mediated bone regeneration.

  11. Environmental Topology and Water Availability Modulates the Catalytic Activity of β-Galactosidase Entrapped in a Nanosporous Silicate Matrix.

    Burgos, M Ines; Velasco, Manuel I; Acosta, Rodolfo H; Perillo, María A


    In the present work we studied the catalytic activity of E. coli β-Gal confined in a nanoporous silicate matrix (Eβ-Gal) at different times after the beginning of the sol-gel polymerization process. Enzyme kinetic experiments with two substrates (ONPG and PNPG) that differed in the rate-limiting steps of the reaction mechanism for their β-Gal-catalyzed hydrolysis, measurements of transverse relaxation times (T2) of water protons through (1)H-NMR, and scanning electron microscopy analysis of the gel nanostructure, were performed. In conjunction, results provided evidence that water availability is crucial for the modulation observed in the catalytic activity of β-Gal as long as water participate in the rate limiting step of the reaction (only with ONPG). In this case, a biphasic rate vs. substrate concentration was obtained exhibiting one phase with catalytic rate constant (kcA), similar to that observed in solution, and another phase with a higher and aging-dependent catalytic rate constant (kcB). More structured water populations (lower T2) correlates with higher catalytic rate constants (kcB). The T2-kcB negative correlation observed along the aging of gels within the 15-days period assayed reinforces the coupling between water structure and the hydrolysis catalysis inside gels.

  12. Biological Assessment of a Calcium Silicate Incorporated Hydroxyapatite-Gelatin Nanocomposite: A Comparison to Decellularized Bone Matrix

    Dong Joon Lee


    Full Text Available Our laboratory utilized biomimicry to develop a synthetic bone scaffold based on hydroxyapatite-gelatin-calcium silicate (HGCS. Here, we evaluated the potential of HGCS scaffold in bone formation in vivo using the rat calvarial critical-sized defect (CSD. Twelve Sprague-Dawley rats were randomized to four groups: control (defect only, decellularized bone matrix (DECBM, and HGCS with and without multipotent adult progenitor cells (MAPCs. DECBM was prepared by removing all the cells using SDS and NH4OH. After 12 weeks, the CSD specimens were harvested to evaluate radiographical, histological, and histomorphometrical outcomes. The in vitro osteogenic effects of the materials were studied by focal adhesion, MTS, and alizarin red. Micro-CT analysis indicated that the DECBM and the HGCS scaffold groups developed greater radiopaque areas than the other groups. Bone regeneration, assessed using histological analysis and fluorochrome labeling, was the highest in the HGCS scaffold seeded with MAPCs. The DECBM group showed limited osteoinductivity, causing a gap between the implant and host tissue. The group grafted with HGCS+MAPCs resulting in twice as much new bone formation seems to indicate a role for effective bone regeneration. In conclusion, the novel HGCS scaffold could improve bone regeneration and is a promising carrier for stem cell-mediated bone regeneration.

  13. Preparation and Evaluation of Solid Dispersion Tablets by a Simple and Manufacturable Wet Granulation Method Using Porous Calcium Silicate.

    Fujimoto, Yumi; Hirai, Nobuaki; Takatani-Nakase, Tomoka; Takahashi, Koichi


    The aim of this study was to prepare and evaluate solid dispersion tablets containing a poorly water-soluble drug using porous calcium silicate (PCS) by a wet granulation method. Nifedipine (NIF) was used as the model poorly water-soluble drug. Solid dispersion tablets were prepared with the wet granulation method using ethanol and water by a high-speed mixer granulator. The binder and disintegrant were selected from 7 and 4 candidates, respectively. The dissolution test was conducted using the JP 16 paddle method. The oral absorption of NIF was studied in fasted rats. Xylitol and crospovidone were selected as the binder and disintegrant, respectively. The dissolution rates of NIF from solid dispersion formulations were markedly enhanced compared with NIF powder and physical mixtures. Powder X-ray diffraction (PXRD) confirmed the reduced crystallinity of NIF in the solid dispersion formulations. Fourier transform infrared (FT-IR) showed the physical interaction between NIF and PCS in the solid dispersion formulations. NIF is present in an amorphous state in granules prepared by the wet granulation method using water. The area under the plasma concentration-time curve (AUC) and peak concentration (C(max)) values of NIF after dosing rats with the solid dispersion granules were significantly greater than those after dosing with NIF powder. The solid dispersion formulations of NIF prepared with PCS using the wet granulation method exhibited accelerated dissolution rates and superior oral bioavailability. This method is very simple, and may be applicable to the development of other poorly water-soluble drugs.

  14. Solid lipid excipients - matrix agents for sustained drug delivery.

    Rosiaux, Yvonne; Jannin, Vincent; Hughes, Sophie; Marchaud, Delphine


    Lipid excipients are attracting interest from drug developers due to their performance, ease of use, versatility and their potential to generate intellectual property through innovation in drug delivery particularly in the case of modifying drug release systems. Many articles have described the use of lipid excipients to develop matrix modified release dosage forms in a range of processing techniques, therefore a comprehensive review is timely to collect together and analyze key information. This review article focuses on the utility of lipid excipients in solid sustained drug delivery systems with emphasis on the efficiency and robustness of these systems with respect to: (i) the choice of the manufacturing process and impact on drug release, (ii) the fundamental drug release mechanisms, (iii) resistance of the drug formulation under physiological conditions and (iv) long-term stability. Understanding the functionality of these versatile excipients in formulation is elementary for the development of highly robust lipid-based sustained release medicines.

  15. Silicate-entrapped porous coatings for preparing high-efficiency solid-phase microextraction sorbents

    Breton, Francois; Monton, Maria Rowena N. [University of Waterloo, Department of Chemistry, 200 University Ave. West, Waterloo, Ontario N2L 3G1 (Canada); Mullett, Wayne M. [MDS Nordion, 447 Marsh Road, Ottawa, Ontario K2K 1X8 (Canada); Pawliszyn, Janusz, E-mail: [University of Waterloo, Department of Chemistry, 200 University Ave. West, Waterloo, Ontario N2L 3G1 (Canada)


    We present a novel way to prepare SPME fibers using a silicate entrapment of porous particles, followed by derivatization using classical organosilane chemistry. The fibers provide a good platform for on-fiber derivatization of desired extraction phases while providing porosity necessary for high extractions capacities. The porous network was created using potassium silicate and porous silica particles. Fibers derivatized using n-butyl, n-octyl, n-octadecyl and n-triacontyl groups were shown to extract benzodiazepines successfully. The coatings were determined to have an average thickness of ca. 8 {mu}m, as determined by a scanning electron microscope, permitting equilibrium times as fast as 2 min. The fibers also showed very good ruggedness towards a vast range of solvents and prolonged use. It was determined that greater extraction efficiencies could be obtained using triacontyl as an extraction phase. The C18 and C30 fibers were also found to provide good linearity (>0.99) for the model analytes over two orders of magnitude, with limits of detection in the sub ng mL{sup -1} levels. C30 fibers were used to establish a correlation between structurally diverse {beta}-blockers and their literature reported Log P values. The C30 fibers provided a good correlation (R{sup 2} = 0.9255) between {beta}-blockers ranging in hydrophobicity from Log P{sub literature} 0.16-4.15 and their respective experimentally determined Log K{sub spme} values.

  16. Solid-state autocatalysis and oscillatory reactions in silicate glass systems

    Canning, John; Sørensen, Henrik Rokkjær; Kristensen, Martin


    We report the first demonstration of autocatalysis and oscillatory behaviour in the solid-state where no decomposition process is involved. Our material system is solid-state silica glass impregnated with hydrogen. It is at the heart of photosensitivity in glass-based optical waveguides and devic...... is carried out optically, opening up a new approach to characterisation of such catalytic processes generally....

  17. Development of an immobilization process for heavy metal containing galvanic solid wastes by use of sodium silicate and sodium tetraborate

    Aydın, Ahmet Alper, E-mail: [Chair of Urban Water Systems Engineering, Technische Universität München, Am Coulombwall, 85748 Garching (Germany); Aydın, Adnan [Istanbul Bilim University, School of Health, Esentepe, Istanbul, Sisli, 34394 (Turkey)


    Highlights: • A new physico-chemical process below 1000 °C for immobilization of galvanic sludges. • Sodium tetraborate and sodium silicate have been used as additives. • A strategy for adjustment of solid waste/additive mixture composition is presented. • Strategy is valid for wastes of hydrometallurgical and electro-plating processes. • Lower energy consumption and treated waste volume, shorter process time are provided. - Abstract: Heavy metal containing sludges from wastewater treatment plants of electroplating industries are designated as hazardous waste since their improper disposal pose high risks to environment. In this research, heavy metal containing sludges of electroplating industries in an organized industrial zone of Istanbul/Turkey were used as real-sample model for development of an immobilization process with sodium tetraborate and sodium silicate as additives. The washed sludges have been precalcined in a rotary furnace at 900 °C and fritted at three different temperatures of 850 °C, 900 °C and 950 °C. The amounts of additives were adjusted to provide different acidic and basic oxide ratios in the precalcined sludge-additive mixtures. Leaching tests were conducted according to the toxicity characteristic leaching procedure Method 1311 of US-EPA. X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscope-energy dispersive spectrometer (SEM-EDS) and flame atomic absorption spectroscopy (FAAS) have been used to determine the physical and chemical changes in the products. Calculated oxide molar ratios in the precalcined sludge-additive mixtures and their leaching results have been used to optimize the stabilization process and to determine the intervals of the required oxide ratios which provide end-products resistant to leaching procedure of US-EPA. The developed immobilization-process provides lower energy consumption than sintering-vitrification processes of glass–ceramics.

  18. Barium boron aluminum silicate glass system for solid state optical gas sensors

    Da Silva, M. J.; Karczewski, J.; Jasinski, P.; Chrzan, A.; Kalinowski, P.; Szymczewska, D.; Jasinski, G.


    Recent increasing demand for new eco-friendly materials and for low cost fabrication process for use in optical sensors field, raise concern about alternative materials for this application. We have designed two glass-ceramics compositions from the quaternary ROAl2O3- SiO2-B2O3(R=Ba) alkali-earth aluminum silicate system, labeled B72 and B69, with high refractive index (>1.6), large values of Abbe number (94.0 and 53.0, respectively), and free of lead and arsenic. We present an analysis and discussion of experimental optical properties, thermal and thermo-chemical stability along with important properties such as transition temperature (Tg), onset of crystallization (Tx) as well transport properties as ionic conductivity behavior in the quaternary glass-ceramic system containing boron for use as optical sensors. Complex Impedance Spectra (Bode Plot) and Potentiodynamic Polarization curves (Tafel plots) measurements were carried out in the temperature range of 600 to 850°C. The most probable conductivity mechanism is a thermally activated process of mobile ions overcoming a potential barrier (EA), according to the Arrhenius regime. Here we report that charge transfer is caused by the flux of electrons, in the region of elevated temperatures (>700°C), and is affected by immiscibility of crystals, nucleation and growth type, that causes phase separation. We found conductivity (σ) values from 10-9 to 10-5 S/cm at temperatures between 700 and 850°C. Our results highlight a need for research on ion mobility in the glassy network above the transition range, and the effect cause by metastable immiscibility in the alkaline-earth glasses are exposed. The two glass compositions B72 and B69 can be tailored by proper use as glassy optical sensor.

  19. Photoluminescence properties of europium doped di-strontium magnesium di-silicate phosphor by solid state reaction method

    Ishwar Prasad Sahu


    Full Text Available Europium doped di-strontium magnesium di-silicate phosphor namely (Sr2MgSi2O7:Eu3+ was prepared by the traditional high temperature solid state reaction method. The phase structure of sintered phosphor was akermanite type structure which belongs to the tetragonal crystallography with space group P42¯1m, this structure is a member of the melilite group and forms a layered compound. The EDX and FTIR spectra confirm the present elements in Sr2MgSi2O7:Eu3+ phosphor. Photoluminescence measurements showed that the phosphor exhibited strong emission peak with good intensity, corresponding to 5D0 → 7F2 (613 nm red emission and weak 5D0 → 7F1 (590 nm orange emission. The excitation spectra monitored at 613 nm show broad band from 220 to 300 nm ascribed to O–Eu charge-transfer band (CTB centered at about 269 nm, and the other peaks in the range of 300–400 nm originated from f–f transitions of Eu3+ ions. The strongest band at 395 nm can be assigned to 7F0 / 5L6 transition of Eu3+ ions due to the typical f–f transitions within Eu3+ of 4f6 configuration.

  20. Solid-state syntheses and single-crystal characterizations of three tetravalent thorium and uranium silicates

    Jin, Geng Bang; Soderholm, L.


    Colorless crystals of ThSiO4 (huttonite) (1) and (Ca0.5Na0.5)2NaThSi8O20 (2) have been synthesized by the solid-state reactions of ThO2, CaSiO3, and Na2WO4 at 1073 K. Green crystals of (Ca0.5Na0.5)2NaUSi8O20 (3) have been synthesized by the solid-state reactions of UO2, CaSiO3, and Na2WO4 at 1003 K. All three compounds have been characterized by single-crystal X-ray diffraction. Compound 1 adopts a monazite-type three-dimensional condensed structure, which is built from edge- and corner-shared ThO9 polyhedra and SiO4 tetrahedra. Compounds 2 and 3 are isostructural and they crystallize in a steacyite-type structure. The structure consists of discrete pseudocubic [Si8O20]8- polyanions, which are connected by An4+ cations into a three-dimensional framework. Each An atom coordinates to eight monodentate [Si8O20]8- moieties in a square antiprismatic geometry. Na+ and Ca2+ ions reside in the void within the framework. Raman spectra of 1, 2, and 3 were collected on single crystal samples. 1 displays more complex vibrational bands than thorite. Raman spectra of 2 and 3 are analogous with most of vibrational bands located at almost the same regions.

  1. Solid-matrix luminescence analysis. Progress report, 15 June 1992--31 October 1994

    Hurtubise, R.J.


    Interaction models were developed for moisture effects on room-temperature fluorescence (RTF) and room-temperature phosphorescence (RTP) of compounds adsorbed on filter paper. The models described both dynamic and matrix quenching and also related the Young modulus of filter paper to quenching of phosphor on moist filter paper. Photophysical parameters for lumiphors in solution and on solid matrices were compared. Results showed that for some compounds, solid-matrix luminescence has greater analytical potential than solution luminescence. Also, the solid-matrix systems into one of two categories depending on how the intersystem crossing rate constants change with temperature. The first study was carried out on effects of heavy atom on solid-matrix luminescence. With some heavy atoms, maximum solid-matrix phosphorescence quantum yield was obtained at room temperature, and there was no need to use low temperature to obtain a strong phosphorescence signal. By studying solid-matrix luminescence properties of phosphors adsorbed on sodium acetate and deuterated sodium acetate, an interaction model was developed for p-aminobenzoic acid anion adsorbed on sodium acetate. It was shown that the energy-gap law was applicable to solid-matrix luminescence. Also, deuterated phenanthrene and undeuterated phenanthrene were used to study nonradiative transition of excited triplet state of adsorbed phosphors. Heat capacities of several solid matrices were obtained vs temperature and related to vibrational coupling of solid matrix with phosphor. Photophysical study was performed on the hydrolysis products of benzo(a)pyrene-DNA adducts. Also, an analytical method was developed for tetrols in human lung fractions. Work was initiated on the formation of room temperature glasses with glucose and trehalose. Also, work has begun for the development of an oxygen sensor by measuring the RTP quenching of triphenylene on filter paper.

  2. Nanostructured silicate polymer concrete

    Figovskiy Oleg L'vovich


    Full Text Available It has been known that acid-resistant concretes on the liquid glass basis have high porosity (up to 18~20 %, low strength and insufficient water resistance. Significant increasing of silicate matrix strength and density was carried out by incorporation of special liquid organic alkali-soluble silicate additives, which block superficial pores and reduce concrete shrinkage deformation. It was demonstrated that introduction of tetrafurfuryloxisilane additive sharply increases strength, durability and shock resistance of silicate polymer concrete in aggressive media. The experiments showed, that the strength and density of silicate polymer concrete increase in case of decreasing liquid glass content. The authors obtained optimal content of silicate polymer concrete, which possesses increased strength, durability, density and crack-resistance. Diffusive permeability of concrete and its chemical resistance has been investigated in various corroding media.

  3. Europium doped di-calcium magnesium di-silicate orange–red emitting phosphor by solid state reaction method

    Ishwar Prasad Sahu


    Full Text Available A new orange–red europium doped di-calcium magnesium di-silicate (Ca2MgSi2O7:Eu3+ phosphor was prepared by the traditional high temperature solid state reaction method. The prepared Ca2MgSi2O7:Eu3+ phosphor was characterized by X-ray diffractometer (XRD, transmission electron microscopy (TEM, field emission scanning electron microscopy (FESEM with energy dispersive x-ray spectroscopy (EDX, fourier transform infrared spectra (FTIR, photoluminescence (PL and decay characteristics. The phase structure of sintered phosphor was akermanite type structure which belongs to the tetragonal crystallography with space group P4¯21m, this structure is a member of the melilite group and forms a layered compound. The chemical composition of the sintered Ca2MgSi2O7:Eu3+ phosphor was confirmed by EDX spectra. The PL spectra indicate that Ca2MgSi2O7:Eu3+ can be excited effectively by near ultraviolet (NUV light and exhibit bright orange–red emission with excellent color stability. The fluorescence lifetime of Ca2MgSi2O7:Eu3+ phosphor was found to be 28.47 ms. CIE color coordinates of Ca2MgSi2O7:Eu3+ phosphor is suitable as orange-red light emitting phosphor with a CIE value of (X = 0.5554, Y = 0.4397. Therefore, it is considered to be a new promising orange–red emitting phosphor for white light emitting diode (LED application.

  4. Probing local structures of siliceous zeolite frameworks by solid-state NMR and first-principles calculations of 29Si-O-29Si scalar couplings.

    Cadars, Sylvian; Brouwer, Darren H; Chmelka, Bradley F


    Subtle structural details of siliceous zeolites are probed by using two-bond scalar (J) coupling constants to characterize covalently bonded 29Si-O-29Si site pairs and local framework order. Solid-state two-dimensional (2D) 29Si{29Si} NMR measurements and first-principles calculations of 2J(29Si-O-29Si) couplings shed insights on both the local structures of siliceous zeolites Sigma-2 and ZSM-12, as well as the sensitivity of J couplings for detailed characterization analyses. DFT calculations on a model linear silicate dimer show that 2J(Si-O-Si) couplings have complicated multiple angular dependencies that make semi-empirical treatments impractical, but which are amenable to cluster approaches for accurate J-coupling calculations in zeolites. DFT calculations of 2J(29Si-O-29Si) couplings of the siliceous zeolite Sigma-2, whose framework structure is known to high accuracy from single-crystal X-ray diffraction studies, yield excellent agreement between calculated and experimentally measured 2J(Si-O-Si) couplings. For the siliceous zeolite ZSM-12, calculated 2J(29Si-O-29Si) couplings based on less-certain powder X-ray diffraction analyses deviate significantly from experimental values, while a refined structure based on 29Si chemical-shift-tensor analyses shows substantially improved agreement. 29Si J-coupling interactions can be used as sensitive probes of local structures of zeolitic frameworks and offer new opportunities for refining and solving complicated structures, in combination with complementary scattering, modeling, and other nuclear spin interactions.

  5. Thixoforming of SiC ceramic matrix composites in pseudo-semi-solid state

    CHENG Yuan-sheng; LUO Shou-jing; DU Zhi-ming


    A new forming process, ceramic matrix composites thixoforming in pseudo-semi-solid state, was proposed based on powder metallurgy technology combined with the semi-solid metal forming process. The satellite angle-frames were prepared by this technology with Alp and SiCp materials mixed with different volume fractions. It is proved that it is feasible for the forming of the ceramic matrix composites by this technology through metallographic analyses and tensile tests. The results also show that the microstructures of samples are homogeneous and they have high hardness and certain plasticity.

  6. NASA's Advanced Environmental Barrier Coatings Development for SiC/SiC Ceramic Matrix Composites: Understanding Calcium Magnesium Alumino-Silicate (CMAS) Degradations and Resistance

    Zhu, Dongming


    Environmental barrier coatings (EBCs) and SiCSiC ceramic matrix composites (CMCs) systems will play a crucial role in next generation turbine engines for hot-section component applications because of their ability to significantly increase engine operating temperatures with improved efficiency, reduce engine weight and cooling requirements. The development of prime-reliant environmental barrier coatings is essential to the viability and reliability of the envisioned CMC engine component applications, ensuring integrated EBC-CMC system durability and designs are achievable for successful applications of the game-changing component technologies and lifing methodologies.This paper will emphasize recent NASA environmental barrier coating developments for SiCSiC turbine airfoil components, utilizing advanced coating compositions, state-of-the-art processing methods, and combined mechanical and environment testing and durability evaluations. The coating-CMC degradations in the engine fatigue-creep and operating environments are particularly complex; one of the important coating development aspects is to better understand engine environmental interactions and coating life debits, and we have particularly addressed the effect of Calcium-Magnesium-Alumino-Silicate (CMAS) from road sand or volcano-ash deposits on the durability of the environmental barrier coating systems, and how the temperature capability, stability and cyclic life of the candidate rare earth oxide and silicate coating systems will be impacted in the presence of the CMAS at high temperatures and under simulated heat flux conditions. Advanced environmental barrier coating systems, including HfO2-Si with rare earth dopant based bond coat systems, will be discussed for the performance improvements to achieve better temperature capability and CMAS resistance for future engine operating conditions.

  7. Preparation of bioconjugates by solid-phase conjugation to ion exchange matrix-adsorbed carrier proteins

    Houen, G.; Olsen, D.T.; Hansen, P.R.;


    A solid-phase conjugation method utilizing carrier protein bound to an ion exchange matrix was developed. Ovalbumin was adsorbed to an anion exchange matrix using a batch procedure, and the immobilized protein was then derivatized with iodoacetic acid N-hydroxysuccinimid ester. The activated......, and immunization experiments with the eluted conjugates showed that the more substituted conjugates gave rise to the highest titers of glutathione antibodies. Direct immunization with the conjugates adsorbed to the ion exchange matrix was possible and gave rise to high titers of glutathione antibodies. Conjugates...... of ovalbumin and various peptides were prepared in a similar manner and used for production of peptide antisera by direct immunization with the conjugates bound to the ion exchanger. Advantages of the method are its solid-phase nature, allowing fast and efficient reactions and intermediate washings...

  8. Solid-matrix luminescence interactions and analytical aspects of phenylphenol isomers on filter paper

    Purdy, B.B.


    The solid-matrix luminescence limits of detection, percent relative standard deviation, and linear concentration ranges were obtained for model compounds adsorbed on four different solid-matrices. Filter paper showed the best analytical merit. Several solid-matrix luminescence properties of phenylphenol isomers adsorbed on Whatman filter paper were investigated. In the presence of sodium halide salts, the luminescence intensity, lifetime, quantum yield and modulus data were obtained to study heavy-atom effects, quenching effects by salts and moisture, and photophysical processes and molecular interactions in the solid-matrix. For 4-phenylphenol, 3-phenylphenol, and 2-phenylphenol, heavy-atom effects were observed for the room-temperature luminescence intensities. The room-temperature phosphorescence was sensitive to the structural differences among the isomers. The quenching of room-temperature fluorescence by halides was best described by a modified Perrin quenching model which considered a quenching sphere volume and residual fluorescence. At room temperature, the phosphorescence intensities were quenched by moisture while the phosphorescence lifetimes and fluorescence intensities were slightly affected by moisture for 4-phenylphenol and 2-phenylphenol with sodium halides. It was concluded that the adsorption of moisture on the filter paper matrix decreased the matrix rigidity, and thus the phosphorescence intensities of adsorbed phosphors were diminished. The phosphors were well-protected in the matrix, and water molecules could not diffuse effectively to the phosphor molecules. The photophysical data showed how the absorbed energy was channeled into the various radiative and nonradiative processes. Modulus experiments showed there were no differences in the Young's modulus values of filter paper containing NaCl, NaBr, or NaI. A correlation was found between Young's modulus and phosphorescence intensity as a function of the water content adsorbed on

  9. Spectroscopy of lithium atoms sublimated from isolation matrix of solid Ne

    Sacramento, R. L.; Scudeller, L. A.; Lambo, R.; Crivelli, P.; Cesar, C. L.


    We have studied, via laser absorption spectroscopy, the velocity distribution of 7Li atoms released from a solid neon matrix at cryogenic temperatures. The Li atoms are implanted into the Ne matrix by laser ablation of a solid Li precursor. A heat pulse is then applied to the sapphire substrate sublimating the matrix together with the isolated atoms at around 12 K. We find interesting differences in the velocity distribution of the released Li atoms from the model developed for our previous experiment with Cr [R. Lambo, C. C. Rodegheri, D. M. Silveira, and C. L. Cesar, Phys. Rev. A 76, 061401-R (2007)], 10.1103/PhysRevA.76.061401. This may be due to the sublimation regime, which is at much lower flux for the Li experiment than for the Cr experiment, as well as to the different collisional cross sections between those species to the Ne gas. We find a drift velocity compatible with Li being thermally sublimated at 11-13 K, while the velocity dispersion around this drift velocity is low, around 5-7 K. With a slow sublimation of the matrix we can determine the penetration depth of the laser ablated Li atoms into the Ne matrix, an important information that is not usually available in most matrix isolation spectroscopy setups. The present results with Li, together with the previous results with Cr suggest this to be a general technique for obtaining cryogenic atoms, for spectroscopic studies, as well as for trap loading. The release of the isolated atoms is also a useful tool to study and confirm details of the matrix isolated atoms which are masked or poorly understood in the solid.

  10. Spectroscopy of lithium atoms sublimated from isolation matrix of solid Ne.

    Sacramento, R L; Scudeller, L A; Lambo, R; Crivelli, P; Cesar, C L


    We have studied, via laser absorption spectroscopy, the velocity distribution of (7)Li atoms released from a solid neon matrix at cryogenic temperatures. The Li atoms are implanted into the Ne matrix by laser ablation of a solid Li precursor. A heat pulse is then applied to the sapphire substrate sublimating the matrix together with the isolated atoms at around 12 K. We find interesting differences in the velocity distribution of the released Li atoms from the model developed for our previous experiment with Cr [R. Lambo, C. C. Rodegheri, D. M. Silveira, and C. L. Cesar, Phys. Rev. A 76, 061401(R) (2007)]. This may be due to the sublimation regime, which is at much lower flux for the Li experiment than for the Cr experiment, as well as to the different collisional cross sections between those species to the Ne gas. We find a drift velocity compatible with Li being thermally sublimated at 11-13 K, while the velocity dispersion around this drift velocity is low, around 5-7 K. With a slow sublimation of the matrix we can determine the penetration depth of the laser ablated Li atoms into the Ne matrix, an important information that is not usually available in most matrix isolation spectroscopy setups. The present results with Li, together with the previous results with Cr suggest this to be a general technique for obtaining cryogenic atoms, for spectroscopic studies, as well as for trap loading. The release of the isolated atoms is also a useful tool to study and confirm details of the matrix isolated atoms which are masked or poorly understood in the solid. © 2011 American Institute of Physics

  11. Recent advances in lipid nanoparticle formulations with solid matrix for oral drug delivery.

    Das, Surajit; Chaudhury, Anumita


    Lipid nanoparticles based on solid matrix have emerged as potential drug carriers to improve gastrointestinal (GI) absorption and oral bioavailability of several drugs, especially lipophilic compounds. These formulations may also be used for sustained drug release. Solid lipid nanoparticle (SLN) and the newer generation lipid nanoparticle, nanostructured lipid carrier (NLC), have been studied for their capability as oral drug carriers. Biodegradable, biocompatible, and physiological lipids are generally used to prepare these nanoparticles. Hence, toxicity problems related with the polymeric nanoparticles can be minimized. Furthermore, stability of the formulations might increase than other liquid nano-carriers due to the solid matrix of these lipid nanoparticles. These nanoparticles can be produced by different formulation techniques. Scaling up of the production process from lab scale to industrial scale can be easily achieved. Reasonably high drug encapsulation efficiency of the nanoparticles was documented. Oral absorption and bioavailability of several drugs were improved after oral administration of the drug-loaded SLNs or NLCs. In this review, pros and cons, different formulation and characterization techniques, drug incorporation models, GI absorption and oral bioavailability enhancement mechanisms, stability and storage condition of the formulations, and recent advances in oral delivery of the lipid nanoparticles based on solid matrix will be discussed. © 2010 American Association of Pharmaceutical Scientists

  12. Soxhlet-assisted matrix solid phase dispersion to extract flavonoids from rape (Brassica campestris) bee pollen.

    Ma, Shuangqin; Tu, Xijuan; Dong, Jiangtao; Long, Peng; Yang, Wenchao; Miao, Xiaoqing; Chen, Wenbin; Wu, Zhenhong


    Soxhlet-assisted matrix solid phase dispersion (SA-MSPD) method was developed to extract flavonoids from rape (Brassica campestris) bee pollen. Extraction parameters including the extraction solvent, the extraction time, and the solid support conditions were investigated and optimized. The best extraction yields were obtained using ethanol as the extraction solvent, silica gel as the solid support with 1:2 samples to solid support ratio, and the extraction time of one hour. Comparing with the conventional solvent extraction and Soxhlet method, our results show that SA-MSPD method is a more effective technique with clean-up ability. In the test of six different samples of rape bee pollen, the extracted content of flavonoids was close to 10mg/g. The present work provided a simple and effective method for extracting flavonoids from rape bee pollen, and it could be applied in the studies of other kinds of bee pollen.

  13. Ultra-thin Solid-State Li-Ion Electrolyte Membrane Facilitated by a Self-Healing Polymer Matrix.

    Whiteley, Justin M; Taynton, Philip; Zhang, Wei; Lee, Se-Hee


    Thin solid membranes are formed by a new strategy, whereby an in situ derived self-healing polymer matrix that penetrates the void space of an inorganic solid is created. The concept is applied as a separator in an all-solid-state battery with an FeS2 -based cathode and achieves tremendous performance for over 200 cycles. Processing in dry conditions represents a paradigm shift for incorporating high active-material mass loadings into mixed-matrix membranes.

  14. Application of Deep Eutectic Solvents in Hybrid Molecularly Imprinted Polymers and Mesoporous Siliceous Material for Solid-Phase Extraction of Levofloxacin from Green Bean Extract.

    Li, Xiaoxia; Row, Kyung Ho


    Deep eutectic solvents (DES) are potential ecofriendly surfactants for the preparation of materials. In this study, both molecularly imprinted polymers (MIPs) and mesoporous siliceous materials (MSMs) were modified by betaine-based DES. Six materials were employed as solid phase extraction (SPE) adsorbents for the rapid purification of levofloxacin. The DES-based materials showed better selective adsorption than the conventional materials. The adsorption curves of DES-MIP showed superior molecular recognition ability and binding capability for levofloxacin compared to the other materials. The limit of detection and limit of quantitation of the method were 0.01 and 0.03 μg/mL for levofloxacin, respectively. The method recoveries at three spiked levels were 97.2 - 100.2% for DES-MIP, with an RSD <1.8%. DES-MIP showed the highest selective recovery (95.2%) for levofloxacin from the green bean extract, and could remove the interferent effectively.

  15. Structure and disorder in iron-bearing sodium silicate glasses and melts: High-resolution 29Si and 17O solid-state NMR study

    Kim, H.; Lee, S.


    Understanding of the effect of iron content on the structure (Si coordination environment and the degree of polymerization) of iron-bearing silicate melts and glasses is essential for studying their macroscopic properties and diverse geological processes in Earth's interior. Although the recent advances in high-resolution solid-state NMR techniques provide detailed structural information of a diverse iron-free oxide glasses with varying composition (e.g., Lee, P. Natl. Acad. Sci. USA., 2011, 108, 6847; Lee and Sung, Chem. Geol., 2008, 256, 326; Park and Lee, Geochim. Cosmochim. Acta, 2012, 80, 125; Lee et al., Phys. Rev., 103, 095501, 2009), their application to iron-bearing silicate glasses has a limited usefulness in resolving atomic configurations due to the effect of paramagnetic cation (i.e., Fe) on the NMR spectra. Here, we report the first ^{29}Si and ^{17}O NMR spectra for sodium-iron silicate glasses with varying iron content (Na_{2}O-Fe_{2}O_{3}-SiO_{2} glasses, up to 34.60 wt% Fe_{2}O_{3}), revealing previously unknown details of iron-induced changes in structure and disorder. While signal intensity decreases and peak width increases exponentially with increasing iron content [=Fe_{2}O_{3}/(Na_{2}O+Fe_{2}O_{3})], ^{29}Si MAS NMR spectra for sodium-iron silicate glasses present the slight peak shift and an asymmetrical peak broadening toward higher Q^{n} species with increasing iron content. This result implies an increase in the degree of polymerization with increasing iron content. Additionally, ^{29}Si spin-relaxation time (T_{1}) for the glasses decreases with increasing of iron content by several orders of magnitude. ^{17}O 3QMAS NMR spectra for the glasses show well-resolved non-bridging oxygen (NBO, Na-O-Si) and bridging oxygen (BO, Si-O-Si) even at relatively high iron content, providing the first direct experimental estimation of the degree of polymerization. In sodium-iron silicate glasses, the fraction of NBO decreases with increasing iron

  16. Composite Coatings with Ceramic Matrix Including Nanomaterials as Solid Lubricants for Oil-Less Automotive Applications

    Posmyk A.


    Full Text Available The paper presents the theoretical basis of manufacturing and chosen applications of composite coatings with ceramic matrix containing nanomaterials as a solid lubricant (AHC+NL. From a theoretical point of view, in order to reduce the friction coefficient of sliding contacts, two materials are required, i.e. one with a high hardness and the other with low shear strength. In case of composite coatings AHC+NL the matrix is a very hard and wear resistant anodic oxide coating (AHC whereas the solid lubricant used is the nanomaterial (NL featuring a low shear strength such as glassy carbon nanotubes (GC. Friction coefficient of cast iron GJL-350 sliding against the coating itself is much higher (0.18-0.22 than when it slides against a composite coating (0.08-0.14. It is possible to reduce the friction due to the presence of carbon nanotubes, or metal nanowires.

  17. Solid-state NMR and short-range order in crystalline oxides and silicates: a new tool in paramagnetic resonances.

    Stebbins, Jonathan F; McCarty, Ryan J; Palke, Aaron C


    Most applications of high-resolution NMR to questions of short-range order/disorder in inorganic materials have been made in systems where ions with unpaired electron spins are of negligible concentration, with structural information extracted primarily from chemical shifts, quadrupolar coupling parameters, and nuclear dipolar couplings. In some cases, however, the often-large additional resonance shifts caused by interactions between unpaired electron and nuclear spins can provide unique new structural information in materials with contents of paramagnetic cations ranging from hundreds of ppm to several per cent and even higher. In this brief review we focus on recent work on silicate, phosphate, and oxide materials with relatively low concentrations of paramagnetic ions, where spectral resolution can remain high enough to distinguish interactions between NMR-observed nuclides and one or more magnetic neighbors in different bonding configurations in the first, second, and even farther cation shells. We illustrate the types of information available, some of the limitations of this approach, and the great prospects for future experimental and theoretical work in this field. We give examples for the effects of paramagnetic transition metal, lanthanide, and actinide cation substitutions in simple oxides, pyrochlore, zircon, monazite, olivine, garnet, pyrochlores, and olivine structures.

  18. CH{sub 3} spin probe in solid Kr: Matrix structure and guest–host interaction

    Dmitriev, Yu.A., E-mail: [Ioffe Institute, 26 Politekhnicheskaya ul., 194021 St. Petersburg (Russian Federation); Melnikov, V.D. [Ioffe Institute, 26 Politekhnicheskaya ul., 194021 St. Petersburg (Russian Federation); Styrov, K.G. [Institute of Computing and Control, St. Petersburg State Polytechnical University, 29 Politekhnicheskaya ul., 195251 St. Petersburg (Russian Federation); Benetis, N.P. [Department of Pollution Control, Technological Education Institution, TEI, West Macedonia, Kozani 501 00 (Greece)


    Experimental EPR data obtained for the methyl, CH{sub 3}, radical trapped in quench condensed solid Kr are analyzed rendering the radical a probe for determination of regional disorder in Kr and similar solid matrices. Formation of regions of a highly disordered local matrix structure is proved. An attempt is presented of assessing a disorder parameter, based on the line broadening. The new structure is shown to be very effective in accumulating the radicals which are transiently mobile at the Kr 4.2 K surface. We discuss a model of the trapped radical rotation, which includes somewhat different mechanism than the hindrance of the rotation about the C{sub 3} axis and the rotation about the in-plane C{sub 2} axes. The level of the thermal contact of the radical spin-rotation motion with the lattice degrees of freedom in regions of varying order in the Kr solid matrix was assessed by progressive saturation curve-fitting parameters related to the spin-lattice relaxation time T{sub 1} of the radical.


    Mariana A. Melaj


    Full Text Available The main purpose of this work was to optimize the preparation conditions of solid polymeric matrix based on Chitosan and Xanthan, to be used in the controlled release of fertilizers. KNO3 was chosen as model agrochemical to be released. Both individual polymers and the Xanthan:Chitosan complex are biocompatible, leaving a residue on the soil which is non-toxic. The influence of different variables on the release pattern was studied: the type of polymer, the pressed conditions of the tablets and the presence of a drug-free polymeric coating. The polymer that presented a more promising release profile was Xanthan. The compression pressure applied to prepare the tablets was a more relevant variable than the compression time, in its effect on the kinetics of release. It was determined that the coating of the polymer matrix with crosslinked chitosan-glutaraldehyde allows getting a larger release time.

  20. Mechanism of the radiation-induced transformations of fluoroform in solid noble gas matrixes

    Sosulin, Ilya S.; Shiryaeva, Ekaterina S.; Feldman, Vladimir I.


    The X-ray induced transformations in the CHF3/Ng systems (Ng=Ne, Ar, Kr or Xe) at 6 K were studied by FTIR spectroscopy. The radiation-induced decomposition of CHF3 was found to be rather inefficient in solid xenon with low ionization energy, which suggests primary significance of the positive hole transfer from matrix to the fluoroform molecule. CF3•, :CF2, CHF2• and CF4 were identified as the products of low-temperature radiolysis in all the noble gas matrixes. In addition, the anionic complex HF ⋯ CF2- was detected in Ne and Ar matrixes. The radiolysis also resulted in formation of noble gas compounds (HArF in argon, HKrF in krypton, and XeF2 in xenon). While XeF2 and HArF were essentially formed directly after irradiation (presumably due to reactions of 'hot' fluorine atoms), HKrF mainly resulted from annealing of irradiated samples below 20 K due to thermally induced mobility of trapped fluorine atoms. In both krypton and xenon matrixes, the thermally induced reactions of F atoms occur at lower temperatures than those of H atoms, while the opposite situation is observed in argon. The mechanisms of the radiation-induced processes and their implications are discussed.

  1. Solid-matrix luminescence analysis. Final technical report, June 15, 1986--June 14, 1995

    Hurtubise, R.J.


    In this report, the major results and conclusions of the research over the last two years and five months will be considered. The report discusses the physicochemical interactions discovered that are important for solid-matrix luminescence (SML), and the development of new interaction models which are very useful for the understanding the phenomena that are relevant for SML. The SML of 4-phenylphenol and 2-phenyl phenol adsorbed on filter paper is described. In addition, some new analytical methodology and applications are discussed.

  2. A transverse isotropic model for microporous solids: Application to coal matrix adsorption and swelling

    Espinoza, D. N.; Vandamme, M.; Dangla, P.; Pereira, J.-M.; Vidal-Gilbert, S.


    Understanding the adsorption-induced swelling in coal is critical for predictable and enhanced coal bed methane production. The coal matrix is a natural anisotropic disordered microporous solid. We develop an elastic transverse isotropic poromechanical model for microporous solids which couples adsorption and strain through adsorption stress functions and expresses the adsorption isotherm as a multivariate function depending on fluid pressure and solid strains. Experimental data from the literature help invert the anisotropic adsorptive-mechanical properties of Brzeszcze coal samples exposed to CO2. The main findings include the following: (1) adsorption-induced swelling can be modeled by including fluid-specific and pressure-dependent adsorption stress functions into equilibrium equations, (2) modeling results suggest that swelling anisotropy is mostly caused by anisotropy of the solid mechanical properties, and (3) the total amount of adsorbed gas measured by immersing coal in the adsorbate overestimates adsorption amount compared to in situ conditions up to ˜20%. The developed fully coupled model can be upscaled to determine the coal seam permeability through permeability-stress relationships.

  3. Thermochemistry of Silicates

    Costa, Gustavo; Jacobson, Nathan


    The thermodynamic properties of vapor and condensed phases of silicates are crucial in many fields of science. These quantities address fundamental questions on the formation, stability, transformation, and physical properties of silicate minerals and silicate coating compositions. Here the thermodynamic activities of silica and other species in solid solution have been measured by the analysis of the corresponding high temperature vapors using Knudsen Effusion Mass Spectrometry (KEMS). In first set of experiments KEMS has been used to examine the volatility sequence of species (Fe, SiO, Mg, O2 and O) present in the vapor phase during heating of fosterite-rich olivine (Fo93Fa7) up to 2400 C and to measure the Fe, SiO and Mg activities in its solid solution. The data of fosterite-rich olivine are essential for thermochemical equilibrium models to predict the atmospheric and surface composition of hot, rocky exoplanets (Lava Planets). In the second set of experiments the measured thermodynamic activities of the silica in Y2O3-SiO2 and Yb2O3-SiO2 systems are used to assess their reactivity and degradation recession as environmental barrier coatings (EBCs) in combustion environments (e.g. non-moveable parts of gas turbine engine).

  4. A relationship to estimate the excess entropy of mixing: Application in silicate solid solutions and binary alloys.

    Benisek, Artur; Dachs, Edgar


    The paper presents new calorimetric data on the excess heat capacity and vibrational entropy of mixing of Pt-Rh and Ag-Pd alloys. The results of the latter alloy are compared to those obtained by calculations using the density functional theory. The extent of the excess vibrational entropy of mixing of these binaries and of some already investigated binary mixtures is related to the differences of the end-member volumes and the end-member bulk moduli. These quantities are used to roughly represent the changes of the bond length and stiffness in the substituted and substituent polyhedra due to compositional changes, which are assumed to be the important factors for the non-ideal vibrational behaviour in solid solutions.

  5. Solid-matrix luminescence analysis. Progress report, 1 November 1991--15 January 1993

    Hurtubise, R.J.


    Several interactions with lumiphors adsorbed on filter paper were elucidated from experiments with moisture, modulus and heavy-atom salts. The data were interpreted using static and dynamic quenching models, heavy-atom theory, and a theory related to the modulus of paper. With cyclodextrin-salt matrices, it was shown that 10% {alpha}-cyclodextrin/NaCl was very effective for obtaining strong room-temperature fluorescence and moderate room-temperature phosphorescence from adsorbed stereoisomeric tetrols. Extensive photophysical information was obtained for the four tetrols on 10% {alpha}-cyclodextrin/NaCl. The photophysical information acquired was used to develop a method for characterizing two of the tetrols. Work with model compounds adsorbed on deuterated sodium acetate showed that C-H vibrations in the undeuterated sodium acetate were not responsible for the deactivation of the excited triplet state in the model phosphors investigated. A considerable amount of solution luminescence and solid-matrix luminescence data were compared. The most important finding was that in several cases the room-temperature solid-matrix luminescence quantum yields were greater than the solution low-temperature quantum yield values.

  6. [Determination of aflatoxins in hot chilli products by matrix solid-phase dispersion and liquid chromatography].

    Zheng, Ping; Sheng, Xuan; Yu, Xiaofeng; Hu, Yanyun


    A new method based on matrix solid-phase dispersion (MSPD) extraction with neutral alumina and co-column purification with graphitized carbon black has been developed to determine aflatoxins B1, B2, G1, G2 in hot chilli products. The method includes liquid chromatography and fluorescence detection with on-line post-column derivatization with bromine. Optimization of different parameters, such as the type of solid supports for matrix dispersion and co-column clean-up was carried out. The recoveries of aflatoxins B1, B2, G1 and G2 were 95.4%, 87.3%, 91.5% and 92.6%, respectively, with relative standard deviations ranging from 3.3% to 6.1%. The limits of detection were in the range of 0.10 ng/g (B2, G2) to 0.25 ng/g (B1, G1). In addition, the comparison of the extraction and purification effect of MSPD with immunity affinity column showed that, MSPD is a valid method to analyze aflatoxins in hot chilli products.

  7. Determination of aflatoxins in rice samples by ultrasound-assisted matrix solid-phase dispersion.

    Manoochehri, Mahboobeh; Asgharinezhad, Ali Akbar; Safaei, Mahdi


    This work describes the application of ultrasound-assisted matrix solid-phase dispersion as an extraction and sample preparation approach for aflatoxins (B1, B2, G1 and G2) and subsequent determination of them by high-performance liquid chromatography-fluorescence detection. A Box-Behnken design in combination with response surface methodology was used to determine the affecting parameters on the extraction procedure. The influence of different variables including type of dispersing phase, sample-to-dispersing phase ratio, type and quantity of clean-up phase, ultrasonication time, ultrasonication temperature, nature and volume of the elution solvent was investigated in the optimization study. C18, primary-secondary amine (PSA) and acetonitrile were selected as dispersing phase, clean-up phase and elution solvent, respectively. The obtained optimized values were sample-to-dispersing phase ratio of 1 : 1, 60 mg of PSA, 11 min ultrasonication time, 30°C ultrasonication temperature and 4 mL acetonitrile. Under the optimal conditions, the limits of detection were ranged from 0.09 to 0.14 ng g(-1) and the precisions [relative standard deviation (RSD%)] were <8.6%. The recoveries of the matrix solid-phase dispersion process ranged from 78 to 83% with RSD <10% in all cases. Finally, this method was successfully applied to the extraction of trace amounts of aflatoxins in rice samples. © The Author [2014]. Published by Oxford University Press. All rights reserved. For Permissions, please email:

  8. Final report on the safety assessment of aluminum silicate, calcium silicate, magnesium aluminum silicate, magnesium silicate, magnesium trisilicate, sodium magnesium silicate, zirconium silicate, attapulgite, bentonite, Fuller's earth, hectorite, kaolin, lithium magnesium silicate, lithium magnesium sodium silicate, montmorillonite, pyrophyllite, and zeolite.

    Elmore, Amy R


    This report reviews the safety of Aluminum, Calcium, Lithium Magnesium, Lithium Magnesium Sodium, Magnesium Aluminum, Magnesium, Sodium Magnesium, and Zirconium Silicates, Magnesium Trisilicate, Attapulgite, Bentonite, Fuller's Earth, Hectorite, Kaolin, Montmorillonite, Pyrophyllite, and Zeolite as used in cosmetic formulations. The common aspect of all these claylike ingredients is that they contain silicon, oxygen, and one or more metals. Many silicates occur naturally and are mined; yet others are produced synthetically. Typical cosmetic uses of silicates include abrasive, opacifying agent, viscosity-increasing agent, anticaking agent, emulsion stabilizer, binder, and suspending agent. Clay silicates (silicates containing water in their structure) primarily function as adsorbents, opacifiers, and viscosity-increasing agents. Pyrophyllite is also used as a colorant. The International Agency for Research on Cancer has ruled Attapulgite fibers >5 microm as possibly carcinogenic to humans, but fibers mining and processing of Aluminum Silicate, Calcium Silicate, Zirconium Silicate, Fuller's Earth, Kaolin, Montmorillonite, Pyrophyllite, and Zeolite. The Cosmetic Ingredient Review (CIR. The Cosmetic Ingredient Review (CIR) Expert Panel concluded that the extensive pulmonary damage in humans was the result of direct occupational inhalation of the dusts and noted that lesions seen in animals were affected by particle size, fiber length, and concentration. The Panel considers that most of the formulations are not respirable and of the preparations that are respirable, the concentration of the ingredient is very low. Even so, the Panel considered that any spray containing these solids should be formulated to minimize their inhalation. With this admonition to the cosmetics industry, the CIR Expert Panel concluded that these ingredients are safe as currently used in cosmetic formulations. The Panel did note that the cosmetic ingredient, Talc, is a hydrated magnesium silicate

  9. Model Predictive Control of A Matrix-Converter Based Solid State Transformer for Utility Grid Interaction

    Xue, Yaosuo [ORNL


    The matrix converter solid state transformer (MC-SST), formed from the back-to-back connection of two three-to-single-phase matrix converters, is studied for use in the interconnection of two ac grids. The matrix converter topology provides a light weight and low volume single-stage bidirectional ac-ac power conversion without the need for a dc link. Thus, the lifetime limitations of dc-bus storage capacitors are avoided. However, space vector modulation of this type of MC-SST requires to compute vectors for each of the two MCs, which must be carefully coordinated to avoid commutation failure. An additional controller is also required to control power exchange between the two ac grids. In this paper, model predictive control (MPC) is proposed for an MC-SST connecting two different ac power grids. The proposed MPC predicts the circuit variables based on the discrete model of MC-SST system and the cost function is formulated so that the optimal switch vector for the next sample period is selected, thereby generating the required grid currents for the SST. Simulation and experimental studies are carried out to demonstrate the effectiveness and simplicity of the proposed MPC for such MC-SST-based grid interfacing systems.

  10. Thorium silicate compound as a solid-state target for production of isomeric thorium-229 nuclei by electron beam irradiation

    Borisyuk, P. V.; Vasilyev, O. S.; Lebedinskii, Y. Y.; Krasavin, A. V.; Tkalya, E. V.; Troyan, V. I.; Habibulina, R. F.; Chubunova, E. V.; Yakovlev, V. P.


    In this paper, we discuss an idea of the experiment for excitation of the isomeric transition in thorium-229 nuclei by irradiating with electron beam targets with necessary physical characteristics. The chemical composition and bandgap of ThSi10O22 were determined by X-ray photoelectron spectroscopy and reflection electron energy loss spectroscopy. It was found that the energy gap is equal to 7.7 eV and does not change when the target is exposed to a medium energy electron beam for a long time. This indicates that the compound possesses high electron-beam resistance. A quantitative estimation of the output function of isomeric thorium-229 nuclei generated by interaction of nuclei with the secondary electron flow formed by irradiating the solid-state ThSi10O22-based target is given. The estimation shows that ThSi10O22 is a promising thorium-containing target for investigating excitation of the nuclear low-lying isomeric transition in the thorium-229 isotope using medium-energy electrons.

  11. Mechanical evaluation of calcium-zirconium-silicate (baghdadite) obtained by a direct solid-state synthesis route.

    Schumacher, Thomas C; Volkmann, Eike; Yilmaz, Rumeysa; Wolf, Artur; Treccani, Laura; Rezwan, Kurosch


    Ca3ZrSi2O9 (baghdadite) has become a major research focus within the biomaterial community due to its remarkable in-vitro and in-vivo bioactivity. Although baghdadite seems to exhibit interesting biological properties, as yet there has been no data published concerning its mechanical properties. This lack of knowledge hinders targeting this novel bioactive material towards potential applications. In this study we prepare dense Ca3ZrSi2O9 bulk ceramics for the first time, allowing the evaluation of its mechanical properties including hardness, bending strength, Young׳s modulus, and fracture toughness. The preparation of baghdadite has been accomplished by a direct solid-state synthesis in combination with conventional sintering at 1350-1450°C for 3h. Our results show that samples sintered at 1400°C exhibit the best mechanical properties, resulting in a bending strength, fracture toughness, and hardness of 98±16MPa, 1.3±0.1MPam(0.5), and 7.9±0.2GPa. With a comparable mechanical strength to hydroxyapatite, but with an increased fracture toughness by 30% and hardness by 13% baghdadite is highly suitable for potential applications in non-load bearing areas (e.g. coatings or filler materials).

  12. Thorium silicate compound as a solid-state target for production of isomeric thorium-229 nuclei by electron beam irradiation

    P. V. Borisyuk


    Full Text Available In this paper, we discuss an idea of the experiment for excitation of the isomeric transition in thorium-229 nuclei by irradiating with electron beam targets with necessary physical characteristics. The chemical composition and bandgap of ThSi10O22 were determined by X-ray photoelectron spectroscopy and reflection electron energy loss spectroscopy. It was found that the energy gap is equal to 7.7 eV and does not change when the target is exposed to a medium energy electron beam for a long time. This indicates that the compound possesses high electron-beam resistance. A quantitative estimation of the output function of isomeric thorium-229 nuclei generated by interaction of nuclei with the secondary electron flow formed by irradiating the solid-state ThSi10O22-based target is given. The estimation shows that ThSi10O22 is a promising thorium-containing target for investigating excitation of the nuclear low-lying isomeric transition in the thorium-229 isotope using medium-energy electrons.

  13. Solid waste bin level detection using gray level co-occurrence matrix feature extraction approach.

    Arebey, Maher; Hannan, M A; Begum, R A; Basri, Hassan


    This paper presents solid waste bin level detection and classification using gray level co-occurrence matrix (GLCM) feature extraction methods. GLCM parameters, such as displacement, d, quantization, G, and the number of textural features, are investigated to determine the best parameter values of the bin images. The parameter values and number of texture features are used to form the GLCM database. The most appropriate features collected from the GLCM are then used as inputs to the multi-layer perceptron (MLP) and the K-nearest neighbor (KNN) classifiers for bin image classification and grading. The classification and grading performance for DB1, DB2 and DB3 features were selected with both MLP and KNN classifiers. The results demonstrated that the KNN classifier, at KNN = 3, d = 1 and maximum G values, performs better than using the MLP classifier with the same database. Based on the results, this method has the potential to be used in solid waste bin level classification and grading to provide a robust solution for solid waste bin level detection, monitoring and management.

  14. Solid-phase extraction of galloyl- and caffeoylquinic acids from natural sources (Galphimia glauca and Arnicae flos) using pure zirconium silicate and bismuth citrate powders as sorbents inside micro spin columns.

    Hussain, Shah; Schönbichler, Stefan A; Güzel, Yüksel; Sonderegger, Harald; Abel, Gudrun; Rainer, Matthias; Huck, Christian W; Bonn, Günther K


    Galloyl- and caffeoylquinic acids are among the most important pharmacological active groups of natural compounds. This study describes a pre-step in isolation of some selected representatives of these groups from biological samples. A selective solid-phase extraction (SPE) method for these compounds may help assign classes and isomer designations within complex mixtures. Pure zirconium silicate and bismuth citrate powders (325 mesh) were employed as two new sorbents for optimized SPE of phenolic acids. These sorbents possess electrostatic interaction sites which accounts for additional interactions for carbon acid moieties as compared to hydrophilic and hydrophobic sorbents alone. Based on this principle, a selective SPE method for 1,3,4,5-tetragalloylquinic acid (an anti-HIV and anti-asthamatic agent) as a starting compound was developed and then deployed upon other phenolic acids with success. The recoveries and selectivities of both sorbents were compared to most commonly applied and commercially available sorbents by using high performance liquid chromatography. The nature of interaction between the carrier sorbent and the acidic target molecules was investigated by studying hydrophilic (silica), hydrophobic (C18), mixed-mode (ionic and hydrophobic: Oasis(®) MAX) and predominantly electrostatic (zirconium silicate) materials. The newly developed zirconium silicate and bismuth citrate stationary phases revealed promising results for the selective extraction of galloyl- and caffeoylquinic acids from natural sources. It was observed that zirconium silicate exhibited maximum recovery and selectivity for tetragalloylquinic acid (84%), chlorogenic acid (82%) and dicaffeoylquinic acid (94%) among all the tested sorbents.

  15. Continuum modeling of a porous solid with pressure-sensitive dilatant matrix

    Guo, T. F.; Faleskog, J.; Shih, C. F.

    The pressure-sensitive plastic response of a material has been studied in terms of the intrinsic sensitivity of its yield stress to pressure and the presence and growth of cavities. This work focuses on the interplay between these two distinctly different mechanisms and the attendant material behavior. To this end, a constitutive model is proposed taking both mechanisms into account. Using Gurson's homogenization, an upper bound model is developed for a voided solid with a plastically dilatant matrix material. This model is built around a three-parameter axisymmetric velocity field for a unit sphere containing a spherical void. The void is also subjected to internal pressure; this can be relevant for polymeric adhesives permeated by moisture that vaporizes at elevated temperatures. The plastic response of the matrix material is described by Drucker-Prager's yield criterion and an associated flow rule. The resulting yield surface and porosity evolution law of the homogenized constitutive model are presented in parametric form. Using the solutions to special cases as building blocks, approximate models with explicit forms are proposed. The parametric form and an approximate explicit form are compared against full-field solutions obtained from finite element analysis. They are also studied for loading under generalized tension conditions. These computational simulations shed light on the interplay between the two mechanisms and its enhanced effect on yield strength and plastic flow. Among other things, the tensile yield strength of the porous solid is greatly reduced by the internal void pressure, particularly when a liquid/vapor phase is the source of the internal pressure.

  16. Application of matrix solid-phase dispersion and high-performance liquid chromatography for determination of sulfonamides in honey.

    Zou, Qiong-Hui; Wang, Jin; Wang, Xiang-Feng; Liu, Yuan; Han, Jie; Hou, Feier; Xie, Meng-Xia


    A novel method for simultaneous determination of 8 sulfonamide residues (sulfathiazole, sulfapyridine, sulfadiazine, sulfamerazine, sulfamonome-thoxine, sulfachloropyridazine, sulfamethoxazole, and sulfadimethoxine) in honey samples by high-performance liquid chromatography (HPLC) has been developed on the basis of precolumn derivatization with 9-fluorenylmethyl-chloroformate (FMOC-Cl). Sulfonamide residues in honey samples were extracted and purified by matrix solid-phase dispersion with C18 as the solid support. The residues were derivatized by FMOC-CI, and the FMOC-sulfonamide derivatives were further purified by solid-phase extraction with silica gel as the solid support prior to HPLC analysis. The average recoveries for most sulfonamide compounds at different spiking levels (from 10 to 250 microg/kg) were > 70% with relative standard deviations < 16%, and their limits of detection were 4.0 microg/kg. The established analytical method has high sensitivity and repeatability and can be applicable for determining the sulfonamide residues in various honey matrixes.

  17. Study of complex matrix effect on solid phase microextraction for biological sample analysis.

    Jiang, Ruifen; Xu, Jianqiao; Zhu, Fang; Luan, Tiangang; Zeng, Feng; Shen, Yong; Ouyang, Gangfeng


    Solid phase microextraction (SPME) has become a useful tool for in vivo monitoring the behavior of environmental organic pollutants in biological species due to its simplicity, relatively non-invasive, and cost-effective manner. However, the complex matrices in biological samples could significantly influence the extraction kinetic, and bias the quantification result. In this study, we investigated the effect of complex matrix on the extraction kinetic of SPME for biological sample analysis. Two sample matrices, phosphate-buffered saline (PBS) with bovine serum albumin (BSA) and agarose gel with BSA were used to simulate the biological fluid and tissue. Results showed that the addition of BSA significantly enhanced the mass transfer of organic compounds onto SPME fiber in both PBS buffer and gel sample. Enhancement factors ranging from 1.3 to 27, and 2.0 to 80 were found for all selected polyaromatic hydrocarbons (PAHs) in PBS buffer and agarose gel with BSA concentration of 0.1-5%, respectively. Then, an improved theoretical model was applied to quantify the observed enhancement effect, and the result showed that the predicted sampling time constant agreed well with the experimental one in complex matrix. Furthermore, a simplified equation was proposed for the real biological sample analysis.

  18. Evaluation of Solid Modeling Software for Finite Element Analysis of Woven Ceramic Matrix Composites

    Nemeth, Noel N.; Mital, Subodh; Lang, Jerry


    Three computer programs, used for the purpose of generating 3-D finite element models of the Repeating Unit Cell (RUC) of a textile, were examined for suitability to model woven Ceramic Matrix Composites (CMCs). The programs evaluated were the open-source available TexGen, the commercially available WiseTex, and the proprietary Composite Material Evaluator (COMATE). A five-harness-satin (5HS) weave for a melt-infiltrated (MI) silicon carbide matrix and silicon carbide fiber was selected as an example problem and the programs were tested for their ability to generate a finite element model of the RUC. The programs were also evaluated for ease-of-use and capability, particularly for the capability to introduce various defect types such as porosity, ply shifting, and nesting of a laminate. Overall, it was found that TexGen and WiseTex were useful for generating solid models of the tow geometry; however, there was a lack of consistency in generating well-conditioned finite element meshes of the tows and matrix. TexGen and WiseTex were both capable of allowing collective and individual shifting of tows within a ply and WiseTex also had a ply nesting capability. TexGen and WiseTex were sufficiently userfriendly and both included a Graphical User Interface (GUI). COMATE was satisfactory in generating a 5HS finite element mesh of an idealized weave geometry but COMATE lacked a GUI and was limited to only 5HS and 8HS weaves compared to the larger amount of weave selections available with TexGen and WiseTex.

  19. Matrix compatible solid phase microextraction coating, a greener approach to sample preparation in vegetable matrices.

    Naccarato, Attilio; Pawliszyn, Janusz


    This work proposes the novel PDMS/DVB/PDMS fiber as a greener strategy for analysis by direct immersion solid phase microextraction (SPME) in vegetables. SPME is an established sample preparation approach that has not yet been adequately explored for food analysis in direct immersion mode due to the limitations of the available commercial coatings. The robustness and endurance of this new coating were investigated by direct immersion extractions in raw blended vegetables without any further sample preparation steps. The PDMS/DVB/PDMS coating exhibited superior features related to the capability of the external PDMS layer to protect the commercial coating, and showed improvements in terms of extraction capability and in the cleanability of the coating surface. In addition to having contributed to the recognition of the superior features of this new fiber concept before commercialization, the outcomes of this work serve to confirm advancements in the matrix compatibility of the PDMS-modified fiber, and open new prospects for the development of greener high-throughput analytical methods in food analysis using solid phase microextraction in the near future.

  20. Quasi-solid-state dye-sensitized solar cells with cyanoacrylate as electrolyte matrix

    Lu, Shengli [Linz Institute for Organic Solar Cells (LIOS), Johannes Kepler University Linz, Altenbergerstr. 69, A-4040 Linz (Austria); Institute for Organic Solar Energy Opto-Electronic Materials, College of Biological and Chemical Engineering, Zhejiang University of Science and Technology, Hangzhou 310012 (China); Koeppe, Robert; Guenes, Serap; Sariciftci, Niyazi Serdar [Linz Institute for Organic Solar Cells (LIOS), Johannes Kepler University Linz, Altenbergerstr. 69, A-4040 Linz (Austria)


    A quasi-solid-state dye-sensitized solar cells (DSSCs) employing a commercial glue (''SuperGlue {sup registered} '') as electrolyte matrix was fabricated. The cyano groups of the cyanoacrylate can form a supramolecular complex with tetrapropylammonium cations. This immobilizes the cations and therefore might lead to a favored anionic charge transport necessary for a good performance of the iodide/triiodide electrolytic conductor. Obtaining energy conversion efficiencies of more than 4% under 100 mW/cm{sup 2} of simulated A.M. 1.5 illumination, the cyanoacrylate quasi-solid-state electrolyte is an ordinary and low-cost compound which has fast drying property and offers significant advantages in the fabrication of solar cells and modules as it is in itself is a very good laminating agent. The influences of different porous layer thicknesses of titanium oxide and various kinds of cations on DSSC performance and long-term stability are presented. (author)

  1. Fabrication of metal matrix composite by semi-solid powder processing

    Wu, Yufeng [Iowa State Univ., Ames, IA (United States)


    Various metal matrix composites (MMCs) are widely used in the automotive, aerospace and electrical industries due to their capability and flexibility in improving the mechanical, thermal and electrical properties of a component. However, current manufacturing technologies may suffer from insufficient process stability and reliability and inadequate economic efficiency and may not be able to satisfy the increasing demands placed on MMCs. Semi-solid powder processing (SPP), a technology that combines traditional powder metallurgy and semi-solid forming methods, has potential to produce MMCs with low cost and high efficiency. In this work, the analytical study and experimental investigation of SPP on the fabrication of MMCs were explored. An analytical model was developed to understand the deformation mechanism of the powder compact in the semi-solid state. The densification behavior of the Al6061 and SiC powder mixtures was investigated with different liquid fractions and SiC volume fractions. The limits of SPP were analyzed in terms of reinforcement phase loading and its impact on the composite microstructure. To explore adoption of new materials, carbon nanotube (CNT) was investigated as a reinforcing material in aluminum matrix using SPP. The process was successfully modeled for the mono-phase powder (Al6061) compaction and the density and density distribution were predicted. The deformation mechanism at low and high liquid fractions was discussed. In addition, the compaction behavior of the ceramic-metal powder mixture was understood, and the SiC loading limit was identified by parametric study. For the fabrication of CNT reinforced Al6061 composite, the mechanical alloying of Al6061-CNT powders was first investigated. A mathematical model was developed to predict the CNT length change during the mechanical alloying process. The effects of mechanical alloying time and processing temperature during SPP were studied on the mechanical, microstructural and

  2. Sulfur Solubility In Silicate Melts: A Thermochemical Model

    Moretti, R.; Ottonello, G.

    A termochemical model for calculating sulfur solubility of simple and complex silicate melts has been developed in the framework of the Toop-Samis polymeric approach combined with a Flood - Grjotheim theoretical treatment of silicate slags [1,2]. The model allows one to compute sulfide and sulfate content of silicate melts whenever fugacity of gaseous sulphur is provided. "Electrically equivalent ion fractions" are needed to weigh the contribution of the various disproportion reactions of the type: MOmelt + 1/2S2 ,gas MSmelt+1/2O2 ,gas (1) MOmelt + 1/2S2 ,gas + 3/2O2 ,gas MSO4 ,melt (2) Eqs. 1 and 2 account for the oxide-sulfide and the oxide-sulfate disproportiona- tion in silicate melt. Electrically equivalent ion fractions are computed, in a fused salt Temkin notation, over the appropriate matrixes (anionic and cationic). The extension of such matrixes is calculated in the framework of a polymeric model previously developed [1,2,3] and based on a parameterization of acid-base properties of melts. No adjustable parameters are used and model activities follow the raoultian behavior implicit in the ion matrix solution of the Temkin notation. The model is based on a huge amount of data available in literature and displays a high heuristic capability with virtually no compositional limits, as long as the structural role assigned to each oxide holds. REFERENCES: [1] Ottonello G., Moretti R., Marini L. and Vetuschi Zuccolini M. (2001), Chem. Geol., 174, 157-179. [2] Moretti R. (2002) PhD Thesis, University of Pisa. [3] Ottonello G. (2001) J. Non-Cryst. Solids, 282, 72-85.


    V. N. Yaglov


    Full Text Available The paper proposes a technology for obtaining bricks on the basis of lime-silica mixtures where chemical interactions are practically completely realized in dispersive state at the stage of preparation of binding contact maturing and raw mixture as a whole. The role of forming operation (moulding is changed in principle because in this case conversion of dispersive system into a rock-like solid occurs and due to this the solid obtains complete water-resistance in contact with water immediately after forming operation. Theoretical basis for the developed technology is capability of silicate dispersive substances (hydrated calcium silicate to transit in non-stable state, to form a rock-like water-resistant solid in the moment of mechanical load application during forming process. Specific feature of the proposed method is an exclusion of additional operations for autoclaving of products from the process of obtaining a silicate brick.Synthetic hydrated calcium silicate in contrast to natural ones are more uniform in composition and structure, they contain less impurities and they are characterized by dispersive composition and due to the mentioned advantages they find wider practical application. Contact-condensation binders permit to manipulate product properties on their basis and ensure maximum correspondence to the requirements of the concrete application. Raw material sources for obtaining synthetic hydrated calcium silicates are practically un-limited because calcium-silicon containing substances are found as in various technogenic wastes so in natural compounds as well. So the problem for obtaining hydrated calcium silicates having contact-condensation ability for structure formation becomes more and more actual one. This transition is considered as dependent principally on arrangement rate of substance particles which determined the level of its instability.

  4. Solid H2 versus solid noble-gas environment: Influence on photoinduced hydrogen-atom transfer in matrix-isolated 4(3H)-pyrimidinone

    Lapinski, Leszek; Nowak, Maciej J.; Rostkowska, Hanna


    UV-induced transformations have been studied for 4(3H)-pyrimidinone monomers isolated in low-temperature Ar, Ne, n-D2, and n-H2 matrices. The observed photochemical behavior of the compound drastically depended on the solid matrix environment. For 4(3H)-pyrimidinone isolated in solid Ar, the UV-induced phototautomeric transformation was clearly the dominating process, leading to a nearly quantitative conversion of the oxo reactant into the hydroxy product. For solid Ne environment, the oxo → hydroxy transformation was still the major photoprocess, but yielding less of the hydroxy product (ca. 64% of the yield in solid Ar). For 4(3H)-pyrimidinone isolated in solid n-H2, the oxo → hydroxy phototautomeric conversion did not occur (or occurred at a very tiny scale). Also for deuterated 4(3D)-pyrimidinone isolated in solid hydrogen, the analogous oxo → deuteroxy phototransformation was not observed. Finally, for the compound trapped in solid n-D2, the oxo → hydroxy phototautomerism clearly occurred, but the yield of the hydroxy tautomer was small (ca. 18% of the yield in solid Ar). Apart from hydrogen-atom-transfer processes, two other phototransformations: generation of open-ring conjugated ketene and valence Dewar isomer were observed for the compound isolated in Ar, Ne, n-D2, and n-H2 matrices.

  5. Molecularly designed lipid microdomains for solid dispersions using a polymer/inorganic carrier matrix produced by hot-melt extrusion.

    Adler, Camille; Schönenberger, Monica; Teleki, Alexandra; Kuentz, Martin


    Amorphous solid dispersions have for many years been a focus in oral formulations, especially in combination with a hot-melt extrusion process. The present work targets a novel approach with a system based on a fatty acid, a polymer and an inorganic carrier. It was intended to adsorb the acidic lipid by specific molecular interactions onto the solid carrier to design disorder in the alkyl chains of the lipid. Such designed lipid microdomains (DLM) were created as a new microstructure to accommodate a compound in a solid dispersion. Vibrational spectroscopy, X-ray powder diffraction, atomic force microscopy as well as electron microscopic imaging were employed to study a system of stearic acid, hydroxypropylcellulose and aluminum magnesium silicate. β-carotene was used as a poorly water-soluble model substance that is difficult to formulate with conventional solid dispersion formulations. The results indicated that the targeted molecular excipient interactions indeed led to DLMs for specific compositions. The different methods provided complementary aspects and important insights into the created microstructure. The novel delivery system appeared to be especially promising for the formulation of oral compounds that exhibit both high crystal energy and lipophilicity.

  6. HRTEM/AEM study of trace metal behavior, sheet silicate reactions, and fluid/solid mass balances in porphyry copper hydrothermal systems

    Veblen, D.R.; Ilton, E.S.


    Transmission electron microscopy has been used to investigate copper (Cu) incorporation into silicates and alteration reactions in porphyry copper deposits. High Cu in biotites results from submicroscopic inclusions of native Cu. The incorporation of Cu in low-temperature alteration lamellae suggests that Cu enrichment occurs during weathering, rather than during the hydrothermal event. Drill core from Cyprus Casa Grande, Arizona, shows systematic variation of Cu in sheet silicates as a function of depth in the weathering column. The aims of the present project are to apply the powerful techniques of transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and analytical electron microscopy (AEM) to understanding the geochemical processes in porphyry copper systems at the near-atomic scale. Our primary goals are to characterize the structural state of anomalously high Cu in silicates, determine the timing and conditions of Cu enrichment in silicates such as biotite, and use these data to suggest how base metals are released and subsequently immobilized under hydrothermal or weathering conditions; and to determine the submicroscopic, atomic-level reaction mechanisms responsible for silicate alteration in porphyry-copper hydrothermal systems, which will allow us to determine reaction stoichiometries and hence mass balances between minerals and hydrothermal fluid. 19 refs., 7 figs., 3 tabs.

  7. Bottom-up and top-down solid-state NMR approaches for bacterial biofilm matrix composition

    Cegelski, Lynette


    The genomics and proteomics revolutions have been enormously successful in providing crucial "parts lists" for biological systems. Yet, formidable challenges exist in generating complete descriptions of how the parts function and assemble into macromolecular complexes and whole-cell assemblies. Bacterial biofilms are complex multicellular bacterial communities protected by a slime-like extracellular matrix that confers protection to environmental stress and enhances resistance to antibiotics and host defenses. As a non-crystalline, insoluble, heterogeneous assembly, the biofilm extracellular matrix poses a challenge to compositional analysis by conventional methods. In this perspective, bottom-up and top-down solid-state NMR approaches are described for defining chemical composition in complex macrosystems. The "sum-of-the-parts" bottom-up approach was introduced to examine the amyloid-integrated biofilms formed by Escherichia coli and permitted the first determination of the composition of the intact extracellular matrix from a bacterial biofilm. An alternative top-down approach was developed to define composition in Vibrio cholerae biofilms and relied on an extensive panel of NMR measurements to tease out specific carbon pools from a single sample of the intact extracellular matrix. These two approaches are widely applicable to other heterogeneous assemblies. For bacterial biofilms, quantitative parameters of matrix composition are needed to understand how biofilms are assembled, to improve the development of biofilm inhibitors, and to dissect inhibitor modes of action. Solid-state NMR approaches will also be invaluable in obtaining parameters of matrix architecture.

  8. Polymer-nanocomposite brush-like architectures as an all-solid electrolyte matrix.

    Gowneni, Soujanya; Ramanjaneyulu, Kota; Basak, Pratyay


    Herein, we report on polymer-nanocomposites with brush-like architectures and evaluate their feasibility as an all-solid electrolyte matrix supporting Li(+)-ion conduction. Showcased as a first example in the domain of electrolyte research, the study probes several key factors, such as (i) core morphology, (ii) surface modifiers/functionality, (iii) grafting length, and (iv) density of the brushes, and determines their role on the overall electrochemical properties of these nanostructured organic-inorganic hybrids. Nanostructured titania was synthesized via wet-chemical approaches using either controlled hydrolysis or hydrothermal methods. Exercising suitable control on reaction parameters led to well-defined morphologies/phases, such as nanoparticles, nanospindles, nanourchins, nanorods or nanotubes, in either anatase, rutile or mixed forms. Covalent anchoring on titania nanostructures was achieved using dopamine, gallic acid and glycerol as small organic moieties. A one-pot process of priming the available surface functional groups postmodification with isocyanate chemistry was followed by grafting polyethylene glycol monomethyl ethers of desired chain lengths. Finally, complexation with lithium salt yielded electrolyte compositions where the ethylene oxide (EO) fractions aid in ion-solvation with ease. The synthesized materials were characterized in detail employing XRD, TEM, DRS-UV, FTIR, micro-Raman, TG-DTA and DSC at each stage to confirm the products and ascertain the physicochemical properties. Comprehensive evaluation using temperature-step electrochemical impedance spectroscopy (EIS) of these brush-like nanocomposites provided crucial leads toward establishing a plausible physical model for the system and understanding the mechanism of ion transport in these all-solid matrices. The preliminary results on ionic conductivity (σ) obtained for some of the compositions are estimated to be within the range of ∼10(-4) to 10(-5) S cm(-1) in the temperature

  9. Semi solid matrix formulations of meloxicam and tenoxicam: an in vitro and in vivo evaluation.

    Alladi, Saritha; Shastri, Nalini R


    The objective of this study was to improve the dissolution and subsequently the therapeutic efficacy of poorly water soluble BCS class-II drugs meloxicam and tenoxicam, by lipid semi solid matrix (SSM) systems filled in hard gelatin capsules by liquid fill technology. The present research involved preparation of SSM formulations using Gelucire 44/14 as a carrier due to its self emulsifying, wetting and hydrophilic properties. The SSM capsules were characterized by assay, in vitro dissolution studies, moisture uptake, FTIR and DSC. The optimized formulations were also evaluated for their in vivo anti inflammatory activity in rat model. Six to ten fold enhancement in vitro drug release, in both acidic and basic media, was obtained with formulations containing drug to carrier in 1:6 ratio. The absence of drug peak in DSC scans indicated complete dissolution of the drug in carrier, while IR revealed no chemical interaction of pure drug and Gelucire 44/14. The optimized SSM formulations of meloxicam and tenoxicam showed a rapid decrease in paw edema with a significant increase in anti-inflammatory activity. The SSM formulations were successful in providing rapid release of drugs with improved dissolution and in vivo anti-inflammatory activity by liquid fill technology in hard gelatin capsules.

  10. Stabilization of pH in solid-matrix hydroponic systems

    Frick, J.; Mitchell, C. A.


    2-[N-morpholino]ethanesulfonic acid (MES) buffer or Amberlite DP-1 (cation-exchange resin beads) were used to stabilize substrate pH of passive-wicking, solid-matrix hydroponic systems in which small canopies of Brassica napus L. (CrGC 5-2, genome : ACaacc) were grown to maturity. Two concentrations of MES (5 or 10 mM) were included in Hoagland 1 nutrient solution. Alternatively, resin beads were incorporated into the 2 vermiculite : 1 perlite (v/v) growth medium at 6% or 12% of total substrate volume. Both strategies stabilized pH without toxic side effects on plants. Average seed yield rates for all four pH stabilization treatments (13.3 to 16.9 g m-2 day-1) were about double that of the control (8.2 g m-2 day-1), for which there was no attempt to buffer substrate pH. Both the highest canopy seed yield rate (16.9 g m-2 day-1) and the highest shoot harvest index (19.5%) occurred with the 6% resin bead treatment, even though the 10 mM MES and 12% bead treatments maintained pH within the narrowest limits. The pH stabilization methods tested did not significantly affect seed oil and protein contents.

  11. Application Of Density Matrix Methods To Quadrupolar Spins In Solid State Nmr And Nqr

    Ageev, S Z


    Spin dynamics in solid state NMR and NQR are studied using spin density matrix theory. First, the response of spin 7/2 subject to the first order quadrupolar interaction, excited by one and two pulse sequences is examined. Specific pulse sequences with appropriate phase cycling designed for detection of MQ coherences developed during the first pulse are calculated analytically. The results are applied to the determination of quadrupolar parameters and true chemical shifts utilizing a 1D nutation experiment. Solomon echoes under soft pulse excitation are also considered for spin 7/2. Second, analytical solutions of off-resonance nutation line intensities for spin 3/2 are presented. The first order quadrupolar interaction is retained during the pulse. The third case puts forward a new theory of composite pulses in NQR. Shaped pulses are also considered. The calculation is valid for a non-zero asymmetry parameter and arbitrary orientation of the rf field. The results are generalized for half integer spins of mag...

  12. A single sorbent for tetracycline enrichment and subsequent solid-matrix time-resolved luminescence

    Liu Linshu [Eastern Regional Research Center, Agriculture Research Service, US Department of Agriculture, 600 East Mermaid Lane, Wyndmoor, PA 19038 (United States)]. E-mail:; Chen Guoying [Eastern Regional Research Center, Agriculture Research Service, US Department of Agriculture, 600 East Mermaid Lane, Wyndmoor, PA 19038 (United States); Fishman, Marshall L. [Eastern Regional Research Center, Agriculture Research Service, US Department of Agriculture, 600 East Mermaid Lane, Wyndmoor, PA 19038 (United States)


    The aim of this study was to search for a sorbent that could act as an extraction phase and as a support for solid-matrix time-resolved luminescence (SMTRL). Four potential sorbents were investigated for this purpose using tetracycline (TC) as a model analyte. Sorbents prepared from C18 silica gel or calcium cross-linked pectin gel were able to extract TC from dilute solutions. Europium(III)-TC complex adsorbed on the surface of C18 generated the most intense TRL signal when measured at {lambda}{sub ex} = 388 nm and {lambda}{sub em} = 615 nm. This method achieved a 1 ng/ml limit of detection (LOD) with a 100 {mu}l sample solution in a repeated spotting mode. Hyphenation of sorbent extraction and SMTRL was demonstrated using C18. This method is suitable for screening of TC in foods or aqueous solutions and can be extended to other luminescent lanthanide-chelating analytes in physiological or environmental samples.

  13. Evaluation of Antibacterial Enrofloxacin in Eggs by Matrix Solid Phase Dispersion-Flow Injection Chemiluminescence

    Xiaocui Duan


    Full Text Available The study based on the chemiluminescence (CL reaction of potassium ferricyanide and luminol in sodium hydroxide medium, enrofloxacin (ENRO could dramatically enhance CL intensities and incorporated with matrix solid-phase dispersion (MSPD technique (Florisil used as dispersant, dichloromethane eluted the target compounds. A simple flow injection chemiluminescence (FL-CL method with MSPD technique for determination of ENRO in eggs was described. Under optimal conditions, the CL intensities were linearly related to ENRO concentration ranging from 4.0×10-8 g.L−1 to 5.0×10-5 g.L−1, with a correlation coefficient of 0.9989 and detection limit of 5.0×10-9 g.L−1. The relative standard deviation was 3.6% at an ENRO concentration of 2.0×10-6 g.L−1. Our testing technique can help ensure food safety, and thus, protect public health.

  14. Stardust silicates from primitive meteorites.

    Nagashima, Kazuhide; Krot, Alexander N; Yurimoto, Hisayoshi


    Primitive chondritic meteorites contain material (presolar grains), at the level of a few parts per million, that predates the formation of our Solar System. Astronomical observations and the chemical composition of the Sun both suggest that silicates must have been the dominant solids in the protoplanetary disk from which the planets of the Solar System formed, but no presolar silicates have been identified in chondrites. Here we report the in situ discovery of presolar silicate grains 0.1-1 microm in size in the matrices of two primitive carbonaceous chondrites. These grains are highly enriched in 17O (delta17O(SMOW) > 100-400 per thousand ), but have solar silicon isotopic compositions within analytical uncertainties, suggesting an origin in an oxygen-rich red giant or an asymptotic giant branch star. The estimated abundance of these presolar silicates (3-30 parts per million) is higher than reported for other types of presolar grains in meteorites, consistent with their ubiquity in the early Solar System, but is about two orders of magnitude lower than their abundance in anhydrous interplanetary dust particles. This result is best explained by the destruction of silicates during high-temperature processing in the solar nebula.

  15. Analytical criterion for porous solids containing cylindrical voids in an incompressible matrix exhibiting tension-compression asymmetry

    Cazacu, Oana; Stewart, Joel B.


    A new analytic plastic potential is developed using a rigorous limit analysis approach. Conditions of homogeneous boundary strain rate are imposed on every cylinder concentric with the cavity. It is shown that, due to the tension-compression asymmetry of the incompressible matrix, the third invariant of the stress deviator has a strong influence on the yielding of the porous solid. New and intriguing results are obtained; namely, for axisymmetric loadings and plane strain conditions, the stress state at yielding is not hydrostatic. In the case when the matrix has the same yield in tension as in compression, the new criterion reduces to Gurson's criterion for cylindrical voids.

  16. Wear of semi-solid rheocast SiCp/Al metal matrix composites

    Curle, UA


    Full Text Available casting of SiC metal matrix composites. The metal matrix consisting of nearly spherical proeutectic a(Al) globules was produced. Spheroidization of fibrous eutectic silicon took place upon heat treatment of the as-cast metal matrix composites (MMCs...

  17. Matrix supported tailored polymer for solid phase extraction of fluoride from variety of aqueous streams

    Thakur, Neha; Kumar, Sanjukta A.; Wagh, D.N. [Analytical Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Das, Sadananda; Pandey, Ashok K. [Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Kumar, Sangita D., E-mail: [Analytical Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Reddy, A.V.R. [Analytical Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India)


    Highlights: Black-Right-Pointing-Pointer Th complexed with poly (bis[2-(methacryloyloxy)-ethyl]phosphate) as tailored polymer membranes. Black-Right-Pointing-Pointer Membranes offered high capacity and selectivity for fluoride in aqueous media. Black-Right-Pointing-Pointer Quantitative uptake (80 {+-} 5%) of fluoride. Black-Right-Pointing-Pointer Fast sorption kinetics. Black-Right-Pointing-Pointer Reusability of polymer membranes. - Abstract: Fluoride related health hazards (fluorosis) are a major environmental problem in many regions of the world. It affects teeth; skeleton and its accumulation over a long period can lead to changes in the DNA structure. It is thus absolutely essential to bring down the fluoride levels to acceptable limits. Here, we present a new inorganic-organic hybrid polymer sorbent having tailored fixed-sites for fluoride sorption. The matrix supported poly (bis[2-(methacryloyloxy)-ethyl]phosphate) was prepared by photo-initiator induced graft-polymerization in fibrous and microporous (sheet) host poly(propylene) substrates. These substrates were conditioned for selective fluoride sorption by forming thorium complex with phosphate groups on bis[2-methacryloyloxy)-ethyl] phosphate (MEP). These tailored sorbents were studied for their selectivity towards fluoride in aqueous media having different chemical conditions. The fibrous sorbent was found to take up fluoride with a faster rate (15 min for Almost-Equal-To 76% sorption) than the sheet sorbent. But, the fluoride loading capacity of sheet sorbent (4320 mg kg{sup -1}), was higher than fibrous and any other sorbent reported in the literature so far. The sorbent developed in the present work was found to be reusable after desorption of fluoride using NaOH solution. It was tested for solid phase extraction of fluoride from natural water samples.

  18. Determination of Sudan Residues in Sausage by Matrix Solid-Phase Dispersion and High-Performance Liquid Chromatography.

    Zhai, Yujuan; Cheng, Jianhua


    A method based on matrix solid-phase dispersion and high-performance liquid chromatography was applied to the determination of four Sudan red residues in sausage. The proposed method required only 0.5 g sample. The neutral alumina was used as the dispersant sorbent while n-hexane containing 10% (v/v) acetone was used as the eluting solvent. The recoveries in samples ranged from 76.4 to 111.0% and relative standard deviations were sausage.

  19. Effect of iron content on the structure and disorder of iron-bearing sodium silicate glasses: A high-resolution 29Si and 17O solid-state NMR study

    Kim, Hyo-Im; Sur, Jung Chul; Lee, Sung Keun


    Despite its geochemical importance and implications for the properties of natural magmatic melts, understanding the detailed structure of iron-bearing silicate glasses remains among the outstanding problems in geochemistry. This is mainly because solid-state NMR techniques, one of the most versatile experimental methods to probe the structure of oxide glasses, cannot be fully utilized for exploring the structural details of iron-bearing glasses as the unpaired electrons in Fe induce strong local magnetic fields that mask the original spectroscopic features (i.e., paramagnetic effect). Here, we report high-resolution 29Si and 17O solid-state NMR spectra of iron-bearing sodium silicate glasses (Na2O-Fe2O3-SiO2, Fe3+/ΣFe = 0.89 ± 0.04, thus containing both ferric and ferrous iron) with varying XFe2O3 [=Fe2O3/(Na2O + Fe2O3)], containing up to 22.9 wt% Fe2O3. This compositional series involves Fe-Na substitution at constant SiO2 contents of 66.7 mol% in the glasses. For both nuclides, the NMR spectra exhibit a decrease in the signal intensities and an increase in the peak widths with increasing iron concentration partly because of the paramagnetic effect. Despite the intrinsic difficulties that result from the pronounced paramagnetic effect, the 29Si and 17O NMR results yield structural details regarding the effect of iron content on Q speciation, spatial distribution of iron, and the extent of polymerization in the iron-bearing silicate glasses. The 29Si NMR spectra show an apparent increase in highly polymerized Q species with increasing XFe2O3 , suggesting an increase in the degree of melt polymerization. The 17O 3QMAS NMR spectra exhibit well-resolved non-bridging oxygen (NBO, Na-O-Si) and bridging oxygen (BO, Si-O-Si) peaks with varying iron concentration. By replacing Na2O with Fe2O3 (and thus with increasing iron content), the fraction of Na-O-Si decreases. Quantitative consideration of this effect confirms that the degree of polymerization is likely to

  20. Evaluation of a molecularly imprinted polymer for determination of steroids in goat milk by matrix solid phase dispersion.

    Gañán, Judith; Morante-Zarcero, Sonia; Gallego-Picó, Alejandrina; Garcinuño, Rosa María; Fernández-Hernando, Pilar; Sierra, Isabel


    A molecularly imprinted polymer-matrix solid-phase dispersion methodology for simultaneous determination of five steroids in goat milk samples was proposed. Factors affecting the extraction recovery such as sample/dispersant ratio and washing and elution solvents were investigated. The molecularly imprinted polymer used as dispersant in the matrix solid-phase dispersion procedure showed high affinity to steroids, and the obtained extracts were sufficiently cleaned to be directly analyzed. Analytical separation was performed by micellar electrokinetic chromatography using a capillary electrophoresis system equipped with a diode array detector. A background electrolyte composed of borate buffer (25mM, pH 9.3), sodium dodecyl sulfate (10mM) and acetonitrile (20%) was used. The developed MIP-MSPD methodology was applied for direct determination of testosterone (T), estrone (E1), 17β-estradiol (17β-E2), 17α-ethinylestradiol (EE2) and progesterone (P) in different goat milk samples. Mean recoveries obtained ranged from 81% to 110%, with relative standard deviations (RSD)≤12%. The molecularly imprinted polymer-matrix solid-phase dispersion method is fast, selective, cost-effective and environment-friendly compared with other pretreatment methods used for extraction of steroids in milk.

  1. A new solid polymer electrolyte incorporating Li10GeP2S12 into a polyethylene oxide matrix for all-solid-state lithium batteries

    Zhao, Yanran; Wu, Chuan; Peng, Gang; Chen, Xiaotian; Yao, Xiayin; Bai, Ying; Wu, Feng; Chen, Shaojie; Xu, Xiaoxiong


    Li10GeP2S12 (LGPS) is incorporated into polyethylene oxide (PEO) matrix to fabricate composite solid polymer electrolyte (SPE) membranes. The lithium ion conductivities of as-prepared composite membranes are evaluated, and the optimal composite membrane exhibits a maximum ionic conductivity of 1.21 × 10-3 S cm-1 at 80 °C and an electrochemical window of 0-5.7 V. The phase transition behaviors for electrolytes are characterized by DSC, and the possible reasons for their enhanced ionic conductivities are discussed. The LGPS microparticles, acting as active fillers incorporation into the PEO matrix, have a positive effect on the ionic conductivity, lithium ion transference number and electrochemical stabilities. In addition, two kinds of all-solid-state lithium batteries (LiFeO4/SPE/Li and LiCoO2/SPE/Li) are fabricated to demonstrate the good compatibility between this new SPE membrane and different electrodes. And the LiFePO4/Li battery exhibits fascinating electrochemical performance with high capacity retention (92.5% after 50 cycles at 60 °C) and attractive capacities of 158, 148, 138 and 99 mAh g-1 at current rates of 0.1 C, 0.2 C, 0.5 C and 1 C at 60 °C, respectively. It is demonstrated that this new composite SPE should be a promising electrolyte applied in solid state batteries based on lithium metal electrode.

  2. Surfactant-Free Solid Dispersions of Hydrophobic Drugs in an Amorphous Sugar Matrix Dried from an Organic Solvent.

    Takeda, Koji; Gotoda, Yuto; Hirota, Daichi; Hidaka, Fumihiro; Sato, Tomo; Matsuura, Tsutashi; Imanaka, Hiroyuki; Ishida, Naoyuki; Imamura, Koreyoshi


    The technique for homogeneously dispersing hydrophobic drugs in a water-soluble solid matrix (solid dispersion) is a subject that has been extensively investigated in the pharmaceutical industry. Herein, a novel technique for dispersing a solid, without the need to use a surfactant, is reported. A freeze-dried amorphous sugar sample was dissolved in an organic solvent, which contained a soluble model hydrophobic component. The suspension of the sugar and the model hydrophobic component was vacuum foam dried to give a solid powder. Four types of sugars and methanol were used as representative sugars and the organic medium. Four model drugs (indomethacin, ibuprofen, gliclazide, and nifedipine) were employed. Differential scanning calorimetry analyses indicated that the sugar and model drug (100:1) did not undergo segregation during the drying process. The dissolution of the hydrophobic drugs in water from the solid dispersion was then evaluated, and the results indicated that the Cmax and AUC0-60 min of the hydrophobic drug in water were increased when the surfactant-free solid dispersion was used. Palatinose and/or α-maltose were superior to the other tested carbohydrates in increasing Cmax and AUC0-60 min for all tested model drugs, and the model drug with a lower water solubility tended to exhibit a greater extent of over-dissolution.

  3. Effect of Zircon Silicate Reinforcements on the Microstructure and Properties of as Cast Al-4.5Cu Matrix Particulate Composites Synthesized via Squeeze Cast Route

    E. G. Okafor


    Full Text Available The as-cast microstructure and properties of Al-4.5Cu/ZrSiO4 particulate composite synthesized via squeezed casting route was studied, varying the percentage ZrSiO4 in the range of 5-25wt%. The result obtained revealed that addition of ZrSiO4 reinforcements, increased the hardness value and apparent porosity by 107.65 and 34.23% respectively and decrease impact energy by 43.16 %. As the weight percent of ZrSiO4 increases in the matrix alloy, the yield and ultimate tensile strength increased by 156.52 and 155.81% up to a maximum of 15% ZrSiO4 addition respectively. The distribution of the brittle ZrSiO4 phase in the ductile matrix alloy led to increase strength and hardness values. These results had shown that, additions of ZrSiO4 particles to Al-4.5Cu matrix alloy improved properties.

  4. Determination of phenolic compounds in wines by novel matrix solid-phase dispersion extraction and gas chromatography/mass spectrometry.

    Minuti, Lucio; Pellegrino, Roberto


    A novel matrix solid-phase dispersion (MSPD) extraction method was developed to extract simultaneously 23 phenolic compounds from wine samples prior to determination by gas chromatography with mass spectrometric detection in the selected ion monitoring mode. Different parameters of the MSPD technique such as dispersant solid-phase, eluting solvent, and sample ionic strength and pH were optimized. The optimized MSPD procedure requires a small volume of wine (1 mL), commercial silica gel (1.5 g) as dispersant solid-phase and a small volume of ethyl acetate (5 mL) as eluting solvent. Under these conditions, the extraction of the studied compounds was almost complete (mean values of recoveries between 87 and 109%) in a short time (15 min). Moreover, satisfactory standard deviations of repeatability (RSD0.993) and detection limits (wines. Application was illustrated by analysis of different wine samples.

  5. Experimental Investigation of Irradiation-driven Hydrogen Isotope Fractionation in Analogs of Protoplanetary Hydrous Silicate Dust

    Roskosz, Mathieu; Laurent, Boris; Leroux, Hugues; Remusat, Laurent


    The origin of hydrogen in chondritic components is poorly understood. Their isotopic composition is heavier than the solar nebula gas. In addition, in most meteorites, hydrous silicates are found to be lighter than the coexisting organic matter. Ionizing irradiation recently emerged as an efficient hydrogen fractionating process in organics, but its effect on H-bearing silicates remains essentially unknown. We report the evolution of the D/H of hydrous silicates experimentally irradiated by electrons. Thin films of amorphous silica, amorphous “serpentine,” and pellets of crystalline muscovite were irradiated at 4 and 30 keV. For all samples, irradiation leads to a large hydrogen loss correlated with a moderate deuterium enrichment of the solid residue. The entire data set can be described by a Rayleigh distillation. The calculated fractionation factor is consistent with a kinetically controlled fractionation during the loss of hydrogen. Furthermore, for a given ionizing condition, the deuteration of the silicate residues is much lower than the deuteration measured on irradiated organic macromolecules. These results provide firm evidence of the limitations of ionizing irradiation as a driving mechanism for D-enrichment of silicate materials. The isotopic composition of the silicate dust cannot rise from a protosolar to a chondritic signature during solar irradiations. More importantly, these results imply that irradiation of the disk naturally induces a strong decoupling of the isotopic signatures of coexisting organics and silicates. This decoupling is consistent with the systematic difference observed between the heavy organic matter and the lighter water typically associated with minerals in the matrix of most carbonaceous chondrites.


    AbstractFour tetrols of benzo[a]pyrene-DNA adducts were separated using reversed-phase high performance liquid chromatography. Chromatographic fractions containing a given tetrol were readily characterized with solid-matrix room temperature luminescence techniques. So...

  7. Evaluation of Iranian Leopold Matrix application in the Environmental Impact Assessment (EIA of solid waste management options in Birjand city

    S Valizadeh


    Full Text Available Background and Objective: Significant increase in population and as a result, the production of excessive waste has recently made attention to municipal solid waste management a necessary issue. The objective of this study was to use matrix-based EIA process in order to determine best waste management option in Birjand City and to suggest appropriate solutions to managers and planners of this city. Materials and Methods: Assessing the environmental impacts of waste management options was done using Iranian Leopold Matrix. Through this method, the environmental impacts of waste management options were determined in the Birjand City. The options were Open dumping, Recycling, Composting, and Sanitary damping. Results: The results indicated that Open dumping with a final score of -3.06 had the highest environmental impact and was introduced as the fourth preference. In addition, composting with final score of -2.34 has the lowest environmental impact compared with other options. Conclusion: About 76.95% of the composition of municipal solid waste of Birjand City is household waste; therefore, putrescible organic materials are the predominant waste. Thus, according to the results of the Iranian Leopold matrix method, composting option was introduced as the first priority and the most logical option for waste management in the Birjand City.

  8. Obtaining calcium silicates by using solid residues as precursors. Influence of water in the process of mixing reagents; Obtencin de silicatos de calcio empleando como precursores residuos solidos. Influencia del mezclado de reactivos en fase seca o fase humeda

    Felipe-Sese, M.; Eliche-Quesada, D.; Corpas-Iglesias, F. A.


    The suitability of re-using residues marble, remaining from cutting marble, as a source of calcium-oxide, as well as the resultant ashes from the combustion of the wastes generated in the process of manufacturing boards from derivates of wood, as a source of silica, as raw material for the production of calcium silicate products has been determined. First of all, the influence of water has been studied in the initial phase of mixing residues. Marble and ashes have been mixed in molar relation CaO:SiO{sub 2} of 1:1 using two different ways: using a planetary ball mill (while in solid state) or agitating at 90 degree centigrade (2 h) using a 60 wt% of water (while in humid state). Later, both mixtures were sintered at 1100 degree centigrade (24 h). In order to use the obtained calcium-silicates as ceramic insulating thermal materials, the samples were compressed at 15 Tm obtaining bricks from which the technological properties have been studied. The ceramic materials obtained from mixing the residues in dry phase, as well as those obtained in the wet phase, can be used as thermal insulators, showing values of conductivity of 0.18 and 0.12 w/m{sup 2}K, with an elevated resistance to compressive strength. (Author) 14 refs.

  9. A menthol-based solid dispersion technique for enhanced solubility and dissolution of sulfamethoxazole from an oral tablet matrix.

    Choonara, Bibi F; Choonara, Yahya E; Kumar, Pradeep; du Toit, Lisa C; Tomar, Lomas K; Tyagi, Charu; Pillay, Viness


    A menthol-based solid dispersion was designed to improve the intrinsic solubility of the poorly soluble sulfamethoxazole- a class II drug molecule of Biopharmaceutics Classification System (BCS) displaying widespread antibacterial activity. Solid dispersions of menthol and sulfamethoxazole were compressed with hydroxypropyl methylcellulose (HPMC) into suitable sulfamethoxazole-loaded matrix tablets for oral drug delivery. The sulfamethoxazole-loaded solid dispersions and compressed tablets were characterized for their physicochemical and physicomechanical properties such as changes in crystallinity, melting point, molecular transitions, and textural analysis for critical analysis of their effects on the solubility and dissolution of sulfamethoxazole. The formulations were further evaluated for swelling, degradation, solubility, and in vitro drug release behavior. In vitro drug release from the sulfamethoxazole-loaded matrix tablets displayed a minimum and maximum fractional release of 0.714 and 0.970, respectively. The tablets further displayed different release rate profiles over the study periods of 12, 16, 48, and 56 h which were attributed to the varying concentrations of menthol within each formulation. Menthol was determined as a suitable hydrophilic carrier for sulfamethoxazole since it functioned as a solubilizing and release-retarding agent for improving the solubility and dissolution of sulfamethoxazole as well as controlling the rate at which it was released.

  10. Enhancing in vitro dissolution and in vivo bioavailability of fenofibrate by solid self-emulsifying matrix combined with SBA-15 mesoporous silica.

    Quan, Guilan; Wu, Qiaoli; Zhang, Xiaoxu; Zhan, Zhengwen; Zhou, Chan; Chen, Bao; Zhang, Zhengzan; Li, Ge; Pan, Xin; Wu, Chuanbin


    Mesoporous silica Santa Barbara amorphous-15 (SBA-15), derived from supermolecular assemblies of surfactant Pluronic(®) P123 with well-ordered 2-D hexagonal pores, was investigated as a reservoir to construct a novel solid self-emulsifying matrix for enhancing the oral bioavailability of fenofibrate (FNB). The emulsification rate and droplet size of a liquid self-emulsifying delivery system (SEDDS) were analyzed for optimization. SBA-15 was then added to the ethanol solution containing liquid SEDDS, and the obtained suspension changed into solid SEDDS matrix via solvent evaporation. The characterizations by SEM and XRD revealed that the solid matrix consisted of particles with smooth surface and FNB was completely transformed into molecular or amorphous state in the formulation. When introduced to aqueous media under gentle agitation, the solid matrix exhibited excellent self-emulsification properties and formed a uniform microemulsion with mean diameter of 117.35 ± 2.33 nm. The solid SEDDS matrix showed faster in vitro release rate than the raw powder and commercial capsule. The absorption of FNB delivered by solid SEDDS matrix was significantly improved in beagle dogs, and its Cmax and AUC values were about 8- and 4-fold greater than those of commercial products, respectively. In conclusion, SBA-15 emerged as a promising reservoir for SEDDS to enhance the bioavailability of poorly water-soluble drugs, which may provide a new strategy for advanced therapies. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. A novel approach for the fabrication of all-inorganic nanocrystal solids: Semiconductor matrix encapsulated nanocrystal arrays

    Moroz, Pavel

    Growing fossil fuels consumption compels researchers to find new alternative pathways to produce energy. Along with new materials for the conversion of different types of energy into electricity innovative methods for efficient processing of energy sources are also introduced. The main criteria for the success of such materials and methods are the low cost and compelling performance. Among different types of materials semiconductor nanocrystals are considered as promising candidates for the role of the efficient and cheap absorbers for solar energy applications. In addition to the anticipated cost reduction, the integration of nanocrystals (NC) into device architectures is inspired by the possibility of tuning the energy of electrical charges in NCs via nanoparticle size. However, the stability of nanocrystals in photovoltaic devices is limited by the stability of organic ligands which passivate the surface of semiconductors to preserve quantum confinement. The present work introduces a new strategy for low-temperature processing of colloidal nanocrystals into all-inorganic films: semiconductor matrix encapsulated nanocrystal arrays (SMENA). This methodology goes beyond the traditional ligand-interlinking scheme and relies on the encapsulation of morphologically-defined nanocrystal arrays into a matrix of a wide-band gap semiconductor, which preserves optoelectronic properties of individual nanoparticles. Fabricated solids exhibit excellent thermal stability, which is attributed to the heteroepitaxial structure of nanocrystal-matrix interfaces. The main characteristics and properties of these solids were investigated and compared with ones of traditionally fabricated nanocrystal films using standard spectroscopic, optoelectronic and electronic techniques. As a proof of concept, we. We also characterized electron transport phenomena in different types of nanocrystal films using all-optical approach. By measuring excited carrier lifetimes in either ligand-linked or

  12. Rovibrational matrix elements of the multipole moments and of the polarizability of the H2 molecule in the solid phase: Effect of intermolecular potential

    Adya Prasad Mishra; T K Balasubramanian


    Rovibrational matrix elements of the multipole moments ℓ up to rank 10 and of the linear polarizability of the H2 molecule in the condensed phase have been computed taking into account the effect of the intermolecular potential. Comparison with gas phase matrix elements shows that the effect of solid state interactions is marginal.

  13. Hydrothermal Synthesis of Metal Silicates

    Lii Kwang-Hwa


    Organically templated metal phosphates have been extensively studied because of interesting structural chemistry and potential applications in catalysis. However, in most cases the organic templates cannot be removed without collapse of the frameworks. This is in contrast to the high thermal stability and extensive applications of zeolites in refinery and petrochemical processes.Therefore, studies have been directed to the synthesis of transition metal silicates to produce more stable frameworks. Our synthetic methods are twofold, namely mild hydrothermal reactions in Teflon-lined autoclaves at 100-200 ℃ using organic amines as templates and high-temperature,high-pressure hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca. 550 ℃ and 150 Mpa using alkali metal cations as templates. In this presentation I will report the high-temperature, high-pressure hydrothermal synthesis, crystal structures, and solid-state NMR spectroscopy of a number of new silicates of indium, uranium, and transition metals.

  14. Modeling of transverse welds formation during liquid–solid extrusion directly following vacuum infiltration of magnesium matrix composite

    Jian Liu


    Full Text Available Liquid–solid extrusion directly following vacuum infiltration (LSEVI is an infiltration–extrusion integrated forming technique, and transverse weld between upper residual magnesium alloy and magnesium matrix composites is a common internal defect, which can severely reduce the yield of composite products. To improve current understanding on the mechanism of transverse welding phenomenon, a thermo-mechanical numerical model of LSEVI for magnesium matrix composites was developed. The formation of transverse weld during extrusion was visualized using finite element simulation method, and the formation mechanism was discussed from the aspect of velocity field using a point tracking technique. The simulation results were verified by the experimental results in term of weld shape.

  15. Characterization of silicate/Si(001) interfaces

    Copel, M.; Cartier, E.; Narayanan, V.; Reuter, M. C.; Guha, S.; Bojarczuk, N.


    Many of the proposed high permittivity gate dielectrics for silicon-based microelectronics rely on a stack configuration, with an SiO2 buffer layer to provide an interface. We describe a means for creating gate dielectrics with a direct yttrium silicate-silicon interface through the solid-state reaction of yttria and silicon oxynitride, avoiding the preparation of an oxide-free silicon surface. Characterization by medium-energy ion scattering indicates complete consumption of the underlying oxide through silicate formation during high-temperature annealing. Furthermore, the silicate dielectric exhibits small flat-band voltage shifts, indicating low quantities of charge, without passivation steps. Creation of a silicate-silicon interfaces by a simple route may enable the study of an alternate class of dielectrics.

  16. Polarizable continuum model study on the solvent effect of polymer matrix in poly(ethylene oxide)-based solid electrolyte.

    Eilmes, Andrzej; Kubisiak, Piotr


    The Polarizable Continuum Model has been used to study the effect of polymer matrix on Li (+) and Mg (2+) complexation in poly(ethylene oxide)-based solid electrolyte. Structures of complexes, stabilization energies, and vibrational frequencies are compared with corresponding vacuum values. The solvent effect of the polymer decreases with increasing cation coordination number. Optimized complex geometries do not differ significantly compared to vacuum calculations. Calculated shifts in vibrational frequencies depend on the complex structure; for hexacoordinated ion most frequencies are slightly red-shifted. The most important effect is the decrease of differences between relative stabilities of different structures in the solvent.

  17. Surfactant-free solid dispersion of fat-soluble flavour in an amorphous sugar matrix.

    Satoh, Tomo; Hidaka, Fumihiro; Miyake, Kento; Yoshiyama, Natsuki; Takeda, Koji; Matsuura, Tsutashi; Imanaka, Hiroyuki; Ishida, Naoyuki; Imamura, Koreyoshi


    A solid dispersion technique to homogeneously disperse hydrophobic ingredients in a water-soluble solid without using surfactant was examined as follows: first, freeze-dried amorphous sugar was dissolved in an organic medium that contained a soluble model hydrophobic component. Second, the mixed solution of sugar and the model hydrophobic component was vacuum dried into a solid (solid dispersion). Methanol and six fat-soluble flavours, including cinnamaldehyde, were used as organic media and model hydrophobic components. The retention of flavours in the solid dispersion during drying and storage under vacuum was evaluated. The amorphised disaccharides dissolved in methanol up to 100mg/mL, even temporarily (20s to 10 days) and could be solidified without any evidence of crystallisation and segregation from flavour. The solid dispersion, prepared using α-maltose usually showed 65-95% flavour retention during drying (and storage for cinnamaldehyde), whereas ⩾ 50% of the flavour was lost when the flavour was O/W emulsified with a surfactant and then freeze-dried with sugar.

  18. Very fast dissolving acid carboxymethylcellulose-rifampicin matrix: Development and solid-state characterization.

    Luciani-Giacobbe, Laura C; Ramírez-Rigo, María V; Garro-Linck, Yamila; Monti, Gustavo A; Manzo, Ruben H; Olivera, María E


    One of the main obstacles to the successful treatment of tuberculosis is the poor and variable oral bioavailability of rifampicin (RIF), which is mainly due to its low hydrophilicity and dissolution rate. The aim of this work was to obtain a hydrophilic new material that allows a very fast dissolution rate of RIF and therefore is potentially useful in the development of oral solid dosage forms. The acid form of carboxymethylcellulose (CMC) was co-processed with RIF by solvent impregnation to obtain CMC-RIF powder, which was characterized by polarized optical microscopy, powder x-ray diffraction, DSC-TGA, hot stage microscopy, (13)C and (15)N solid-state NMR and FT-IR spectroscopy. In addition, the CMC-RIF matrices were subjected to water uptake and dissolution studies to assess hydrophilicity and release kinetics. CMC-RIF is a crystalline solid dispersion. Solid-state characterization indicated that no ionic interaction occurred between the components, but RIF crystallized as a zwitterion over the surface of CMC, which drastically increased the hydrophilicity of the solid. The CMC-RIF matrices significantly improved the water uptake of RIF and disintegrated in a very short period immediately releasing RIF. As CMC improves the hydrophilicity and delivery properties of RIF, CMC-RIF is very useful in the design of oral solid dosage forms with very fast dissolution of RIF, either alone or in combination with other antitubercular drugs. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Sealing of cracks in cement using microencapsulated sodium silicate

    Giannaros, P.; Kanellopoulos, A.; Al-Tabbaa, A.


    Cement-based materials possess an inherent autogenous self-healing capability allowing them to seal, and potentially heal, microcracks. This can be improved through the addition of microencapsulated healing agents for autonomic self-healing. The fundamental principle of this self-healing mechanism is that when cracks propagate in the cementitious matrix, they rupture the dispersed capsules and their content (cargo material) is released into the crack volume. Various healing agents have been explored in the literature for their efficacy to recover mechanical and durability properties in cementitious materials. In these materials, the healing agents are most commonly encapsulated in macrocontainers (e.g. glass tubes or capsules) and placed into the material. In this work, microencapsulated sodium silicate in both liquid and solid form was added to cement specimens. Sodium silicate reacts with the calcium hydroxide in hydrated cement paste to form calcium-silicate-hydrate gel that fills cracks. The effect of microcapsule addition on rheological and mechanical properties of cement is reported. It is observed that the microcapsule addition inhibits compressive strength development in cement and this is observed through a plateau in strength between 28 and 56 days. The improvement in crack-sealing for microcapsule-containing specimens is quantified through sorptivity measurements over a 28 day healing period. After just seven days, the addition of 4% microcapsules resulted in a reduction in sorptivity of up to 45% when compared to specimens without any microcapsule addition. A qualitative description of the reaction between the cargo material and the cementitious matrix is also provided using x-ray diffraction analysis.

  20. Solid dispersion matrix tablet comprising indomethacin-PEG-HPMC fabricated with fusion and mold technique

    Mesnukul A


    Full Text Available The purpose of this study is to fabricate the polyethylene glycol matrix tablet by mold technique. Indomethacin and hydroxypropylmethylcellulose were used as model drug and polymer, respectively, in PEG matrix system. The physical and drug release characteristics of developed matrix tablet were studied. This inert carrier system comprising 7:3 polyethylene glycol 4000: polyethylene glycol 400 could effectively enhance the solubility of indomethacin and an addition of hydroxypropylmethylcellulose could sustain the drug release. Scanning electron microscope photomicrograph indicated the drug diffusion outward through the porous network of this developed matrix tablet into the dissolution fluid. Least square fitting the experimental dissolution data to the mathematical expressions (power law, first-order, Higuchi′s and zero-order indicated the drug release kinetics primarily as Fickian diffusion. Both the enhancement of drug dissolution and the prolongation of the drug release could be achieved for aqueous insoluble drug such as, indomethacin, by using polyethylene glycol-hydroxypropylmethylcellulose matrix system prepared with melting and mold technique.

  1. Biofilms produced by Burkholderia cenocepacia: influence of media and solid supports on composition of matrix exopolysaccharides.

    Pellizzoni, Elena; Ravalico, Fabio; Scaini, Denis; Delneri, Ambra; Rizzo, Roberto; Cescutti, Paola


    Bacteria usually grow forming biofilms, which are communities of cells embedded in a self-produced dynamic polymeric matrix, characterized by a complex three-dimensional structure. The matrix holds cells together and above a surface, and eventually releases them, resulting in colonization of other surfaces. Although exopolysaccharides (EPOLs) are important components of the matrix, determination of their structure is usually performed on samples produced in non-biofilm conditions, or indirectly through genetic studies. Among the Burkholderia cepacia complex species, Burkholderia cenocepacia is an important pathogen in cystic fibrosis (CF) patients and is generally more aggressive than other species. In the present investigation, B. cenocepacia strain BTS2, a CF isolate, was grown in biofilm mode on glass slides and cellulose membranes, using five growth media, one of which mimics the nutritional content of CF sputum. The structure of the matrix EPOLs was determined by 1H-NMR spectroscopy, while visualization of the biofilms on glass slides was obtained by means of confocal laser microscopy, phase-contrast microscopy and atomic force microscopy. The results confirmed that the type of EPOLs biosynthesized depends both on the medium used and on the type of support, and showed that mucoid conditions do not always lead to significant biofilm production, while bacteria in a non-mucoid state can still form biofilm containing EPOLs.

  2. Solid-phase synthesis of succinylhydroxamate peptides : Functionalized matrix metalloproteinase inhibitors

    Leeuwenburgh, MA; Geurink, PP; Klein, T; Kauffman, HF; van der Marel, GA; Bischoff, R; Overkleeft, HS


    A novel solid-phase synthesis strategy toward succinylhydroxamate peptides, using an appropriately protected hydroxamate building block, is described. Rapid and efficient access is gained to amine-functionalized peptides, which can be decorated with, for instance, a fluorescent label. In addition, w

  3. Evaluation of alternative environmentally friendly matrix solid phase dispersion solid supports for the simultaneous extraction of 15 pesticides of different chemical classes from drinking water treatment sludge.

    Soares, Karina Lotz; Cerqueira, Maristela Barnes Rodrigues; Caldas, Sergiane Souza; Primel, Ednei Gilberto


    This study describes the development, optimization and validation of a method for the extraction of 15 pesticides of different chemical classes in drinking water treatment sludge (DWTS) by vortex-assisted Matrix Solid Phase Dispersion (MSPD) with determination by gas chromatography coupled to mass spectrometry. It focused on the application of alternative and different solid supports to the extraction step of the MSPD. The main parameters that influenced the extraction were studied in order to obtain better recovery responses. Recoveries ranged from 70 to 120% with RSD below 20% for all analytes. Limits of quantification (LOQ) of the method ranged from 5 to 500 μg kg(-1) whereas the analytical curves showed correlation coefficients above 0.997. The method under investigation used low volume of solvent (5 mL), low sample mass (1.5 g) and low mass of chitin (0.5 g), an environmentally friendly support. It has advantages, such as speed, simplicity and low cost material, over other methods. When the method was applied, 4 out of 15 pesticides were detected in the DWTS samples in concentrations below the LOQ. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Thermodynamics and Kinetics of Silicate Vaporization

    Jacobson, Nathan S.; Costa, Gustavo C. C.


    Silicates are a common class of materials that are often exposed to high temperatures. The behavior of these materials needs to be understood for applications as high temperature coatings in material science as well as the constituents of lava for geological considerations. The vaporization behavior of these materials is an important aspect of their high temperature behavior and it also provides fundamental thermodynamic data. The application of Knudsen effusion mass spectrometry (KEMS) to silicates is discussed. There are several special considerations for silicates. The first is selection of an appropriate cell material, which is either nearly inert or has well-understood interactions with the silicate. The second consideration is proper measurement of the low vapor pressures. This can be circumvented by using a reducing agent to boost the vapor pressure without changing the solid composition or by working at very high temperatures. The third consideration deals with kinetic barriers to vaporization. The measurement of these barriers, as encompassed in a vaporization coefficient, is discussed. Current measured data of rare earth silicates for high temperature coating applications are discussed. In addition, data on magnesium-iron-silicates (olivine) are presented and discussed.

  5. Formation of Splats from Suspension Particles with Solid Inclusions Finely Dispersed in a Melted Metal Matrix

    Solonenko, O. P.


    A theoretical model has been developed to describe the splats formation from composite particles of several tens of micrometers in size whose liquid metal binder contains a high volume concentration of ultra-fine refractory solid inclusions uniformly distributed in the binder. A theoretical solution was derived, enabling evaluation of splat thickness and diameter, and also the contact temperature at the particle-substrate interface, under complete control of key physical parameters (KPPs) of the spray process (impact velocity, temperature, and size of the particle, and substrate temperature) versus the concentration of solid inclusions suspended in the metal-binder melt. Using the solution obtained, the calculations performed demonstrate the possibility of formulating adequate requirements on the KPPs of particle-substrate interaction providing a deposition of ceramic-metal coatings with predictable splat thickness and degree of particle flattening on the substrate, and also with desired contact temperature during the formation of the first coating monolayer.

  6. Adaptation response of Pseudomonas fragi on refrigerated solid matrix to a moderate electric field

    Chen, Wenbo; HU, HONGHAI; Zhang, Chunjiang; HUANG, Feng; Zhang, Dequan; Zhang, Hong


    Background Moderate electric field (MEF) technology is a promising food preservation strategy since it relies on physical properties—rather than chemical additives—to preserve solid cellular foods during storage. However, the effectiveness of long-term MEF exposure on the psychrotrophic microorganisms responsible for the food spoilage at cool temperatures remains unclear. Results The spoilage-associated psychrotroph Pseudomonas fragi MC16 was obtained from pork samples stored at 7 °C. Continu...

  7. Solid Matrix Transformation and Tracer Addition using Molten Ammonium Bifluoride Salt as a Sample Preparation Method for Laser Ablation Inductively Coupled Plasma Mass Spectrometry

    Grate, Jay W.; Gonzalez, Jhanis J.; O' Hara, Matthew J.; Kellogg, Cynthia M.; Morrison, Samuel S.; Koppenaal, David W.; Chan, George C.; Mao, Xianglei; Zorba, Vassilia; Russo, Richard


    Laser ablation (LA) is a means of sample introduction to inductively coupled plasma (ICP) mass spectrometry (MS) that avoids acid dissolution and chemical separation steps conventionally associated with solid sample analysis. At the same time, certain features of LA-ICP-MS are often mentioned in critical reviews including solid matrix variability and its influence on the ablation process, matrix dependent elemental fractionation, lack of matrix matched standards for external calibration, and limitations to internal calibration because it is challenging to add and distribute spikes into solid samples. In this paper we introduce the concept of a synergistic minimal sample preparation method that is used in combination with LA-ICP-MS as a means to overcome these limitations. The aim of this minimal sample preparation procedure is to reactively transform the original matrix to a more consistent matrix for LA-based analysis, thus reducing the effects of matrix variability, while enabling the addition of tracers. In conjunction with ICP-MS, we call this MTR-LA-ICP-MS, where MTR is derived from matrix transformation including the option to add tracers

  8. Nanostructure of Calcium Silicate Hydrates in Cements

    Skinner, L. B.


    Calcium silicate hydrate (CSH) is the major volume phase in the matrix of Portland cement concrete. Total x-ray scattering measurements with synchrotron x rays on synthetic CSH(I) shows nanocrystalline ordering with a particle diameter of 3.5(5) nm, similar to a size-broadened 1.1 nm tobermorite crystal structure. The CSH component in hydrated tricalcium silicate is found to be similar to CSH(I). Only a slight bend and additional disorder within the CaO sheets is required to explain its nanocrystalline structure. © 2010 The American Physical Society.

  9. Accelerated formation of strontium silicate by solid-state reaction in NaCl-H2O(v) system at lower temperature

    Zhang, Junhao; Qiu, Yushi; Huang, Man; Zheng, Hongjuan; Yanagisawa, Kazumichi


    An environmentally friendly NaCl-H2O system was developed to prepare SrSiO3 nanostructures from commercially available raw materials, SrCO3 and amorphous SiO2 (α-SiO2), by a one-step solid state reaction at 600 °C for 2 h. The formation of SrSiO3 was accelerated by NaCl-H2O(v) system. The results demonstrate that both NaCl and H2O played vital roles to accelerate the formation of SrSiO3 nanostructures at lower temperature. NaCl was considered to enhance the diffusivity of starting materials and the rate of solid state reactions, and promote the crystallization of products at lower temperature. Additionally, two different phases of SrSiO3 (JPDS 00-032-1257) and SrSiO3 (JPDS 00-006-0415) were abtained without or with the addition of NaCl. Water vapor accelerated the decomposition of SrCO3, and absorbed water on the surface of solid materials dissolved NaCl to form an aqueous ionic liquid composed of Na and Cl ions, which was similar to a hydrothermal process, and further increased the diffusivity of components and reduced the reaction temperature.

  10. Matrix solid-phase dispersion as a tool for phytochemical and bioactivities characterisation: Crataegus oxyacantha L._A case study.

    Benabderrahmane, Wassila; Lores, Marta; Lamas, Juan Pablo; Benayache, Samir


    The use of a matrix solid-phase dispersion (MSPD) process to extract polyphenols from hawthorn (Crataegus oxyacantha L.) a deciduous shrub with an expected rich phytochemical profile, has been evaluated. MSPD extracts of fruits and leaves have an outstanding content of polyphenols, although the particular phenolic profile is solvent dependent. The extracts were analysed by HPLC-DAD for the accurate identification of the major bioactive polyphenols, some of which have never been described for this species. MSPD has proven to be a good alternative to the classic methods of obtaining natural extracts, fast and with low consumption of organic solvents, therefore, environmentally friendly. The bioactivities can be considered also very remarkable, revealing extracts with high levels of antioxidant activity.

  11. Lipid nanoparticles with a solid matrix (SLN, NLC, LDC) for oral drug delivery.

    Muchow, Marc; Maincent, Philippe; Muller, Rainer H


    Solid lipid nanoparticles (SLN), nanostructured lipid carriers (NLC), and lipid-drug conjugates (LDC), commonly produced by high-pressure homogenization, are interesting vectors for oral delivery of lipophilic and, to a certain extent, hydrophilic substances. Their production can be done without the use of organic solvents. Techniques to make them a physically stable delivery system have been developed. Scaling up of the production process from lab-size to large-scale dimensions using high-pressure homogenization can be easily achieved by using a different type of homogenizer. The machines used for large-scale production often yield an even better product quality than the lab-scale types. This review article covers the methods of production, characterization, mechanisms of oral bioavailability enhancement, scale-up, final oral dosage forms, and regulatory aspects of lipid nanoparticles for oral drug delivery. It focuses mainly on high-pressure homogenization production methods.

  12. Bioactivity and mineralization of hydroxyapatite with bioglass as sintering aid and bioceramics with Na{sub 3}Ca{sub 6}(PO{sub 4}){sub 5} and Ca{sub 5}(PO{sub 4}){sub 2}SiO{sub 4} in a silicate matrix

    Demirkiran, Hande [Materials Science and Engineering Department, University of Texas at Arlington, Arlington, TX 76019 (United States); Mohandas, Arunesh; Dohi, Motokazi; Fuentes, Alonso; Nguyen, Kytai [Bioengineering Department, University of Texas at Arlington, Arlington, TX 76019 (United States); Aswath, Pranesh, E-mail: [Materials Science and Engineering Department, University of Texas at Arlington, Arlington, TX 76019 (United States)


    Hydroxyapatite and Bioglass-45S5 were sintered together creating new ceramic compositions that yielded increased apatite deposition and osteoblast differentiation and proliferation in vitro compared to hydroxyapatite. The sintered products characterized by X-ray diffraction, revealed hydroxyapatite as the main phase when small quantities (1, 2.5 and 5 wt.%) of bioglass was added. Bioglass behaved as a sintering aid with {beta}-TCP (Ca{sub 3}(PO{sub 4}){sub 2}) being the minor phase. The amount of {beta}-TCP increased with the amount of bioglass added. In compositions with larger additions of bioglass (10 and 25 wt.%), new phases with compositions of calcium phosphate silicate (Ca{sub 5}(PO{sub 4}){sub 2}SiO{sub 4}) and sodium calcium phosphate (Na{sub 3}Ca{sub 6}(PO{sub 4}){sub 5}) were formed respectively within amorphous silicate matrices. In vitro cell culture studies of the ceramic compositions were examined using bone marrow stromal cell (BMSC). Cell proliferation and differentiation of bone marrow stromal cells into osteoblasts were determined by Pico Green DNA assays and alkaline phosphatase (ALP) activity, respectively. All hydroxyapatite-bioglass co-sintered ceramics exhibited larger cell proliferation compared to pure hydroxyapatite samples. After 6 days in cell culture, the ceramic with Ca{sub 5}(PO{sub 4}){sub 3}SiO{sub 4} in a silicate matrix formed by reacting hydroxyapatite with 10 wt.% bioglass exhibited the maximum proliferation of the BMSC's. The ALP activity was found to be largest in the ceramic with Na{sub 3}Ca{sub 6}(PO{sub 4}){sub 5} embedded in a silicate matrix synthesized by reacting hydroxyapatite with 25 wt.% bioglass.

  13. Optical limiting effect in a two-photon absorption dye doped solid matrix

    He, Guang S.; Bhawalkar, Jayant D.; Zhao, Chan F.; Prasad, Paras N.


    We recently reported a new lasing dye, trans-4-[p-(N-ethyl-N-hydroxylethylamino)styryl]-N-methylpyridinium tetraphenylborate (ASPT), which has also been shown to possess a strong two-photon absorption (TPA) and subsequent frequency upconversion fluorescence behavior when excited with near infrared laser radiation. Based on the TPA mechanism, a highly efficient optical limiting performance has been demonstrated in a 2 cm long ASPT-doped epoxy rod pumped with 1.06 μm Q-switched laser pulses at 50-250 MW/cm2 intensity levels. The measured nonlinear absorption coefficient reached 6 cm/GW for the tested sample of dopant concentration d0=4×10-3 M/L. The molecular TPA cross section of ASPT in the epoxy matrix is estimated as σ2=2.5×10-18 cm4/GW or σ2'=4.7×10-46 cm4/photon/s, respectively. Two-photon pumped cavity lasing is also observed in an ASPT-doped polymer rod.

  14. Matrix solid-phase dispersion and solid-phase microextraction applied to study the distribution of fenbutatin oxide in grapes and white wine.

    Montes, R; Canosa, P; Lamas, J Pablo; Piñeiro, A; Orriols, I; Cela, R; Rodríguez, I


    The fate of the acaricide fenbutatin oxide (FBTO) during the elaboration of white wine is evaluated. Matrix solid-phase dispersion (MSPD) and solid-phase microextraction (SPME) were used as sample preparation techniques applied to the semi-solid and the liquid matrices involved in this research, respectively. Selective determination of FBTO was achieved by gas chromatography with atomic emission detection (GC-AED). GC coupled to mass spectrometry was also used to establish the identity of FBTO by-products detected in must and wine samples. MSPD extractions were accomplished using C18 as dispersant and co-sorbent. Sugars and other polar interferences were first removed with water and water/acetone mixtures, then FBTO was recovered with 8 mL of acetone. When used in combination with GC-AED, the MSPD method provided limits of quantification (LOQs) in the low nanogram per gram range, recoveries around 90% and relative standard deviations below 13% for extractions performed in different days. Performance of SPME for must and wine was mainly controlled by the extraction temperature, time and fibre coating. Under final conditions, FBTO was extracted in the headspace mode for 45 min at 100 degrees C, using a 100 microm poly(dimethylsiloxane)-coated fibre. The achieved LOQs remained around or below 0.1 ng mL(-1), depending on the type of sample, and the inter-day precision ranged from 10% to 13%. FBTO residues in grapes stayed mostly on the skin of the fruit. Although FBTO was not removed during must and white wine elaboration, it remained associated with suspended particles existing in must and lees, settled after must fermentation, with a negligible risk of being transferred to commercialised wine. On the other hand, two by-products of FBTO (bis and mono (2-methyl-2-phenylpropyl) tin) were identified, for first time, in must and final white wines obtained from FBTO treated grapes. Found values for the first species ranged from 0.03 to 0.9 ng mL(-1).

  15. Adaptation response of Pseudomonas fragi on refrigerated solid matrix to a moderate electric field.

    Chen, Wenbo; Hu, Honghai; Zhang, Chunjiang; Huang, Feng; Zhang, Dequan; Zhang, Hong


    Moderate electric field (MEF) technology is a promising food preservation strategy since it relies on physical properties-rather than chemical additives-to preserve solid cellular foods during storage. However, the effectiveness of long-term MEF exposure on the psychrotrophic microorganisms responsible for the food spoilage at cool temperatures remains unclear. The spoilage-associated psychrotroph Pseudomonas fragi MC16 was obtained from pork samples stored at 7 °C. Continuous MEF treatment attenuated growth and resulted in subsequent adaptation of M16 cultured on nutrient agar plates at 7 °C, compared to the control cultures, as determined by biomass analysis and plating procedures. Moreover, intracellular dehydrogenase activity and ATP levels also indicated an initial effect of MEF treatment followed by cellular recovery, and extracellular β-galactosidase activity assays indicated no obvious changes in cell membrane permeability. Furthermore, microscopic observations using scanning and transmission electron microscopy revealed that MEF induced sublethal cellular injury during early treatment stages, but no notable changes in morphology or cytology on subsequent days. Our study provides direct evidence that psychrotrophic P. fragi MC16 cultured on nutrient agar plates at 7 °C are capable of adapting to MEF treatment.

  16. Solid Matrix Based Lipidic Nanoparticles in Oral Cancer Chemotherapy: Applications and Pharmacokinetics.

    Ahmad, Javed; Amin, Saima; Rahman, Mahfoozur; Rub, Rehan Abdur; Singhal, Madhur; Ahmad, Mohammad Zaki; Rahman, Ziyaur; Addo, Richard T; Ahmad, Farhan Jalees; Mushtaq, Gohar; Kamal, Mohammad Amjad; Akhter, Sohail


    Chemotherapeutic delivery by oral route in cancer patients has the potential to create "hospitalization free chemotherapy" which is a vision of oncologists, formulation scientists and patients. Such a therapeutic approach will improve patients' compliance, ease the burden of the patients' caregivers and significantly reduce the cost of treatment. In current clinical practice, chemotherapy carried out by intravenous injection or infusion leads to undesired side-effects such as plasma concentrations crossing the maximum safe concentration, rapid body clearance and lower bioavailability. Despite the presence of challenges such as poor aqueous solubility and stability of drugs and the presence of biological barriers like multidrug efflux transporter in the GI tract, oral cancer chemotherapy has the potential to surmount those obstacles. Lipid nanoparticles (LNPs) such as solid lipid nanoparticle, nanostructured lipid carriers, nano lipid-drug conjugates, mixed micelles, liposomes and nanoemulsions have shown some promising results for use in oral anticancer drug delivery through nanotechnological approach. LNPs demonstrate enhanced oral bioavailability owing to their ability to inhibit first pass metabolism via lymphatic absorption by chylomicron-linked and/or M-cell uptake. LNPs reduce the inter- and intrasubject pharmacokinetics variability of administrated drugs. Moreover, certain classes of phospholipids and surfactants used in the formulations of LNPs can suppress the P-glycoprotein efflux system. Here, we shall be discussing the biopharmaceutical challenges in oral cancer chemotherapy and how the LNPs may provide solutions to such challenges. The effect of GI tract environment on LNPs and pharmacokinetics shall also be discussed.


    Nediljka Gaurina-Međimurec


    Full Text Available The silicate-based drilling fluid is a low solids KCl/polymer system with the addition of soluble sodium or potassium silicate to enhance inhibition and wellbore stability. Silicate-based drilling fluids exhibit remarkable shale and chalk stabilizing properties, resulting in gauge hole and the formation of firm cuttings when drilling reactive shales and soft chalks. Silicates protect shales by in-situ gellation when exposed to the neutral pore fluid and precipitation, which occurs on contact with divalent ions present at the surface of the shale. Also, silicates prevent the dispersion and washouts when drilling soft chalk by reacting with the Ca2+ ions present on chalk surfaces of cutting and wellbore to form a protective film. The silicate-based drilling fluid can be used during drilling hole section through shale interbeded anhydrite formations because of its superior shale stabilizing characteristics. However, drilling through the anhydrite can decrease the silicate concentration and change rheological and filtration fluid properties. So, the critical concentration of calcium ions should be investigated by lab tests. This paper details the mechanism of shale inhibition using silicate-based drilling fluid, and presents results of lab tests conducted to ascertain the effect of Ca2+ ions on silicate level in the fluid and the fluid properties.

  18. Polymer-Layer Silicate Nanocomposites

    Potarniche, Catalina-Gabriela

    Nowadays, some of the material challenges arise from a performance point of view as well as from recycling and biodegradability. Concerning these aspects, the development of polymer layered silicate nanocomposites can provide possible solutions. This study investigates how to obtain polymer layered...... silicate nanocomposites and their structure-properties relationship. In the first part of the thesis, thermoplastic layered silicates were obtained by extrusion. Different modification methods were tested to observe the intercalation treatment effect on the silicate-modifier interactions. The silicate...

  19. Simultaneous determination of phenolic compounds in Equisetum palustre L. by ultra high performance liquid chromatography with tandem mass spectrometry combined with matrix solid-phase dispersion extraction.

    Wei, Zuofu; Pan, Youzhi; Li, Lu; Huang, Yuyang; Qi, Xiaolin; Luo, Meng; Zu, Yuangang; Fu, Yujie


    A method based on matrix solid-phase dispersion extraction followed by ultra high performance liquid chromatography with tandem mass spectrometry is presented for the extraction and determination of phenolic compounds in Equisetum palustre. This method combines the high efficiency of matrix solid-phase dispersion extraction and the rapidity, sensitivity, and accuracy of ultra high performance liquid chromatography with tandem mass spectrometry. The influential parameters of the matrix solid-phase dispersion extraction were investigated and optimized. The optimized conditions were as follows: silica gel was selected as dispersing sorbent, the ratio of silica gel to sample was selected to be 2:1 (400/200 mg), and 8 mL of 80% methanol was used as elution solvent. Furthermore, a fast and sensitive ultra high performance liquid chromatography with tandem mass spectrometry method was developed for the determination of nine phenolic compounds in E. palustre. This method was carried out within <6 min, and exhibited satisfactory linearity, precision, and recovery. Compared with ultrasound-assisted extraction, the proposed matrix solid-phase dispersion procedure possessed higher extraction efficiency, and was more convenient and time saving with reduced requirements on sample and solvent amounts. All these results suggest that the developed method represents an excellent alternative for the extraction and determination of active components in plant matrices.

  20. Utilization of chemically treated municipal solid waste (spent coffee bean powder) as reinforcement in cellulose matrix for packaging applications.

    Thiagamani, Senthil Muthu Kumar; Nagarajan, Rajini; Jawaid, Mohammad; Anumakonda, Varadarajulu; Siengchin, Suchart


    As the annual production of the solid waste generable in the form of spent coffee bean powder (SCBP) is over 6 million tons, its utilization in the generation of green energy, waste water treatment and as a filler in biocomposites is desirable. The objective of this article is to analyze the possibilities to valorize coffee bean powder as a filler in cellulose matrix. Cellulose matrix was dissolved in the relatively safer aqueous solution mixture (8% LiOH and 15% Urea) precooled to -12.5°C. To the cellulose solution (SCBP) was added in 5-25wt% and the composite films were prepared by regeneration method using ethyl alcohol as a coagulant. Some SCBP was treated with aq. 5% NaOH and the composite films were also prepared using alkali treated SCBP as a filler. The films of composites were uniform with brown in color. The cellulose/SCBP films without and with alkali treated SCBP were characterized by FTIR, XRD, optical and polarized optical microscopy, thermogravimetric analysis (TGA) and tensile tests. The maximum tensile strength of the composite films with alkali treated SCBP varied between (106-149MPa) and increased with SCBP content when compared to the composites with untreated SCBP. The thermal stability of the composite was higher at elevated temperatures when alkali treated SCBP was used. Based on the improved tensile properties and photo resistivity, the cellulose/SCBP composite films with alkali treated SCBP may be considered for packaging and wrapping of flowers and vegetables. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Development of a poly(dimethylacrylamide) based matrix material for solid phase high density peptide array synthesis employing a laser based material transfer

    Ridder, Barbara; Foertsch, Tobias C.; Welle, Alexander; Mattes, Daniela S.; von Bojnicic-Kninski, Clemens M.; Loeffler, Felix F.; Nesterov-Mueller, Alexander; Meier, Michael A. R.; Breitling, Frank


    Poly(dimethylacrylamide) (PDMA) based matrix materials were developed for laser-based in situ solid phase peptide synthesis to produce high density arrays. In this specific array synthesis approach, amino acid derivatives are embedded into a matrix material, serving as a "solid" solvent material at room temperature. Then, a laser pulse transfers this mixture to the target position on a synthesis slide, where the peptide array is synthesized. Upon heating above the glass transition temperature of the matrix material, it softens, allowing diffusion of the amino acid derivatives to the synthesis surface and serving as a solvent for peptide bond formation. Here, we synthesized PDMA six-arm star polymers, offering the desired matrix material properties, using atom transfer radical polymerization. With the synthesized polymers as matrix material, we structured and synthesized arrays with combinatorial laser transfer. With densities of up to 20,000 peptide spots per cm2, the resolution could be increased compared to the commercially available standard matrix material. Time-of-Flight Secondary Ion Mass Spectrometry experiments revealed the penetration behavior of an amino acid derivative into the prepared acceptor synthesis surface and the effectiveness of the washing protocols.

  2. Matrix molecularly imprinted mesoporous sol-gel sorbent for efficient solid-phase extraction of chloramphenicol from milk.

    Samanidou, Victoria; Kehagia, Maria; Kabir, Abuzar; Furton, Kenneth G


    Highly selective and efficient chloramphenicol imprinted sol-gel silica based inorganic polymeric sorbent (sol-gel MIP) was synthesized via matrix imprinting approach for the extraction of chloramphenicol in milk. Chloramphenicol was used as the template molecule, 3-aminopropyltriethoxysilane (3-APTES) and triethoxyphenylsilane (TEPS) as the functional precursors, tetramethyl orthosilicate (TMOS) as the cross-linker, isopropanol as the solvent/porogen, and HCl as the sol-gel catalyst. Non-imprinted sol-gel polymer (sol-gel NIP) was synthesized under identical conditions in absence of template molecules for comparison purpose. Both synthesized materials were characterized by Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR) and nitrogen adsorption porosimetry, which unambiguously confirmed their significant structural and morphological differences. The synthesized MIP and NIP materials were evaluated as sorbents for molecularly imprinted solid phase extraction (MISPE) of chloramphenicol in milk. The effect of critical extraction parameters (flow rate, elution solvent, sample and eluent volume, selectivity coefficient, retention capacity) was studied in terms of retention and desorption of chloramphenicol. Competition and cross reactivity tests have proved that sol-gel MIP sorbent possesses significantly higher specific retention and enrichment capacity for chloramphenicol compared to its non-imprinted analogue. The maximum imprinting factor (IF) was found as 9.7, whereas the highest adsorption capacity of chloramphenicol by sol-gel MIP was 23 mg/g. The sol-gel MIP was found to be adequately selective towards chloramphenicol to provide the necessary minimum required performance limit (MRPL) of 0.3 μg/kg set forth by European Commission after analysis by LC-MS even without requiring time consuming solvent evaporation and sample reconstitution step, often considered as an integral part in solid phase extraction work-flow. Intra and

  3. Matrix solid phase dispersion assisted enzymatic hydrolysis as a novel approach for cocaine and opiates isolation from human hair.

    Míguez-Framil, Martha; Cabarcos, Pamela; Tabernero, María Jesús; Bermejo, Ana María; Bermejo-Barrera, Pilar; Moreda-Piñeiro, Antonio


    The possibility of assisting enzymatic hydrolysis (EH) procedures by sample disruption mechanisms inherent to matrix solid phase dispersion (MSPD) has been explored in the current study. EH of hair specimens from poly-drug abusers was assisted by dispersing/blending the sample (0.05 g) with alumina (2.25 g) before loading the dissolved enzyme (6 mL of 1 mg mL(-1) Pronase E in 1.4 M/1.4 M Tris/HCl, pH 7.3) through the hair-alumina solid phase packaged inside a disposable MSPD syringe. The MSPD-EH method was developed, and it proved to offer quantitative results when isolating cocaine, benzoylecgonine (BZE), codeine, morphine and 6-monoacethylmorphine (6-MAM) from human hair samples. The procedure allows an on column clean-up/pre-concentration procedure of the isolated targets by attaching a previously conditioned Oasis HLB cartridge to the end of the MSPD syringe. The EH procedure of human hair with Pronase E can therefore be shortened to approximately 30 min. Within this time, sample blending/dispersion, MSPD syringe package, elution (EH when dissolved Pronase E is passing through the sample-dispersant bed), and extract clean-up and target pre-concentration stages are achieved. Gas chromatography-mass spectrometry (GC-MS) was used for determining each target after elution from the Oasis HLB cartridges with 2 mL of 2% (v/v) acetic acid in methanol, concentration by N2 stream evaporation, and dried extract derivatization with N-methyl-tert-butylsilyltrifluoroacetamide (BSTFA) and chlorotrimethylsilane (TMCS). The method was validated according to the guidance for bioanalytical method validation of the US Department of Health and Human Services, Food and Drug Administration. The simplicity of the proposed approach makes it a useful procedure for screening/quantifying drugs of abuse in hair specimens from poly-drug abusers.

  4. Luminescence properties of cerium-doped di-strontium magnesium di-silicate phosphor by the solid-state reaction method

    Prasad Sahu, Ishwar


    A series of Sr2MgSi2O7:xCe3+ (x = 1.0%, 2.0%, 3.0%, 4.0% and 5.0%) phosphors were synthesized by the solid-state reaction method. The phosphor with optimum thermoluminescence, photoluminescence and mechanoluminescence (ML) intensity was characterized by X-ray diffraction, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy and Fourier transform infrared techniques. The trapping parameters (i.e. activation energy, frequency factor and order of the kinetics) of each synthesized phosphor have been calculated using the peak shape method and the results have been discussed. Under ultraviolet excitation (325 nm), Sr2MgSi2O7:xCe3+ phosphors were composed of a broad band peaking at 385 nm, belonging to the broad emission band which emits violet-blue color. Commission International de I'Eclairage coordinates have been calculated for each sample and their overall emission is near violet-blue light. In order to investigate the suitability of the samples for industrial uses, color purity and color rendering index were calculated. An ML intensity of optimum [Sr2MgSi2O7:Ce3+ (3.0%)] phosphor increases linearly with increasing impact velocity of the moving piston which suggests that these phosphors can be used as fracto-ML-based devices. The time of the peak ML intensity and the decay rate did not change significantly with respect to increasing impact velocity of the moving piston.

  5. Evaluation of polycyclic aromatic hydrocarbons in asphalt binder using matrix solid-phase dispersion and gas chromatography.

    Fernandes, Paulo R N; Soares, Sandra de A; Nascimento, Ronaldo F; Soares, Jorge B; Cavalcante, Rivelino M


    A method developed for the extraction and analysis of polycyclic aromatic hydrocarbons (PAHs) in the asphalt binder using a matrix solid-phase dispersion (MSPD) and gas chromatography is presented. The MSPD method was proposed as a rapid and easy approach to determining PAHs present in the maltenic phase of asphalt binder extracted through a mechanical shaking and sonication of the material. The recovery rates ranged from 62.77-89.92% (shaking) and from 56.54-93.6% (sonication) with relative standard deviations lower than 8.8%. The study shows that the recovery rates using shaking and sonication extractions are not significantly different at the p asphalt binder from Brazil. The main PAHs found were BbF, BaP, Per, IncdP, DahA, and BghiP, with average concentrations of 10.2-20.7 mg/kg, but the PAHs Ace and Acy were not detected. However, Nap, Fl, Phen, Ant, Flr, Pyr, Chry, BaA, and BkF were present in average concentrations amounting to less than 10 mg/kg. The results showed that the MSPD method is potentially a valuable tool for the determination of PAHs in the asphalt binder.

  6. Analysis of four toxic metals in a single rice seed by matrix solid phase dispersion -inductively coupled plasma mass spectrometry

    He, Xiufen; Chen, Lixia; Chen, Xin; Yu, Huamei; Peng, Lixu; Han, Bingjun


    Toxic metals in rice pose great risks to human health. Metal bioaccumulation in rice grains is a criterion of breeding. Rice breeding requires a sensitive method to determine metal content in single rice grains to assist the variety selection. In the present study, four toxic metals of arsenic (As), cadmium (Cd), chromium (Cr) and lead (Pb) in a single rice grain were determined by a simple and rapid method. The developed method is based on matrix solid phase dispersion using multi-wall carbon nanotubes (MWCNTs) as dispersing agent and analyzed by inductively coupled plasma mass spectrometry. The experimental parameters were systematically investigated. The limits of detection (LOD) were 5.0, 0.6, 10 and 2.1 ng g‑1 for As, Cd, Cr, and Pb, respectively, with relative standard deviations (n = 6) of microwave digestion. The amount of sample required was reduced approximately 100 fold in comparison with the microwave digestion. The method has a high application potential for other sample matrices and elements with high sensitivity and sample throughput.

  7. Graphene nanoplatelets based matrix solid-phase dispersion microextraction for phenolic acids by ultrahigh performance liquid chromatography with electrochemical detection.

    Peng, Li-Qing; Yi, Ling; Yang, Qiu-Cheng; Cao, Jun; Du, Li-Jing; Zhang, Qi-Dong


    A simple, rapid and eco-friendly approach based on matrix solid-phase dispersion microextraction (MSPDM) followed by ultrahigh performance liquid chromatography coupled with electrochemical detection (UHPLC-ECD) was presented for the microextraction and determination of six phenolic acids in a plant preparation (Danshen tablets). The parameters that influenced the extraction performance of phenolic acids were investigated and optimized. The optimal MSPDM conditions were determined as follows: sorbent, using graphene nanoplatelets with sample/sorbent ratio of 1:1, grinding time set at 60 s, and 0.2 mL of water as elution solvent. Under the optimum conditions, the validation experiments indicated that the proposed method exhibited good linearity (r(2) ≥ 0.9991), excellent precision (RSD ≤ 4.57%), and satisfactory recoveries (82.34-98.34%). The limits of detection were from 1.19 to 4.62 ng/mL for six phenolic acids. Compared with other reported methods, this proposal required less sample, solvent and extraction time. Consequently, the proposed method was successfully used to the extraction and determination of phenolic acids in Danshen tablets.

  8. Novel dummy molecularly imprinted polymers for matrix solid-phase dispersion extraction of eight fluoroquinolones from fish samples.

    Sun, Xiaoli; Wang, Jincheng; Li, Yun; Yang, Jiajia; Jin, Jing; Shah, Syed Mazhar; Chen, Jiping


    A series of novel dummy molecularly imprinted polymers (DMIPs) were prepared as highly class-selective sorbents for fluoroquinolones. A non-poisonous dummy template, daidzein, was used for the first time to create specific molecular recognition sites for fluoroquinolones in the synthesized polymers. The influence of porogen polarity on dummy molecular imprinting effect was studied. The DMIP prepared using dimethylsulfoxide-acetonitrile (1:1.8, v/v) as porogen achieved the highest imprinting factors (IF) for fluoroquinolones over a range of IF 13.4-84.0. This DMIP was then used for selective extraction of eight fluoroquinolones (fleroxacin, ofloxacin, norfloxacin, pefloxacin, ciprofloxacin, lomefloxacin, enrofloxacin and gatifloxacin) from fish samples based on dummy molecularly imprinted matrix solid-phase dispersion (DMI-MSPD). The extracted fluoroquinolones were subsequently analyzed by high-performance liquid chromatography (HPLC) equipped with a fluorescence detector (FLD). The developed method had acceptable recoveries (64.4-102.7%) and precision (RSDs: 1.7-8.5%, n=5) for determination of fluoroquinolones in fish samples fortified at levels of 10 and 100ngg(-1). The limits of detection (LODs) for identification of eight fluoroquinolones ranged between 0.06 and 0.22ngg(-1). The results demonstrated great potential of the optimized method for sample preparation in routine analysis of trace fluoroquinolones in fish samples. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. High-flexibility combinatorial peptide synthesis with laser-based transfer of monomers in solid matrix material.

    Loeffler, Felix F; Foertsch, Tobias C; Popov, Roman; Mattes, Daniela S; Schlageter, Martin; Sedlmayr, Martyna; Ridder, Barbara; Dang, Florian-Xuan; von Bojničić-Kninski, Clemens; Weber, Laura K; Fischer, Andrea; Greifenstein, Juliane; Bykovskaya, Valentina; Buliev, Ivan; Bischoff, F Ralf; Hahn, Lothar; Meier, Michael A R; Bräse, Stefan; Powell, Annie K; Balaban, Teodor Silviu; Breitling, Frank; Nesterov-Mueller, Alexander


    Laser writing is used to structure surfaces in many different ways in materials and life sciences. However, combinatorial patterning applications are still limited. Here we present a method for cost-efficient combinatorial synthesis of very-high-density peptide arrays with natural and synthetic monomers. A laser automatically transfers nanometre-thin solid material spots from different donor slides to an acceptor. Each donor bears a thin polymer film, embedding one type of monomer. Coupling occurs in a separate heating step, where the matrix becomes viscous and building blocks diffuse and couple to the acceptor surface. Furthermore, we can consecutively deposit two material layers of activation reagents and amino acids. Subsequent heat-induced mixing facilitates an in situ activation and coupling of the monomers. This allows us to incorporate building blocks with click chemistry compatibility or a large variety of commercially available non-activated, for example, posttranslationally modified building blocks into the array's peptides with >17,000 spots per cm(2).

  10. Metal-organic framework mixed-matrix disks: Versatile supports for automated solid-phase extraction prior to chromatographic separation.

    Ghani, Milad; Font Picó, Maria Francesca; Salehinia, Shima; Palomino Cabello, Carlos; Maya, Fernando; Berlier, Gloria; Saraji, Mohammad; Cerdà, Víctor; Turnes Palomino, Gemma


    We present for the first time the application of metal-organic framework (MOF) mixed-matrix disks (MMD) for the automated flow-through solid-phase extraction (SPE) of environmental pollutants. Zirconium terephthalate UiO-66 and UiO-66-NH2 MOFs with different size (90, 200 and 300nm) have been incorporated into mechanically stable polyvinylidene difluoride (PVDF) disks. The performance of the MOF-MMDs for automated SPE of seven substituted phenols prior to HPLC analysis has been evaluated using the sequential injection analysis technique. MOF-MMDs enabled the simultaneous extraction of phenols with the concomitant size exclusion of molecules of larger size. The best extraction performance was obtained using a MOF-MMD containing 90nm UiO-66-NH2 crystals. Using the selected MOF-MMD, detection limits ranging from 0.1 to 0.2μgL(-1) were obtained. Relative standard deviations ranged from 3.9 to 5.3% intra-day, and 4.7-5.7% inter-day. Membrane batch-to-batch reproducibility was from 5.2 to 6.4%. Three different groundwater samples were analyzed with the proposed method using MOF-MMDs, obtaining recoveries ranging from 90 to 98% for all tested analytes.

  11. High-flexibility combinatorial peptide synthesis with laser-based transfer of monomers in solid matrix material

    Loeffler, Felix F.; Foertsch, Tobias C.; Popov, Roman; Mattes, Daniela S.; Schlageter, Martin; Sedlmayr, Martyna; Ridder, Barbara; Dang, Florian-Xuan; von Bojničić-Kninski, Clemens; Weber, Laura K.; Fischer, Andrea; Greifenstein, Juliane; Bykovskaya, Valentina; Buliev, Ivan; Bischoff, F. Ralf; Hahn, Lothar; Meier, Michael A. R.; Bräse, Stefan; Powell, Annie K.; Balaban, Teodor Silviu; Breitling, Frank; Nesterov-Mueller, Alexander


    Laser writing is used to structure surfaces in many different ways in materials and life sciences. However, combinatorial patterning applications are still limited. Here we present a method for cost-efficient combinatorial synthesis of very-high-density peptide arrays with natural and synthetic monomers. A laser automatically transfers nanometre-thin solid material spots from different donor slides to an acceptor. Each donor bears a thin polymer film, embedding one type of monomer. Coupling occurs in a separate heating step, where the matrix becomes viscous and building blocks diffuse and couple to the acceptor surface. Furthermore, we can consecutively deposit two material layers of activation reagents and amino acids. Subsequent heat-induced mixing facilitates an in situ activation and coupling of the monomers. This allows us to incorporate building blocks with click chemistry compatibility or a large variety of commercially available non-activated, for example, posttranslationally modified building blocks into the array's peptides with >17,000 spots per cm2.

  12. Application of ionic liquids for elution of bioactive flavonoid glycosides from lime fruit by miniaturized matrix solid-phase dispersion.

    Xu, Jing-Jing; Yang, Rui; Ye, Li-Hong; Cao, Jun; Cao, Wan; Hu, Shuai-Shuai; Peng, Li-Qing


    In this work, two flavonoid glycosides (neohesperidin and naringin) in lime fruit were effectively extracted by miniaturized matrix solid phase dispersion (MSPD), followed by ultra-performance liquid chromatography-ultraviolet detection. The best results were obtained using Florisil (150mg) as the sorbent and 1-butyl-3-methylimidazolium tetrafluoroborate (0.4mL, 250mM) as the elution solvent. This work represents the first attempt of using ionic liquids as a green eluent for extraction of the investigated compounds in miniaturized MSPD. Compared with the conventional methods, the proposed method is advantageous due to improved enrichment factor and reduced reagent consumption. A good linearity was observed with r(2) values (>0.998). Meanwhile, the method gave acceptable recoveries (90.16-96.47%) for the determination of flavonoids in plant samples. The limits of detection of the two analytes ranged between 4.08 and 5.04μg/g. The results showed that the optimized method has a great potential for sample preparation in routine analysis of complex plant samples.

  13. Silicic Large Igneous Provinces

    Scott Bryan


    @@ Large Igneous Provinces (LIPs) are the end-product of huge additions of magma to the continental crust both at the surface and at depth. Since the first categorisation of LIPs by Coffin & Eldholm (1994), it has been recognised that LIPs are more varied inform, age and character, and this includes the recognition of Silicic LIPs. Silicic LIPs are the largest accumulations of primary volcaniclastic rocks at the Earth's surface with areal extents >0.1 Mkm2 and extrusive and subvolcanic intrusive volumes >0.25 Mkm3. The Late Palaeozoic to Cenozoic Silicic LIP events are the best recognised and are similar in terms of their dimension, crustal setting, volcanic architecture and geochemistry.

  14. Six White Dwarfs with Circumstellar Silicates

    Jura, M; Zuckerman, B


    Spitzer Space Telescope spectra reveal 10 micron silicate emission from circumstellar dust orbiting six externally-polluted white dwarfs. Micron-size glasses with an olivine stoichiometry can account for the distinctively broad wings that extend to 12 microns; these particles likely are produced by tidal-disruption of asteroids. The absence of infrared PAH features is consistent with a scenario where extrasolar rocky planets are assembled from carbon-poor solids.

  15. Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction for the determination of sulfonamides in animal tissues using high-performance liquid chromatography.

    Wang, Zhibing; He, Mengyu; Jiang, Chunzhu; Zhang, Fengqing; Du, Shanshan; Feng, Wennan; Zhang, Hanqi


    Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction was developed and applied to the extraction of some sulfonamides, including sulfamerazine, sulfamethazine, sulfathiazole, sulfachloropyridazine, sulfadoxine, sulfisoxazole, and sulfaphenazole, in animal tissues. High-performance liquid chromatography was applied to the separation and determination of the target analytes. The solid sample was directly treated by matrix solid-phase dispersion and the eluate obtained was treated by homogeneous ionic liquid microextraction. The ionic liquid was used as the extraction solvent in this method, which may result in the improvement of the recoveries of the target analytes. To avoid using organic solvent and reduce environmental pollution, water was used as the elution solvent of matrix solid-phase dispersion. The effects of the experimental parameters on recoveries, including the type and volume of ionic liquid, type of dispersant, ratio of sample to dispersant, pH value of elution solvent, volume of elution solvent, amount of salt in eluate, amount of ion-pairing agent (NH4 PF6 ), and centrifuging time, were evaluated. When the present method was applied to the analysis of animal tissues, the recoveries of the analytes ranged from 85.4 to 118.0%, and the relative standard deviations were lower than 9.30%. The detection limits for the analytes were 4.3-13.4 μg/kg.

  16. Matrix molecularly imprinted mesoporous sol–gel sorbent for efficient solid-phase extraction of chloramphenicol from milk

    Samanidou, Victoria, E-mail: [Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University of Thessaloniki (Greece); Kehagia, Maria [Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University of Thessaloniki (Greece); Kabir, Abuzar, E-mail: [International Forensic Research Institute, Department of Chemistry and Biochemistry, Florida International University, Miami, FL (United States); Furton, Kenneth G. [International Forensic Research Institute, Department of Chemistry and Biochemistry, Florida International University, Miami, FL (United States)


    Highly selective and efficient chloramphenicol imprinted sol–gel silica based inorganic polymeric sorbent (sol–gel MIP) was synthesized via matrix imprinting approach for the extraction of chloramphenicol in milk. Chloramphenicol was used as the template molecule, 3-aminopropyltriethoxysilane (3-APTES) and triethoxyphenylsilane (TEPS) as the functional precursors, tetramethyl orthosilicate (TMOS) as the cross-linker, isopropanol as the solvent/porogen, and HCl as the sol–gel catalyst. Non-imprinted sol–gel polymer (sol–gel NIP) was synthesized under identical conditions in absence of template molecules for comparison purpose. Both synthesized materials were characterized by Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR) and nitrogen adsorption porosimetry, which unambiguously confirmed their significant structural and morphological differences. The synthesized MIP and NIP materials were evaluated as sorbents for molecularly imprinted solid phase extraction (MISPE) of chloramphenicol in milk. The effect of critical extraction parameters (flow rate, elution solvent, sample and eluent volume, selectivity coefficient, retention capacity) was studied in terms of retention and desorption of chloramphenicol. Competition and cross reactivity tests have proved that sol–gel MIP sorbent possesses significantly higher specific retention and enrichment capacity for chloramphenicol compared to its non-imprinted analogue. The maximum imprinting factor (IF) was found as 9.7, whereas the highest adsorption capacity of chloramphenicol by sol–gel MIP was 23 mg/g. The sol–gel MIP was found to be adequately selective towards chloramphenicol to provide the necessary minimum required performance limit (MRPL) of 0.3 μg/kg set forth by European Commission after analysis by LC-MS even without requiring time consuming solvent evaporation and sample reconstitution step, often considered as an integral part in solid phase extraction work

  17. Determination of perfluorinated compounds in mollusks by matrix solid-phase dispersion and liquid chromatography-tandem mass spectrometry.

    Villaverde-de-Sáa, Eugenia; Quintana, José Benito; Rodil, Rosario; Ferrero-Refojos, Raúl; Rubí, Elisa; Cela, Rafael


    Perfluorinated compounds (PFCs) have been used for over 40 years in different commercial and industrial applications mainly as surfactants and surface protectors and have become an important class of marine emerging pollutants. This study presents the development and validation of a new analytical method to determine the simultaneous presence of eight PFCs in different kinds of mollusks using matrix solid-phase dispersion (MSPD) followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Simplicity of the analytical procedure, low volume of solvent and quantity of sample required, low global price, and integration of extraction and clean-up into a single step, are the most important advantages of the developed methodology. Solvent, solid support (dispersing agent), clean-up sorbent, and their amounts were optimized by means of an experimental design. In the final method, 0.5 g of sample are dispersed with 0.2 g of diatomaceous earth and transferred into a polypropylene syringe containing 4 g of silica as clean-up sorbent. Then, analytes are eluted with 20 mL of acetonitrile. The extract is finally concentrated to a final volume of 0.5 mL in methanol, avoiding extract dryness in order to prevent evaporation losses and injected in the LC-MS/MS. The combination of this MSPD protocol with LC-MS/MS afforded detection limits from 0.05 to 0.3 ng g(-1). Also, a good linearity was established for the eight PFCs in the range from limit of quantification (LOQ) to 500 ng mL(-1) with R(2) > 0.9917. The recovery of the method was studied with three types of spiked mollusk and was in the 64-126% range. Moreover, a mussel sample was spiked and aged for more than 1 month and analyzed by the developed method and a reference method, ion-pair extraction, for comparison, producing both methods statistically equal concentration values. The method was finally applied to the determination of PFCs in different kinds of mollusks revealing concentrations up to 8.3 ng g(-1) for

  18. Vortex-homogenized matrix solid-phase dispersion for the extraction of short chain chlorinated paraffins from indoor dust samples.

    Chen, Yu-Hsuan; Chang, Chia-Yu; Ding, Wang-Hsien


    A simple and effective method for determining short chain chlorinated paraffins (SCCPs) in indoor dust is presented. The method employed a modified vortex-homogenized matrix solid-phase dispersion (VH-MSPD) prior to its detection by gas chromatography - electron-capture negative-ion mass spectrometry (GC-ECNI-MS) operating in the selected-ion-monitoring (SIM) mode. Under the best extraction conditions, 0.1-g of dust sample was dispersed with 0.1-g of silica gel by using vortex (2min) instead of using a mortar and pestle (3min). After that step, the blend was transferred to a glass column containing 3-g acidic silica gel, 2-g basic silica gel, and 2-g of deactivated silica gel, used as clean-up co-sorbents. Then, target analytes were eluted with 5mL of n-hexane/dichloromethane (2:1, v/v) mixture. The extract was evaporated to dryness under a gentle stream of nitrogen. The residue was then re-dissolved in n-hexane (10μL), and subjected to GC-ECNI-MS analysis. The limits of quantitation (LOQs) ranged from 0.06 to 0.25μg/g for each SCCP congener. Precision was less than 7% for both intra- and inter-day analysis. Trueness was above 89%, which was calculated by mean extraction recovery. The VH-MSPD combined with GC-ECNI-MS was successfully applied to quantitatively detect SCCPs from various indoor dust samples, and the concentrations ranged from 1.2 to 31.2μg/g. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Graphene-encapsulated silica as matrix solid-phase dispersion extraction sorbents for the analysis of poly-methoxylated flavonoids in the leaves of Murraya panaculata (L.) Jack.

    Sun, Ting; Li, Xuwen; Yang, Jie; Li, Lanjie; Jin, Yongri; Shi, Xiaolei


    In this study, graphene-encapsulated silica was synthesized by a hydrothermal reduction strategy. The presence of silica in graphene was identified by Fourier-transform infrared spectrometry, X-ray diffraction and scanning electron microscopy. The graphene-encapsulated silica subsequently was used as adsorbent for matrix solid-phase dispersion extraction of poly-methoxylated flavonoids from the dried leaves of Murraya panaculata (L.) Jack. Compared with the other adsorbents (graphene, silica gel, C18 silica, neutral alumina, diatomaceous earth) and without any adsorbents, better results were obtained. Then a method for analysis of poly-methoxylated flavonoids was established by coupling matrix solid-phase dispersion extraction with ultra high performance liquid chromatography and UV detection. Compared with reflux extraction and ultrasonic extraction, the proposed method is quicker, more efficient and more environmental protection. Less than 10 min is needed from extraction to detection.

  20. Behaviors of Oxide Layer at Interface between Semi-solid Filler Metal and Aluminum Matrix Composites during Vibration

    Lei Shi; Jiuchun Yan; Yanfei Han; Bo Peng


    The joint interface between semi-solid Zn-Al filler metal and SiCp/Al composites with applying vibration for different time was examined. With increasing vibrating time, the oxide layer was disrupted prior at the centre to the periphery of the interface. And the solid grains near the centre of interface in semi-solid filler metal aggregated into two solid regions and compressed the composites during vibration; the solid grains near the periphery of interface moved toward the edge and scraped the composites during vibration. The models of disrupting oxide layer under the vibration condition were developed. At the centre of interface, the oxide layer was tore and stripped during the solid grains in the semi-solid filler metal depressing the composites with a very high compressive stress. At the periphery of interface, the oxide layer was cut and stripped into the filler metal during the solid grains scraping the interface.

  1. Matrix Solid-Phase Dispersion Coupled with High-Performance Liquid Chromatography Diode Array Detection for Simultaneous Determination of Four Lipophilic Constituents from Salvia miltiorrhiza Bunge.

    Wang, Zhibing; Ma, Siyu; Zhang, Qian; He, Shuang; Li, Qing; Hu, Jianxue; Zhang, Hanqi


    A simple, rapid and efficient method based on matrix solid-phase dispersion coupled with high-performance liquid chromatography was developed for determination of lipophilic constituents, including dihydrotanshinone, tanshinone I, cryptotanshinone and tanshinone II A in Salvia miltiorrhiza Bunge Box-Behnken design was employed for optimization of the extraction conditions of matrix solid-phase dispersion, including mass ratio of dispersant to sample, volume of elution solvent, and amount of cleanup reagent. The optimal experimental results were obtained using 0.27 g of acid alumina as dispersant, 13 mL of acetonitrile as elution solvent and 0.36 g of acid alumina as cleanup reagent. The target analytes was determined by high-performance liquid chromatography. The recoveries of tanshinones obtained by analyzing the spiked samples were from 83.81% to 93.74% and relative standard deviations from 2.87% to 6.83%. Matrix solid-phase dispersion integrated the extraction and cleanup into a single step, which provides the advantages of being simple, fast and convenient. Compared with other conventional methods, the present method consumed less time and less organic solvent. The results demonstrate that this method has potential for the determination of active constituents and the quality control of traditional Chinese medicine.

  2. Spectroscopy of low-energy atoms released from a solid noble-gas matrix: Proposal for a trap-loading technique

    Lambo, R.; Rodegheri, C. C.; Silveira, D. M.; Cesar, C. L.


    We have studied the velocity distribution of chromium atoms released from a solid neon matrix at cryogenic temperatures via Doppler spectroscopy. The Ne matrix is grown by directing a small flux of gas onto a cold substrate, while Cr atoms are simultaneously implanted by laser ablation, with the resultant plume directed toward the growing matrix. The atoms are then released by a heat pulse. We have observed neutral Cr atoms at temperatures around 13K with densities close to 1012cm-3 . The released atoms have a large initial drift velocity, explained by simple kinetic theory arguments, due to the light species’ drag force. The scheme could be adapted to produce cryogenic beams of atoms, molecules, and possibly ions, for collisional studies and spectroscopy. However, our main motivation was the construction of a hydrogen trap, and here we discuss the prospects and problems of using this technique for this purpose.

  3. Silicates in Alien Asteroids


    This plot of data from NASA's Spitzer Space Telescopes shows that asteroid dust around a dead 'white dwarf' star contains silicates a common mineral on Earth. The data were taken primarily by Spitzer's infrared spectrograph, an instrument that breaks light apart into its basic constituents. The yellow dots show averaged data from the spectrograph, while the orange triangles show older data from Spitzer's infrared array camera. The white dwarf is called GD 40.

  4. Silicates in Alien Asteroids


    This plot of data from NASA's Spitzer Space Telescopes shows that asteroid dust around a dead 'white dwarf' star contains silicates a common mineral on Earth. The data were taken primarily by Spitzer's infrared spectrograph, an instrument that breaks light apart into its basic constituents. The yellow dots show averaged data from the spectrograph, while the orange triangles show older data from Spitzer's infrared array camera. The white dwarf is called GD 40.

  5. Investigation of the Matrix Effect on the Accuracy of Quantitative Analysis of Trace Metals in Liquids Using Laser-Induced Breakdown Spectroscopy with Solid Substrates.

    Xiu, Junshan; Dong, Lili; Qin, Hua; Liu, Yunyan; Yu, Jin


    The detection limit of trace metals in liquids has been improved greatly by laser-induced breakdown spectroscopy (LIBS) using solid substrate. A paper substrate and a metallic substrate were used as a solid substrate for the detection of trace metals in aqueous solutions and viscous liquids (lubricating oils) respectively. The matrix effect on quantitative analysis of trace metals in two types of liquids was investigated. For trace metals in aqueous solutions using paper substrate, the calibration curves established for pure solutions and mixed solutions samples presented large variation on both the slope and the intercept for the Cu, Cd, and Cr. The matrix effects among the different elements in mixed solutions were observed. However, good agreement was obtained between the measured and known values in real wastewater. For trace metals in lubricating oils, the matrix effect between the different oils is relatively small and reasonably negligible under the conditions of our experiment. A universal calibration curve can be established for trace metals in different types of oils. The two approaches are verified that it is possible to develop a feasible and sensitive method with accuracy results for rapid detection of trace metals in industrial wastewater and viscous liquids by laser-induced breakdown spectroscopy. © The Author(s) 2016.

  6. Thiourea-succinonitrile based polymer matrix for efficient and stable quasi solid state dye sensitized solar cells

    Grover, Rakhi; Jauhari, Himanshi; Saxena, Kanchan


    Dye sensitized solar cells (DSSCs) are considered to be emerging alternatives to the low cost indoor photovoltaic technologies. However, to make the application of these cells economically feasible, the stability of the cells need to be enhanced. This can be achieved by employing solid or quasi solid state electrolytes to reduce the leakage and sealing problems in DSSCs. In the present work, a gel state electrolyte composition was successfully prepared using thiourea and solid state ionic conductor succinonitrile along with other components. The composition has been used for the fabrication of quasi solid state DSSCs using Eosin B as the sensitizer material. The cells fabricated exhibited consistent photovoltaic properties even after 24 hours of storage under ambient conditions without sealing. The present work therefore, demonstrates a rapid and simple preparation of electrolyte medium for quasi solid state DSSCs.

  7. LC/MS method using cloud point extraction for the determination of permitted and illegal food colors in liquid, semiliquid, and solid food matrixes: single-laboratory validation.

    Ates, Ebru; Mittendorf, Klaus; Senyuva, Hamide


    A cloud point extraction method is reported using LC/MS for the determination of regulated water-soluble food colors (Allura Red, Sunset Yellow, erythrosine, and tartrazine) and banned fat-soluble synthetic azo dyes (Sudan I, II, III, and IV; Red B; 7B; Black B; Red G; Metanil Yellow; and Rhodamine B). The extraction of all 14 colors was carried out with cloud point extraction using the nonionic surfactant Triton X 114. Optimized conditions for cloud point extraction were 3% Triton X 114 (w/v), 0.1 M ammonium acetate, and heating at 50 degrees C for 30 min. This approach proved effective in giving quantitative recoveries from a diverse range of food matrixes, and optimized LC gave baseline chromatographic separation for all colors including Sudan IV and Red B. Single-laboratory validation was performed with spiking into liquid matrixes (wine and homemade wine), semiliquid matrixes (sauce and homemade paprika paste), and solid matrixes (spice and homemade chili powder) using the respective blank matrixes for matrix-matched calibration. The LOQ values for water-soluble colors were in the range of 15-150 mg/kg, and for the fat-soluble colors, 0.1-1.5 mg/kg. The mean recovery values were in the range of 69.6-116.0% (except Allura Red and Sunset Yellow in wine, for which recoveries were lower). The mean RSDs for colors were in the range of 4.0-14.8%. A small survey was conducted of samples of confectionery products, dried fruits, wines, bitter sodas, juices, sauces, pastes, and spices, which demonstrated the applicability of the method to a diverse selection of real food samples. Allura Red was detected in strawberry jelly and Sunset Yellow in artificial saffron.

  8. Reproducibility of serum protein profiling by systematic assessment using solid-phase extraction and matrix-assisted laser desorption/ionization mass spectrometry

    Callesen, Anne K; Christensen, René Depont; Madsen, Jonna S


    for serum protein profiling we investigated a range of sample preparation techniques and developed a statistical method based on repeated analyses for evaluation of protein-profiling performance of MALDI MS. Two different solid-phase extraction (SPE) methods were investigated, namely custom......Protein profiling of human serum by matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) is potentially a new diagnostic tool for early detection of human diseases, including cancer. Sample preparation is a key issue in MALDI MS and the analysis of complex samples such as serum......-made microcolumns and commercially available magnetic beads. Using these two methods, nineteen different sample preparation methods for serum profiling by MALDI MS were systematically tested with regard to matrix selection, stationary phase, selectivity, and reproducibility. Microcolumns were tested with regard...

  9. A new and efficient Solid Phase Microextraction approach for analysis of high fat content food samples using a matrix-compatible coating.

    De Grazia, Selenia; Gionfriddo, Emanuela; Pawliszyn, Janusz


    The current work presents the optimization of a protocol enabling direct extraction of avocado samples by a new Solid Phase Microextraction matrix compatible coating. In order to further extend the coating life time, pre-desorption and post-desorption washing steps were optimized for solvent type, time, and degree of agitation employed. Using optimized conditions, lifetime profiles of the coating related to extraction of a group of analytes bearing different physical-chemical properties were obtained. Over 80 successive extractions were carried out to establish coating efficiency using PDMS/DVB 65µm commercial coating in comparison with the PDMS/DVB/PDMS. The PDMS/DVB coating was more prone to irreversible matrix attachment on its surface, with consequent reduction of its extractive performance after 80 consecutive extractions. Conversely, the PDMS/DVB/PDMS coating showed enhanced inertness towards matrix fouling due to its outer smooth PDMS layer. This work represents the first step towards the development of robust SPME methods for quantification of contaminants in avocado as well as other fatty-based matrices, with minimal sample pre-treatment prior to extraction. In addition, an evaluation of matrix components attachment on the coating surface and related artifacts created by desorption of the coating at high temperatures in the GC-injector port, has been performed by GCxGC-ToF/MS.

  10. Simultaneous determination of multiclass emerging contaminants in aquatic plants by ultrasound-assisted matrix solid-phase dispersion and GC-MS.

    Aznar, Ramón; Albero, Beatriz; Sánchez-Brunete, Consuelo; Miguel, Esther; Martín-Girela, Isabel; Tadeo, José L


    A multiresidue method was developed for the simultaneous determination of 31 emerging contaminants (pharmaceutical compounds, hormones, personal care products, biocides, and flame retardants) in aquatic plants. Analytes were extracted by ultrasound-assisted matrix solid-phase dispersion (UA-MSPD) and determined by gas chromatography-mass spectrometry after sylilation, The method was validated for different aquatic plants (Typha angustifolia, Arundo donax, and Lemna minor) and a semiaquatic cultivated plant (Oryza sativa) with good recoveries at concentrations of 100 and 25 ng g(-1) wet weight, ranging from 70 to 120 %, and low method detection limits (0.3 to 2.2 ng g(-1) wet weight). A significant difference of the chromatographic response was observed for some compounds in neat solvent versus matrix extracts, and therefore, quantification was carried out using matrix-matched standards in order to overcome this matrix effect. Aquatic plants taken from rivers located at three Spanish regions were analyzed, and the compounds detected were parabens, bisphenol A, benzophenone-3, cyfluthrin, and cypermethrin. The levels found ranged from 6 to 25 ng g(-1) wet weight except for cypermethrin that was detected at 235 ng g(-1) wet weight in O. sativa samples.

  11. Characterizing Amorphous Silicates in Extraterrestrial Materials

    Fu, X.; Wang, A.; Krawczynski, M. J.


    Amorphous silicates are common in extraterrestrial materials. They are seen in the matrix of carbonaceous chondrites as well as in planetary materials. Tagish Lake is one of the most primitive carbonaceous meteorites in which TEM and XRD analyses found evidence for poorly crystalline phyllosilicate-like species; Raman spectra revealed amorphous silicates with variable degree of polymerization and low crystallinity. On Mars, CheMin discovered amorphous phases in all analyzed samples, and poorly crystalline smectite in mudstone samples. These discoveries pose questions on the crystallinity of phyllosilicates found by remote sensing on Mars, which is directly relevant to aqueous alteration during geologic history of Mars. Our goal is to use spectroscopy to better characterize amorphous silicates. We use three approaches: (1) using silicate glasses synthesized with controlled chemistry to study the effects of silicate polymerization and (2) using phyllosilicates synthesized with controlled hydrothermal treatment to study the effect of crystallinity on vibrational spectroscopy, finally (3) to use the developed correlations in above two steps to study amorphous phases in meteorites, and those found in future missions to Mars. In the 1st step, silicate glasses were synthesized from pure oxides in a range of NBO/T ratios (from 0 to 4). Depending on the targeted NBO/T and composition of mixed oxides, temperatures for each experiment fell in a range from 1260 to 1520 °C, run for ~ 4 hrs. The melt was quenched in liquid N2 or water. Homogeneity of glass was checked under optical microscopy. Raman spectra were taken over 100 spots on small chips free of bubbles and crystals. We have observed that accompanying an increase of NBO/T, there is a strengthening and a position shift of the Raman peak near 1000 cm-1 (Si-Onon-bridging stretching mode), and the weakening of broad Raman peaks near 500 cm-1 (ring breathing mode) and 700cm-1 (Si-Obridging-Si mode). We are building the

  12. Recovery evaluation of organophosphorus pesticides from bee pollen by matrix solid-phase dispersion extraction using sorbents based on silica and titania

    Torres-Perea, C.; Muñoz-Rodríguez, D.; Medina-Peralta, S.; Carrera-Figueiras, C.; Moguel-Ordóñez, Y. B.


    This work focused on the evaluation of the recovery of organophosphorus pesticides from bee pollen after matrix solid phase-dispersion extraction (MSPD). Materials based on silica, titania and titania modified with polivylnylimidazole or polyestirene were used as adsorbents for the extraction of pesticides. Small amounts of fortified pollen (0.1 g, at 1 micro-g/g of pesticides), adsorbent (0.4 g) and solvent elution (1 mL de acetonitrile - ACN) were used in the extractions. For recovery evaluation, pollen extracts were analyzed by gas chromatography coupled with mass spectrometry.

  13. Simulation and Experimental on the Solvation Interaction between the GAP Matrix and Insensitive Energetic Plasticizers in Solid Propellants.

    Zhao, Yu; Zhang, Xiaohong; Zhang, Wei; Xu, Hongjun; Xie, Wuxi; Du, Jiaojiao; Liu, Yingzhe


    Multimethods of simulation and experiment have been performed to investigate the interaction between glycidyl azide polymer (GAP) matrix and insensitive energetic plasticizers N-butyl-N-(2-nitroxy-ethyl)nitramine (Bu-NENA) and bis(2,2-dinitropropyl)formal/acetal (BDNPF/A). To start with, the blending energy distribution and Huggins parameters have been calculated, indicating fine miscibility between the GAP matrix and both plasticizers. The solubility parameter and binding energies show better compatibility between Bu-NENA and the GAP matrix than BDNPF/A, owing to stronger interactions. The interaction mechanism includes both hydrogen bonds and van der Waals forces. The low field NMR physical cross-link density and dynamic rheological behaviors imply larger disentanglement effect of Bu-NENA in the GAP matrix. The dynamic mechanical performance of elastomers show lower glass transition temperature of GAP/Bu-NENA blends, as supportive proof of stronger interactions between the GAP matrix and Bu-NENA in comparison with BDNPF/A.

  14. PMR-15/Layered Silicate Nanocomposites For Improved Thermal Stability And Mechanical Properties

    Campbell, Sandi; Scheiman, Daniel; Faile, Michael; Papadopoulos, Demetrios; Gray, Hugh R. (Technical Monitor)


    Montmorillonite clay was organically modified by co-exchange of an aromatic diamine and a primary alkyl amine. The clay was dispersed into a PMR (Polymerization of Monomer Reactants)-15 matrix and the glass transition temperature and thermal oxidative stability of the resulting nanocomposites were evaluated. PMR-15/ silicate nanocomposites were also investigated as a matrix material for carbon fabric reinforced composites. Dispersion of the organically modified silicate into the PMR-15 matrix enhanced the thermal oxidative stability, the flexural strength, flexural modulus, and interlaminar shear strength of the polymer matrix composite.

  15. Thermal Expansion and Thermal Conductivity of Rare Earth Silicates

    Zhu, Dongming; Lee, Kang N.; Bansal, Narottam P.


    Rare earth silicates are considered promising candidate materials for environmental barrier coatings applications at elevated temperature for ceramic matrix composites. High temperature thermophysical properties are of great importance for coating system design and development. In this study, the thermal expansion and thermal conductivity of hot-pressed rare earth silicate materials were characterized at temperatures up to 1400 C. The effects of specimen porosity, composition and microstructure on the properties were also investigated. The materials processing and testing issues affecting the measurements will also be discussed.

  16. In-line micro-matrix solid-phase dispersion extraction for simultaneous separation and extraction of Sudan dyes in different spices.

    Rajabi, Maryam; Sabzalian, Sedigheh; Barfi, Behruz; Arghavani-Beydokhti, Somayeh; Asghari, Alireza


    A novel, simple, fast, and miniaturized method, termed in-line micro-matrix solid-phase dispersion (in-line MMSPD), coupled with high performance liquid chromatography (HPLC) was developed for the simultaneous extraction and determination of Sudan dyes (i.e. Sudan I-IV, Sudan orange G, Sudan black B, and Sudan red G) with the aid of an experimental design strategy. In this method, a matrix solid-phase dispersion (MSPD) column including a suitable mixture of polar sorbents was inserted in the mobile phase pathway, and while the interfering compounds were retained, the analytes were eluted and entered into the analytical column. In this way, the extraction, elution, and separation of the analytes were performed sequentially. Under the optimal experimental conditions (including the amount of sample, 0.0426g; amount of dispersant phase, 0.0216g of florisil, 0.0227g of silica, 0.0141g of alumina; and blending time, 112s), the limits of detection (LODs), limits of quantification, linear dynamic ranges, and recoveries were obtained to be 0.3-15.3μgkg(-1), 1-50μgkg(-1), 50-28,000μgkg(-1), and 94.5-99.1%, respectively. The results obtained showed that determination of the selected Sudan dyes in food samples using an enough sensitive and a simple analytically validated method like in-line MMSPD may offer a suitable screening method, which could be useful for food analysis and adulteration.

  17. Research on Friction Property of WS2 Matrix Solid Lubricating Coatings%WS2基固体润滑涂层摩擦性能研究

    侯锁霞; 高辉; 贾晓鸣


    The tribological properties of WS2 matrix solid lubricating coating were investigated by friction and wear tests.The results show that,under normal temperature,the tribological coefficient of WS2 matrix solid lubricating coatings are close to that of MoS2 matrix solid lubricating coating,however,the coating quality of WS2 metal matrix is inferior to that of MoS2 ; under high temperature,WS2 matrix coatings have stable friction coefficient,the tribological properties of WS2 coatings are superior to MoS2 matrix solid lubricating coatings.The composite coatings including MoS2,WS2 and Sb2 O3 can play a better role in friction reducing and lubrication,and the friction coefficient can reach to 0.045 under high temperature of 400℃.For the composite coatings including MoS2,WS2 and Sb2 O3,Sb2 O3 reacts preferentially with the oxygen in the air under high temperature,which slows down the oxidation rate of MoS2 and WS2,and elevates the temperature that MoS2 and WS2 can withstand.In the condition of boundary lubrication,the mixed films of FeS and MoS2 are generated by the electrochemical catalysis and heat friction chemical reaction of MoS2,which improves the boundary lubrication.%通过摩擦磨损试验,研究WS2固体润滑剂的摩擦性能.结果表明:常温工况下,WS2固体润滑剂的摩擦因数与MoS2的相近,但WS2涂层在金属基上成膜状态不如MoS2涂层;高温工况下,WS2基涂层摩擦因数稳定,摩擦性能优于MoS2基固体润滑涂层;在400℃的温度条件下,WS2、MoS2、Sb2 O3复合涂层摩擦因数可达0.045,减摩润滑作用显著提高.在高温工况下,WS2、MoS2、Sb2O3复合涂层中Sb2O3优先与空气中的氧发生反应从而减缓MoS2、WS2的氧化速度,提高MoS2、WS2所能承受的温度;在边界润滑条件下,MoS2发生电化学催化和热摩擦化学反应,生成FeS和MoS2混合膜,改善了边界润滑.

  18. Potassium Silicate Foliar Fertilizer Grade from Geothermal Sludge and Pyrophyllite

    Muljani Srie


    Full Text Available Potassium silicate fertilizer grade were successfully produced by direct fusion of silica (SiO2 and potasium (KOH and K2CO3 in furnaces at temperatures up to melting point of mixture. The geothermal sludge (98% SiO2 and the pyrophyllite (95% SiO2 were used as silica sources. The purposes of the study was to synthesise potassium silicate fertilizer grade having solids concentrations in the range of 31-37% K2O, and silica in the range of 48-54% SiO2. The weight ratio of silicon dioxide/potasium solid being 1:1 to 5:1. Silica from geothermal sludge is amorphous, whereas pyrophylite is crystalline phase. The results showed that the amount of raw materials needed to get the appropriate molar ratio of potassium silicate fertilizer grade are different, as well as the fusion temperature of the furnace. Potassium silicate prepared from potassium hydroxide and geothermal sludge produced a low molar ratio (2.5: 1 to 3: 1. The potassium required quite small (4:1 in weight ratio, and on a fusion temperature of about 900 °C. Meanwhile, the potassium silicate prepared from pyrophyllite produced a high molar ratio (1.4 - 9.4 and on a fusion temperature of about 1350 °C, so that potassium needed large enough to meet the required molar ratio for the fertilizer grade. The product potassium silicate solid is amorphous with a little trace of crystalline.

  19. The formation and physical stability of two-phase solid dispersion systems of indomethacin in supercooled molten mixtures with different matrix formers.

    Semjonov, Kristian; Kogermann, Karin; Laidmäe, Ivo; Antikainen, Osmo; Strachan, Clare J; Ehlers, Henrik; Yliruusi, Jouko; Heinämäki, Jyrki


    Amorphous solid dispersions (SDs) are a promising approach to improve the dissolution rate of and oral bioavailability of poorly water-soluble drugs. In some cases multi-phase, instead of single-phase, SD systems with amorphous drug are obtained. While it is widely assumed that one-phase amorphous systems are desirable, two-phase systems may still potentially exhibit enhanced stability and dissolution advantages over undispersed systems. The objective of the present study was to understand the solid-state properties of two-phase SDs with amorphous drug and their relation to physical stability. Two different types of excipients for SD formation were used, one being a polymer and the other a small molecule excipient. The supercooled molten SDs of a poorly water-soluble indomethacin (IND) with a graft copolymer, Soluplus® (SOL) and sugar alcohol, xylitol (XYL) were prepared. Supercooled molten SDs of IND with SOL were two-phase glassy suspension in which the amorphous drug was dispersed in an amorphous polymer matrix. A short-term aging of the SDs led to the formation of glassy suspensions where the crystalline drug was dispersed in an amorphous polymer matrix. These were physically stable at room temperature for the time period studied (RT, 23±2°C), but aging at high-humidity conditions (75% RH) recrystallization to metastable α-IND occurred. Interestingly, the SDs with XYL were two-phase amorphous precipitation systems in which the drug was in an amorphous form in the crystalline sugar alcohol matrix. The SDs of IND and XYL exhibited fast drug recrystallization. In conclusion, the preparation method of two-phase systems via co-melting in association with the rapid quench cooling is a feasible method for the formulation of poorly water-soluble drugs. The physical stability of these two-phase systems, however, is dependent on the carrier material and storage conditions.

  20. Vortex-assisted matrix solid-liquid dispersive microextraction for the analysis of triazole fungicides in cotton seed and honeysuckle by gas chromatography.

    Xue, Jiaying; Li, Huichen; Liu, Fengmao; Jiang, Wenqing; Hou, Fan


    A one-step analytical method termed vortex-assisted matrix solid-liquid dispersive microextraction (VA-MSLDME) was developed for the determination of seven triazole fungicides from cotton seed and honeysuckle prior to gas chromatography with electron capture detection. The VA-MSLDME was performed by mixing the matrix, primary secondary amine, acetonitrile, toluene, and water in one single system. The target fungicides in the sample were extracted, cleaned up and preconcentrated simultaneously in the matrix/acetonitrile/water/toluene system. Meanwhile, the interferences were adsorbed by the cleanup adsorbent. The extraction recoveries of the fungicides from the samples varied from 82.9% to 97.8% with relative standard deviations of 4.4-8.5%. The enrichment factors of the analytes ranged from 22 to 47, and the limits of detection were in the range of 0.05-20 μg/kg. The results demonstrated the significant predominance of VA-MSLDME in the analysis of pesticide residues in cotton seed and honeysuckle samples.

  1. Micro-matrix solid-phase dispersion coupled with MEEKC for quantitative analysis of lignans in Schisandrae Chinensis Fructus using molecular sieve TS-1 as a sorbent.

    Chu, Chu; Wei, Mengmeng; Wang, Shan; Zheng, Liqiong; He, Zheng; Cao, Jun; Yan, Jizhong


    A simple and effective method was developed for determining lignans in Schisandrae Chinensis Fructus by using a micro-matrix solid phase dispersion (MSPD) technique coupled with microemulsion electrokinetic chromatography (MEEKC). Molecular sieve, TS-1, was applied as a solid supporting material in micro MSPD extraction for the first time. Parameters that affect extraction efficiency, such as type of dispersant, mass ratio of the sample to the dispersant, grinding time, elution solvent and volume were optimized. The optimal extraction conditions involve dispersing 25mg of powdered Schisandrae samples with 50mg of TS-1 by a mortar and pestle. A grinding time of 150s was adopted. The blend was then transferred to a solid-phase extraction cartridge and the target analytes were eluted with 500μL of methanol. Moreover, several parameters affecting MEEKC separation were studied, including the type of oil, SDS concentration, type and concentration of cosurfactant, and concentration of organic modifier. A satisfactory linearity (R>0.9998) was obtained, and the calculated limits of quantitation were less than 2.77μg/mL. Finally, the micro MSPD-MEEKC method was successfully applied to the analysis of lignans in complex Schisandrae fructus samples. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. C-Cl activation by group IV metal oxides in solid argon matrixes: matrix isolation infrared spectroscopy and theoretical investigations of the reactions of MOx (M = Ti, Zr; x = 1, 2) with CH3Cl.

    Zhao, Yanying


    Reactions of the ground-state titanium and zirconium monoxide and dioxide molecules with monochloromethane in excess argon matrixes have been investigated in solid argon by infrared absorption spectroscopy and density functional theoretical calculations. The results show that the ground-state MOx (M = Ti, Zr; x = 1, 2) molecules react with CH3Cl to first form the weakly bound MO(CH3Cl) and MO2(CH3Cl) complexes. The MO(CH3Cl) complexes can rearrange to the CH3M(O)Cl isomers with the Cl atom of CH3Cl coordination to the metal center of MO upon UV light irradiation (λ MOx mechanism was interpreted by the calculated potential energy profiles.

  3. Rubber curing chemistry governing the orientation of layered silicate


    Full Text Available The effect of curing systems on the orientation and the dispersion of the layered silicates in acrylonitrile butadiene rubber nanocomposite is reported. Significant differences in X-ray diffraction pattern between peroxide curing and sulfur curing was observed. Intense X-ray scattering values in the XRD experiments from peroxide cured vulcanizates indicate an orientation of the layers in a preferred direction as evinced by transmission electron micrographs. However, sulfur cured vulcanizates show no preferential orientation of the silicate particles. Nevertheless, a closer inspection of transmission electron microscopy (TEM images of peroxide and sulfur cured samples shows exfoliated silicate layers in the acrylonitrile butadiene rubber (NBR matrix. It was revealed in the prevailing study that the use of an excess amount of stearic acid in the formulation of the sulfur curing package leads to almost exfoliated type X-ray scattering pattern.

  4. Matrix effect on the performance of headspace solid phase microextraction method for the analysis of target volatile organic compounds (VOCs) in environmental samples.

    Higashikawa, Fábio S; Cayuela, Maria Luz; Roig, Asunción; Silva, Carlos A; Sánchez-Monedero, Miguel A


    Solid phase microextraction (SPME) is a fast, cheap and solvent free methodology widely used for environmental analysis. A SPME methodology has been optimized for the analysis of VOCs in a range of matrices covering different soils of varying textures, organic matrices from manures and composts from different origins, and biochars. The performance of the technique was compared for the different matrices spiked with a multicomponent VOC mixture, selected to cover different VOC groups of environmental relevance (ketone, terpene, alcohol, aliphatic hydrocarbons and alkylbenzenes). VOC recovery was dependent on the nature itself of the VOC and the matrix characteristics. The SPME analysis of non-polar compounds, such as alkylbenzenes, terpenes and aliphatic hydrocarbons, was markedly affected by the type of matrix as a consequence of the competition for the adsorption sites in the SPME fiber. These non-polar compounds were strongly retained in the biochar surfaces limiting the use of SPME for this type of matrices. However, this adsorption capacity was not evident when biochar had undergone a weathering/aging process through composting. Polar compounds (alcohol and ketone) showed a similar behavior in all matrices, as a consequence of the hydrophilic characteristics, affected by water content in the matrix. SPME showed a good performance for soils and organic matrices especially for non-polar compounds, achieving a limit of detection (LD) and limit of quantification (LQ) of 0.02 and 0.03 ng g(-1) for non-polar compounds and poor extraction for more hydrophilic and polar compounds (LD and LQ higher 310 and 490 ng g(-1)). The characteristics of the matrix, especially pH and organic matter, had a marked impact on SPME, due to the competition of the analytes for active sites in the fiber, but VOC biodegradation should not be discarded in matrices with active microbial biomass.

  5. Environmental silicate nano-biocomposites

    Pollet, Eric


    Environmental Silicate Nano-Biocomposites focuses on nano-biocomposites, which are obtained by the association of silicates such as bioclays with biopolymers. By highlighting recent developments and findings, green and biodegradable nano-composites from both renewable and biodegradable polymers are explored. This includes coverage of potential markets such as packaging, agricultures, leisure and the fast food industry. The knowledge and experience of more than twenty international experts in diverse fields, from chemical and biochemical engineering to applications, is brought together in four different sections covering: Biodegradable polymers and Silicates, Clay/Polyesters Nano-biocomposites, Clay/Agropolymers Nano-biocomposites, and Applications and biodegradation of Nano-biocomposites. By exploring the relationships between the biopolymer structures, the processes, and the final properties Environmental Silicate Nano-Biocomposites explains how to design nano-materials to develop new, valuable, environmenta...

  6. Current state of knowledge when it comes to consumer exposure to nanomaterial embedded in a solid matrix

    Mackevica, Aiga; Hansen, Steffen Foss


    Little is known about consumer exposure to engineered nanomaterials (ENMs) stemming from NM-containing consumer products. Here, we focus especially on studies that have investigated the release of ENMs from consumer products, investigating to what extent the information in the open literature can......, we summarized the studies by identifying nanomaterial(s), product name, product type, Product or Article Category according to REACH; experimental setup, total content in product, information on release, techniques used for characterization of nanomaterials both in product matrix and in the released...

  7. Electron spin-lattice relaxation in solid ethanol: the effect of nitroxyl radical hydrogen bonding and matrix disorder

    Kveder, Marina; Jokić, Milan; Makarević, Janja; Rakvin, Boris


    The electron spin-lattice relaxation of TEMPO and TEMPONE was measured at temperatures between 5 and 80 K in crystalline and glassy ethanol using X-band electron paramagnetic resonance spectroscopy. The experimental data at the lowest temperatures studied were explained in terms of electron-nuclear dipolar interaction between the paramagnetic center and the localized excitations, whereas at higher temperatures low-frequency vibrational modes from the host matrix and Raman processes should be considered. The strong impact of hydrogen bonding between the dopant molecule and ethanol host on the spin relaxation was observed in ethanol glass whereas in crystalline ethanol both paramagnetic guest molecules behaved similarly.

  8. Strong work-hardening behavior induced by the solid solution strengthening of dendrites in TiZr-based bulk metallic glass matrix composites

    Ma, D.Q. [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Jiao, W.T. [College of Education, Hebei Normal University of Science and Technology, Qinhuangdao 066004 (China); Zhang, Y.F. [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Hebei Vocational and Technical College of Building Materials, Qinhuangdao 066004 (China); Wang, B.A.; Li, J.; Zhang, X.Y. [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Ma, M.Z., E-mail: [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Liu, R.P. [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China)


    Highlights: • Hardness of dendrite of TiZr-based BMGMCs increases. • Strong work-hardening behavior is obtained after solid solution strengthening. • Lattice distortions of dendrite suffering from rapid cooling are detected. - Abstract: A series of TiZr-based bulk metallic glass matrix composites (BMGMCs) with distinguished mechanical properties are successfully fabricated by adding different volume fractions of Ta (Ti{sub 38.8}Zr{sub 28.8}Cu{sub 6.2}Be{sub 16.2}Nb{sub 10} as the basic composition, denoted as Ta{sub 0.0}–Ta{sub 8.0}). Along with the growth of precipitated phase, typical dendritic morphology is fully developed in the TiZr-based BMGMCs of Ta{sub 8.0}. Energy-dispersive spectrometry analysis of the dendrites and glass matrix indicates that the metallic elements of Nb and Ta should preferentially form solid solution into dendrites. The chaotic structure of high-temperature precipitate phase is trapped down by the rapid cooling of the copper-mould. The detected lattice distortions in the dendrites are attributed to the strong solid solution strengthening of the metallic elements of Ti, Zr, Nb, and Ta. These lattice distortions increase the resistance of the dislocation motion and pin the dislocations, thus the strength and hardness of dendrite increase. Dendrites create a strong barrier for the shear band propagation and generate multiple shear bands after solid solution strengthening, thereby providing the TiZr-based BMGMCs with greatly improved capacity to sustain plastic deformation and resistance to brittle fracture. Thus, the TiZr-based BMGMCs possess distinguished work-hardening capability. Among these TiZr-based BMGMCs, the sample Ta{sub 0.5} possesses the largest plastic strain (ε{sub p}) at 20.3% and ultimate strength (σ{sub max}) of 2613 MPa during compressive loading. In addition, the sample of Ta{sub 0.5} exhibits work-hardening up to an ultrahigh tensile strength of 1680 MPa during the tensile process, and then progressively

  9. Serum protein profiling by miniaturized solid-phase extraction and matrix-assisted laser desorption/ionization mass spectrometry

    Callesen, Anne K; Mohammed, Shabaz; Bunkenborg, Jakob;


    for translation of MALDI-MS based diagnostic methods to clinical applications. We have investigated a number of MALDI matrices and several miniaturized solid-phase extraction (SPE) methods for serum protein concentration and desalting with the aim of generating reproducible, high-quality protein profiles by MALDI...... mass spectra (m/z 1000-12,000) to be obtained from serum. In a proof-of-principle application, SPE with chelating material and MALDI-MS identified protein peaks in serum that had been previously reported for distinguishing a person diagnosed with breast cancer from a control. These preliminary results...

  10. Electrical field assisted matrix solid phase dispersion as a powerful tool to improve the extraction efficiency and clean-up of fluoroquinolones in bovine milk.

    da Silva, Mariana Cristina; Orlando, Ricardo Mathias; Faria, Adriana Ferreira


    This work presents a new method by electrical matrix solid phase dispersion for the extraction and clean-up of marbofloxacin, ofloxacin, norfloxacin, ciprofloxacin, enrofloxacin, difloxacin and sarafloxacin in bovine milk. Composition and pH of the eluent, applied electrical potential and polarity were optimized by experimental designs. The combination of the chromatographic and electrophoretic mechanisms allowed the extraction and clean-up in one step with low organic solvent consumption, high extraction throughput and elution automation. Linearity, precision, trueness and limit of quantification were evaluated and provided values in accordance with other methods recently developed for the analysis of fluoroquinolones in milk. This technique proved to be promising for the extraction and clean-up of ionizable analytes in different milk matrices. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Tracer aroma compound transfer from a solid and complex-flavored food matrix packed in treated papers or plastic packaging film.

    Dury-Brun, Cécile; Lequin, Sonia; Chalier, Pascale; Desobry, Stéphane; Voilley, Andrée


    The objective of this work was to study the transfer of four aroma compounds (ethyl butyrate, ethyl hexanoate, cis-3-hexenol, and benzaldehyde) from a solid and complex-flavored food matrix (sponge cake) toward and through packaging films placed in indirect contact during storage in accelerated aging conditions (38 degrees C and 86% relative humidity gradient). The efficiency of treated papers relative to that of standard paper and plastic as barrier was tested. Before storage, aroma compound volatility in the sponge cake was measured, and similar values were found between aroma compounds, due to the fat content of the sponge cake. Whatever the aroma compound, permeability values during storage were similar for the same packaging film. The plastic film was the highest barrier, whereas calendering and coating treatments applied to treated papers decreased effectively their permeability. An opposite trend was observed for aroma compound sorption into packaging films during storage.

  12. Rotational States of Methyl Radical Monitored by EPR Line Shape of Matrix-Isolated CH3 in CO2 and N2O Solids

    Dmitriev, Yu. A.; Melnikov, V. D.; Zelenetckii, I. A.; Benetis, N. P.


    Methyl radicals, CH3, were trapped in matrices of solid CO2 and N2O by condensing the methyl along with the matrix constituents from the gas phase. The obtained EPR spectra were analyzed using EasySpin and/ or SimFonia simulation software and ab-initio computed quantum-chemistry parameters. We focus on two distinguished features of the spectra: the temperature-dependent linewidth anisotropy and the origin of the weak satellite doublets. The low-temperature spectral analysis of the satellites was based on the coupled representation of the three proton spins of CH3 and a recently obtained parameterization of the spin Hamiltonian based on one nuclear quartet and two doublets within the D3 group. These features were closely correlated to the state of rotation of the trapped radical.

  13. Application of matrix solid-phase dispersion followed by GC-MS/MS to the analysis of emerging contaminants in vegetables.

    Albero, Beatriz; Sánchez-Brunete, Consuelo; Miguel, Esther; Tadeo, José L


    A multiresidue method for the determination of 17 emerging contaminants in vegetables was developed based on ultrasound-assisted matrix solid-phase dispersion (MSPD). The analysis was performed using isotope dilution gas chromatography tandem mass spectrometry. In the development of the MSPD procedure, different parameters such as sonication and the type of sorbent or extraction solvent were assayed. Manual and in situ derivatization was assayed and the chromatographic response was higher when the reaction takes place in the injection port. The limits of detection obtained for the studied compounds were in the range of 0.1-0.4ngg(-1) for the different vegetables analyzed. The developed method was applied to vegetables obtained from several local markets. At least one of the organophosphates was detected in the analyzed samples at levels ranging from 0.6 to 4.6ngg(-1) and bisphenol A was detected in all the samples at concentration up to 16ngg(-1).

  14. Determination of the major constituents in fruit of Arctium lappa L. by matrix solid-phase dispersion extraction coupled with HPLC separation and fluorescence detection.

    Liu, He; Zhang, Yupu; Sun, Yantao; Wang, Xue; Zhai, Yujuan; Sun, Ye; Sun, Shuo; Yu, Aimin; Zhang, Hanqi; Wang, Yinghua


    The arctiin and arctigenin in the fruit of Arctium lappa L. were extracted by matrix solid-phase dispersion (MSPD) and determined by high-performance liquid chromatography (HPLC) with fluorescence detection. The experimental conditions for the MSPD were optimized. Silica gel was selected as dispersion adsorbent and methanol as elution solvent. The calibration curve showed good relationship (r>0.9998) in the concentration range of 0.010-5.0μgmL(-1) for arctiin and 0.025-7.5μgmL(-1) for arctigenin. The recoveries were between 74.4% and 100%. The proposed method consumed less sample, time and solvent compared with conventional methods, including ultrasonic and Soxhlet extraction.

  15. New method based on combining ultrasonic assisted miniaturized matrix solid-phase dispersion and homogeneous liquid-liquid extraction for the determination of some organochlorinated pesticides in fish

    Rezaei, Farahnaz [Department of Analytical Chemistry, Faculty of Chemistry, Iran University of Science and Technology, Narmak, Tehran 16846 (Iran, Islamic Republic of); Hosseini, Mohammad-Reza Milani, E-mail: [Department of Analytical Chemistry, Faculty of Chemistry, Iran University of Science and Technology, Narmak, Tehran 16846 (Iran, Islamic Republic of); Electroanalytical Chemistry Research Center, Iran University of Science and Technology, Narmak, Tehran 16846 (Iran, Islamic Republic of)


    Highlights: {yields} Ultrasonic assisted miniaturized matrix solid-phase dispersion combined with HLLE was developed as a new method for the extraction of OCPs in fish. {yields} The goal of this combination was to enhance the selectivity of HLLE procedure and to extend its application in biological samples. {yields} This method proposed the advantages of good detection limits, lower consumption of reagents, and does not need any special instrumentation. - Abstract: In this study, ultrasonic assisted miniaturized matrix solid-phase dispersion (US-MMSPD) combined with homogeneous liquid-liquid extraction (HLLE) has been developed as a new method for the extraction of organochlorinated pesticides (OCPs) in fish prior to gas chromatography with electron capture detector (GC-ECD). In the proposed method, OCPs (heptachlor, aldrin, DDE, DDD, lindane and endrin) were first extracted from fish sample into acetonitrile by US-MMSPD procedure, and the extract was then used as consolute solvent in HLLE process. Optimal condition for US-MMSPD step was as follows: volume of acetonitrile, 1.5 mL; temperature of ultrasound, 40 deg. C; time of ultrasound, 10 min. For HLLE step, optimal results were obtained at the following conditions: volume of chloroform, 35 {mu}L; volume of aqueous phase, 1.5 mL; volume of double distilled water, 0.5 mL; time of centrifuge, 10 min. Under the optimum conditions, the enrichment factors for the studied compounds were obtained in the range of 185-240, and the overall recoveries were ranged from 39.1% to 81.5%. The limits of detection were 0.4-1.2 ng g{sup -1} and the relative standard deviations for 20 ng g{sup -1} of the OCPs, varied from 3.2% to 8% (n = 4). Finally, the proposed method has been successfully applied to the analysis of the OCPs in real fish sample, and satisfactory results were obtained.

  16. A Solid Binding Matrix/Mimic Receptor-Based Sensor System for Trace Level Determination of Iron Using Potential Measurements

    Ayman H. Kamel


    Full Text Available Iron(II-(1,10-phenanthroline complex imprinted membrane was prepared by ionic imprinting technology. In the first step, Fe(II established a coordination linkage with 1,10-phenanthroline and functional monomer 2-vinylpyridine (2-VP. Next, the complex was copolymerized with ethylene glycol dimethacrylate (EGDMA as a crosslinker in the presence of benzoyl peroxide (BPO as an initiator. Potentiometric chemical sensors were designed by dispersing the iron(II-imprinted polymer particles in 2-nitrophenyloctyl ether (o-NPOE plasticizer and then embedded in poly vinyl chloride (PVC matrix. The sensors showed a Nernstian response for [Fe(phen3]2+ with limit of detection 3.15 ng mL−1 and a Nernstian slope of 35.7 mV per decade.

  17. Density matrix treatment of combined instantaneous and delayed dissipation for an electronically excited adsorbate on a solid surface

    Leathers, Andrew S.; Micha, David A.; Kilin, Dmitri S.


    The interaction of an excited adsorbate with a medium undergoing electronic and vibrational transitions leads to fast dissipation due to electronic energy relaxation and slow (or delayed) dissipation from vibrational energy relaxation. A theoretical and computational treatment of these phenomena has been done in terms of a reduced density matrix satisfying a generalized Liouville-von Neumann equation, with instantaneous dissipation constructed from state-to-state transition rates, and delayed dissipation given by a memory term derived from the time-correlation function (TCF) of atomic displacements in the medium. Two representative applications are presented here, where electronic excitation may enhance vibrational relaxation of an adsorbate. They involve femtosecond excitation of (a) a CO molecule adsorbed on the Cu(001) metal surface and (b) a metal cluster on a semiconductor surface, Ag3Si(111):H, both electronically excited by visible light and undergoing electron transfer and dissipative dynamics by electronic and vibrational relaxations. Models have been parametrized in both cases from electronic structure calculations and known TCFs for the medium, which are slowly decaying in case (a) and fast decaying in case (b). This requires different numerical procedures in the solution of the integrodifferential equations for the reduced density matrix, which have been solved with an extension of the Runge-Kutta algorithm. Results for the populations of vibronic states versus time show that they oscillate due to vibrational coupling through dissipative interaction with the substrate and show quantum coherence. The total population of electronic states is, however, little affected by vibrational motions. Vibrational relaxation is important only at very long times to establish thermal equilibrium.

  18. Development of surface imprinted core-shell nanoparticles and their application in a solid-phase dispersion extraction matrix for methyl parathion.

    Tan, Lei; Li, Weiming; Li, He; Tang, Youwen


    Applying molecular imprinting techniques to the surface of functionalized SiO2 allows the preparation of molecularly imprinted polymers (MIPs) with accessible, high affinity and surface exposed binding sites. This paper demonstrates a new strategy for producing such hybrid organic-inorganic surface imprinted silica nanoparticles for specific recognition of methyl parathion. The technique provides surface grafting imprinting in chloroform using amino modified silica nanoparticles as supports, acrylamide as the functional monomer, γ-methacryloxypropyl trimethoxy silane as the grafting agent, and methyl parathion as a template. The amino propyl functional monomer layer directs the selective occurrence of imprinting polymerization at the silica surface through copolymerization of grafting agents with functional monomers, but also acts as an assistive monomer to drive the template into the formed polymer shells to create effective recognition sites. The resulting MIPs-SiO2 nanoparticles display three-dimensional core-shell architectures and large surface areas. The molecularly imprinted shell provides recognition sites for methyl parathion, with the materials exhibiting excellent performance for selecting the template. Using MIPs-SiO2 nanoparticles as a matrix of solid-phase dispersion extraction sorbents, trace amounts of methyl parathion are selectivity extracted from pear and green vegetable samples while simultaneously eliminating matrix interferences, attaining recoveries of 84.7-94.4% for the samples.

  19. Matrix effect on leaching of Bisphenol A diglycidyl ether (BADGE) from epoxy resin based inner lacquer of aluminium tubes into semi-solid dosage forms.

    Lipke, Uwe; Haverkamp, Jan Boris; Zapf, Thomas; Lipperheide, Cornelia


    To study the impact of different semi-solid dosage form components on the leaching of Bisphenol A (BPA) and Bisphenol A diglycidyl ether (BADGE) from the epoxy resin-based inner lacquer of aluminium tubes, the tubes were filled with different matrix preparations and stored at an elevated temperature. Despite compliance with the European Standards EN 15348 and EN 15766 on porosity and polymerisation of internal coatings of aluminium tubes, the commercially available tubes used in the study contained an increased amount of polymerisation residues, such as unbound BPA, BADGE and BADGE derivatives in the lacquer, as determined by acetonitrile extraction. Storage of Macrogol ointments in these tubes resulted in an almost quantitative migration of the unbound polymerisation residues from the coating into the ointment. In addition, due to alterations observed in the RP-HPLC chromatograms of the matrix spiked with BADGE and BADGE derivatives it is supposed that the leachates can react with formulation components. The contamination of the medicinal product by BPA, BADGE and BADGE derivatives can be precluded by using aluminium tubes with an internal lacquer with a low degree of unbound polymerisation residues. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

  20. Silicate mineralogy at the surface of Mercury

    Namur, Olivier; Charlier, Bernard


    NASA's MESSENGER spacecraft has revealed geochemical diversity across Mercury's volcanic crust. Near-infrared to ultraviolet spectra and images have provided evidence for the Fe2+-poor nature of silicate minerals, magnesium sulfide minerals in hollows and a darkening component attributed to graphite, but existing spectral data is insufficient to build a mineralogical map for the planet. Here we investigate the mineralogical variability of silicates in Mercury's crust using crystallization experiments on magmas with compositions and under reducing conditions expected for Mercury. We find a common crystallization sequence consisting of olivine, plagioclase, pyroxenes and tridymite for all magmas tested. Depending on the cooling rate, we suggest that lavas on Mercury are either fully crystallized or made of a glassy matrix with phenocrysts. Combining the experimental results with geochemical mapping, we can identify several mineralogical provinces: the Northern Volcanic Plains and Smooth Plains, dominated by plagioclase, the High-Mg province, strongly dominated by forsterite, and the Intermediate Plains, comprised of forsterite, plagioclase and enstatite. This implies a temporal evolution of the mineralogy from the oldest lavas, dominated by mafic minerals, to the youngest lavas, dominated by plagioclase, consistent with progressive shallowing and decreasing degree of mantle melting over time.

  1. Synbeads porous-rigid methacrylic support: application to solid phase peptide synthesis and characterization of the polymeric matrix by FTIR microspectroscopy and high resolution magic angle spinning NMR.

    Sinigoi, Loris; Bravin, Paola; Ebert, Cynthia; D'Amelio, Nicola; Vaccari, Lisa; Ciccarelli, Laura; Cantone, Sara; Basso, Alessandra; Gardossi, Lucia


    Porous and rigid methacrylic Synbeads were optimized and applied efficiently to the solid phase peptide synthesis with the objective of improving significantly volumetric yields (0.33 mol/L calculated on the basis of maximum chemical accessibility, i.e. the maximum number of functional groups that can be acylated by FmocCl) as compared to swelling commercial polymers (from 0.06 to 0.12 mol/L). The effects of the density of functional groups and spacer length were investigated obtaining a chemical accessibility of the functional groups up to 1 mmol/g(dry). High resolution magic angle spinning (HR-MAS) was exploited to evidence the presence of "solution-like" flexible linkers anchored on the rigid methacrylic backbone of Synbeads and to study the degree of functionalization by the Wang linker. To demonstrate the efficiency of the optimized Synbeads, the peptides Somatostatin and Terlipressin were synthesized. In the case of Somatostatin, final synthetic yields of 45 and 60% were achieved by following the HCTU/DIPEA and DIC/HOBt routes respectively, with the HPLC purity always higher than 83%. In the case of Terlipressin, the synthesis was carried out in parallel on Synbeads and also on TentaGel, ChemMatrix, and PS-DVB for comparison (DIC/HOBt route). The profiles describing the synthetic efficiency demonstrated that Synbeads leads to synthetic efficiency (86%) comparable to PS-DVB (96%) or ChemMatrix (84%). In order to gain a more precise picture of chemical and morphological features of Synbeads, their matrix was also characterized by exploiting innovative approaches based on FTIR microspectroscopy with a conventional source and with synchrotron radiation. A uniform distribution of the functional groups was evidenced through a detailed chemical mapping.

  2. Identification of an Extremely 180-Rich Presolar Silicate Grain in Acfer 094

    Nguyen, A. N.; Messenger, S.


    Presolar silicate grains have been abundantly identified since their first discovery less than a decade ago [1,2,3]. The O isotopic compositions of both silicate and oxide stardust indicate the vast majority (>90%) condensed around Orich asymptotic giant branch (AGB) stars. Though both presolar phases have average sizes of 300 nm, grains larger than 1 m are extremely uncommon for presolar silicates. Thus, while numerous isotopic systems have been measured in presolar oxide grains [4], very few isotopic analyses for presolar silicates exist outside of O and Si [2,5]. And still, these measurements suffer from isotopic dilution with surrounding matrix material [6]. We conduct a search for presolar silicates in the primitive carbonaceous chondrite Acfer 094 and in some cases obtain high spatial resolution, high precision isotopic ratios.

  3. Determination of N,N-dimethyltryptamine in Mimosa tenuiflora inner barks by matrix solid-phase dispersion procedure and GC-MS.

    Gaujac, Alain; Aquino, Adriano; Navickiene, Sandro; de Andrade, Jailson Bittencourt


    N,N-dimethyltryptamine (DMT) is a potent hallucinogen found in beverages consumed in religion rituals and neo-shamanic practices over the world. Two of these religions, Santo Daime and União do Vegetal (UDV), are represented in countries including Australia, the United States and several European nations. In some of this countries there have been legal disputes concerning the legalization of ayahuasca consumption during religious rituals, a beverage rich in DMT. In Brazil, even children and pregnant women are legally authorized to consume ayahuasca in a religious context. A simple and low-cost method based on matrix solid-phase dispersion (MSPD) and gas chromatography with mass spectrometric detection (GC-MS) has been optimized for the determination of N,N-dimethyltryptamine in Mimosa tenuiflora inner bark. The experimental variables that affect the MSPD method, such as the amounts of solid-phase and herbal sample, solvent nature, eluate volume and NaOH concentration were optimized using an experimental design. The method showed good linearity (r = 0.9962) and repeatability (RSD < 7.4%) for DMT compound, with detection limit of 0.12 mg/g. The proposed method was used to analyze 24 samples obtained locally. The results showed that concentrations of the target compound in M. tenuiflora barks, ranged from 1.26 to 9.35 mg/g for these samples. Copyright © 2011 Elsevier B.V. All rights reserved.

  4. EPR spectrum of the Y@C82 metallofullerene isolated in solid argon matrix: hyperfine structure from EPR spectroscopy and relativistic DFT calculations.

    Misochko, Eugenii Ya; Akimov, Alexander V; Belov, Vasilii A; Tyurin, Daniil A; Bubnov, Vyacheslav P; Kareev, Ivan E; Yagubskii, Eduard B


    The EPR spectrum of the Y@C(82) molecules isolated in solid argon matrix was recorded for the first time at a temperature of 5 K. The isotropic hyperfine coupling constant (hfcc) A(iso) = 0.12 +/- 0.02 mT on the nucleus (89)Y as derived from the EPR spectrum is found in more than two times greater than that obtained in previous EPR measurements in liquid solutions. Comparison of the measured hfcc on a metal atom with that predicted by density-functional theory calculations (PBE/L22) indicate that relativistic method provides good agreement between experiment in solid argon and theory. Analysis of the DFT calculated dipole-dipole hf-interaction tensor and electron spin distribution in the endometallofullerenes with encaged group 3 metal atoms Sc, Y and La has been performed. It shows that spin density on the scandium atom represents the Sc d(yz) orbital lying in the symmetry plane of the C(2v) fullerene isomer and interacting with two carbon atoms located in the para-position on the fullerene hexagon. In contrast, the configuration of electron spin density on the heavier atoms, Y and La, is associated with the hybridized orbital formed by interaction of the metal d(yz) and p(y) electronic orbitals.

  5. Miniaturized matrix solid-phase dispersion combined with ultrasound-assisted dispersive liquid-liquid microextraction for the determination of three pyrethroids in soil.

    Wang, Hui; Yan, Hongyuan; Qiao, Jindong


    A simple and miniaturized pretreatment procedure combining matrix solid-phase dispersion (MSPD) with ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) technique was proposed in first time for simultaneous determination of three pyrethroids (fenpropathrin, cyhalothrin and fenvalerate) in soils. The solid samples were directly extracted using MSPD procedure, and the eluent of MSPD was used as the dispersive solvent of the followed DLLME procedure for further purification and enrichment of the analytes before GC-ECD analysis. Good linear relationships were obtained for all the analytes in a range of 5.0-500.0 ng/g with LOQs (S/N=10) ranged from 1.51 to 3.77 ng/g. Average recoveries at three spiked levels were in a range of 83.6-98.5% with RSD≤7.3%. The present method combined the advantages of MSPD and DLLME, and was successfully applied for the determination of three pyrethroids in soil samples.

  6. [Determination of gibberellins in Arabidopsis thaliana by matrix solid-phase dispersion extraction and high performance liquid chromatography-tandem mass spectrometry].

    Wang, Lu; Wu, Qian; Duan, Chunfeng; Wu, Dapeng; Guan, Yafeng


    A method for the analysis of gibberellin A1 (GA1), gibberellin A3 (GA3) and gibberellin A4 (GA4) in Arabidopsis thaliana by matrix solid-phase dispersion extraction (MSPD) and high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed. The solid sample of Arabidopsis thaliana was gently blended with C18 to obtain a homogeneous mixture. This mixture was transferred to an SPE cartridge filled with 0.5 g C18 to form a MSPD column. GA1, GA3 and GA4 were eluted with cold 80% methanol aqueous solution. The target compounds were separated on a C18 column with a gradient elution of 0.05% formic acid aqueous solution and acetonitrile as the mobile phase. The identification and quantification were carried out by using electrospray ionization in negative ion mode (ESI-) with multiple reaction monitoring (MRM). The linear ranges for GA1, GA3 and GA4 were all from 10 to 300 ng/g with correlation coefficients greater than 0.98. The limits of detection were in the range of 1.1-4.1 ng/g. The average recoveries and relative standard deviations were 54.7%-102.6% and 3.2%-12.8% respectively in the spiked range of 10-50 ng/g. The method is simple, sensitive, efficient and accurate. It is suitable for the confirmation and quantitative determination of GA1, GA3 and GA4 in Arabidopsis thaliana.

  7. Optimization of matrix solid-phase dispersion for the rapid determination of salicylate and benzophenone-type UV absorbing substances in marketed fish.

    Tsai, Dung-Ying; Chen, Chien-Liang; Ding, Wang-Hsien


    A simple and effective method for the rapid determination of five salicylate and benzophenone-type UV absorbing substances in marketed fish is described. The method involves the use of matrix solid-phase dispersion (MSPD) prior to their determination by on-line silylation gas chromatography tandem mass spectrometry (GC-MS/MS). The parameters that affect the extraction efficiency were optimized using a Box-Behnken design method. The optimal extraction conditions involved dispersing 0.5g of freeze-dried powdered fish with 1.0g of Florisil using a mortar and pestle. This blend was then transferred to a solid-phase extraction (SPE) cartridge containing 1.0g of octadecyl bonded silica (C18), as the clean-up co-sorbent. The target analytes were then eluted with 7mL of acetonitrile. The extract was derivatized on-line in the GC injection-port by reaction with a trimethylsilylating (TMS) reagent. The TMS-derivatives were then identified and quantitated by GC-MS/MS. The limits of quantitation (LOQs) were less than 0.1ng/g. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. Participation of bacteria in weathering processes of silicates

    Peter Javorský


    Full Text Available Biological processes presented by the metabolic activity of different species of bacteria adhered at the mineral surfaces are a part of the geochemical processes. These bacteria accelerate, by the production of organic acids into the minerals structural bonds, the leaching of elements and their subsequent and gradual transformation to the secondary minerals. Microbial destructions of silicates are studied in order to processing low-quality mineral raw-materials and the remediation of soils, sediments and waters contaminated by industrial pollutants. The samples of material, used in our research, were obtained at 9 deposits of non-metallic raw-materials in Slovakia. The sediment sample was taken from the area of Baikal Lake. The presence of microorganisms in the matrix most frequently was determined by a subsequent isolation of microorganisms and identification of bacterial species presented in the silicate matrix. The species of Bacillus and Pseudomonas genus were the common representative of the microorganisms.

  9. Solid matrix priming with chitosan enhances seed germination and seedling invigoration in mung bean under salinity stress

    Sujoy SEN


    Full Text Available The objective of present study was to evaluate the response of the mung bean seeds of ‘Sonali B1’ variety primed with chitosan in four different concentrations (0, 0.1%, 0.2% and 0.5% under salinity stress of five different concentrations (i.e., 0, 4, 6, 8 and 12 dS*mm-1 and halotolerance pattern by applying Celite as matrix at three different moisture levels (5%, 10% and 20%. Improved germination percentage, germination index, mean germination time, coefficient of velocity of germination along with root and shoot length was observed comparing with control. Germination stress tolerance index (GSI, plant height stress tolerance index (PHSI and root length stress tolerance index (RLSI were used to evaluate the tolerance of the mung bean seeds against salinity stress induced by chitosan. Results of GSI, PHSI, RLSI showing noteworthy inhibitory effect of salinity stress in control set was significantly less pronounced in chitosan treated seedlings. Chitosan can remarkably alleviate the detrimental effect of salinity up to the level of 6 dS*m-1, beyond which no improvement was noticed. In conclusion present investigation revealed that chitosan is an ideal elicitor for enhancing the speed of germination and seedling invigoration that synchronize with emergence of radicle and salinity stress tolerance.

  10. Calibration of the complex matrix effects on the sampling of polycyclic aromatic hydrocarbons in milk samples using solid phase microextraction.

    Lin, Wei; Wei, Songbo; Jiang, Ruifen; Zhu, Fang; Ouyang, Gangfeng


    Solid phase microextraction (SPME), a simple, fast and promising sampling technique, has been widely used for complex sample analysis. However, complex matrices could modify the absorption property of coatings as well as the uptake kinetics of analytes, eventually biasing the quantification results. In the current study, we demonstrated the feasibility of a developed calibration method for the analysis of polycyclic aromatic hydrocarbons (PAHs) in complex milk samples. Effects of the complex matrices on the SPME sampling process and the sampling conditions were investigated. Results showed that short exposure time (pre-equilibrium SPME, PE-SPME) could increase the lifetime of coatings, and the complex matrices in milk samples could significantly influence the sampling kinetics of SPME. In addition, the optimized sampling time, temperature and dilution factor for PAHs were 10 min, 85 °C and 20, respectively. The obtained LODs and LOQs of all the PAHs were 0.1-0.8 ng/mL and 1.4-4.7 ng/mL, respectively. Furthermore, the accuracy of the proposed PE-SPME method for milk sampling was validated by the recoveries of the studied compounds in two concentration levels, which ranged from 75% to 110% for all the compounds. Finally, the proposed method was applied to the screening of PAHs in milk samples.

  11. Oligo-lysine Induced Formation of Silica Particles in Neutral Silicate Solution


    Oligo-(lysine)n (n = 1-4) containing different numbers of lysine residues was used to induce the condensation of silicic acid to form silica particles in neutral silicate solution. It was found that the condensation rate and the formation of silica particles are dependent on the number of lysine residues in an oligo-lysine. Oligo-lysine with more lysine residues can link more silicic acid together to form a matrix that promotes the effective aggregation of the condensed silica pieces to form large silica particles.

  12. Mineral stimulation of subsurface microorganisms: release of limiting nutrients from silicates

    Roger, Jennifer Roberts; Bennett, Philip C.


    accelerated weathering and release of Si into solution as well as the accelerated degradation of the model substrate 3,4 DHBA. We propose that silicate-bound P and Fe inclusions are bioavailable, and microorganisms may use organic ligands to dissolve the silicate matrix and access these otherwise limiting nutrients.

  13. Mechanical and thermal properties of sodium silicate treated moso bamboo particles reinforced PVC composites


    The main objective of this research was to study the potential of sodium silicate modification on moso bamboo particles as reinforcements for thermoplastic. Moso bamboo particles were modified with sodium silicate aqueous solutions (of 0.5%, 1%, 2%, 5% and 10% concentrations). The mechanical properties of sodium silicate treated moso bamboo particles reinforced PVC composites (BPPC) were calculated and compared with raw bamboo particles filled samples. The thermal characteristics of the BPPC were studied to investigate the feasibility of sodium silicate treatment on moso bamboo particles. The particle morphology and BPPC microstructure were investigated by scanning electron microscopy. Results showed that the tensile strength and modulus of elasticity of the BPPC increased before the concentration of sodium silicate solution reached 5% and got their maximum values of 15.72 MPa and 2956.80 MPa, respectively at 5% concentration. The modulus of rupture obtained the maximum value of 27.73 MPa at 2% concentration. The mechanical curve decreased as the concentration of solution went higher. Differential scanning calorimetric analysis illustrated that the sodium silicate solution treated BPPC possesses a better compatibility. More uniform dispersion of moso bamboo particles in PVC matrix was obtained after the sodium silicate treatment. Hence, the sodium silicate was a feasible and competitive agent of creating moso bamboo particles reinforced PVC composites.

  14. Sodium Silicate Behavior in Porous Media Applied for In-Depth Profile Modifications

    Hossein A. Akhlaghi Amiri


    Full Text Available This paper addresses alkaline sodium silicate (Na-silicate behavior in porous media. One of the advantages of the Na-silicate system is its water-like injectivity during the placement stage. Mixing Na-silicate with saline water results in metal silicate precipitation as well as immediate gelation. This work demonstrated that low salinity water (LSW, sea water diluted 25 times could be used as a pre-flush in flooding operations. A water override phenomenon was observed during gel formation which is caused by gravity segregation. Dynamic adsorption tests in the sand-packed tubes showed inconsiderable adsorbed silicon density (about 8.5 × 10−10 kg/cm3 for a solution with 33 mg/L silicon content, which is less than the estimated mono-layer adsorption density of 1.4 × 10−8 kg/cm3. Na-silicate enhanced water sweep efficiency after application in a dual-permeability sand-pack system, without leak off into the oil-bearing low permeability (LP zone. Field-scale numerical sensitivity studies in a layered reservoir demonstrated that higher permeability and viscosity contrasts and lower vertical/horizontal permeability ratio result in lower Na-silicate leakoff into the matrix. The length of the mixing zone between reservoir water and the injected Na-silicate solution, which is formed by low salinity pre-flush, acts as a buffer zone.

  15. AC electrical breakdown phenomena of epoxy/layered silicate nanocomposite in needle-plate electrodes.

    Park, Jae-Jun; Lee, Jae-Young


    Epoxy/layered silicate nanocomposite for the insulation of heavy electric equipments were prepared by dispersing 1 wt% of a layered silicate into an epoxy matrix with a homogenizing mixer and then AC electrical treeing and breakdown tests were carried out. Wide-angle X-ray diffraction (WAXD) analysis and transmission electron microscopy (TEM) observation showed that nano-sized monolayers were exfoliated from a multilayered silicate in the epoxy matrix. When the nano-sized silicate layers were incorporated into the epoxy matrix, the breakdown rate in needle-plate electrode geometry was 10.6 times lowered than that of the neat epoxy resin under the applied electrical field of 520.9 kV/mm at 30 degrees C, and electrical tree propagated with much more branches in the epoxy/layered silicate nanocomposite. These results showed that well-dispersed nano-sized silicate layers retarded the electrical tree growth rate. The effects of applied voltage and ambient temperature on the tree initiation, growth, and breakdown rate were also studied, and it was found that the breakdown rate was largely increased, as the applied voltage and ambient temperature increased.

  16. Mineralogical Characterization of Fe-Bearing AGB and Supernova Silicate Grains From the Queen Alexandra Range 99177 Meteorite

    Nguyen, A. N.; Keller, L. P.; Messenger, S.; Rahman, Z.


    Spectroscopic observations of the circumstellar envelopes of evolved O-rich stars indicate the dust is mostly amorphous silicate with olivine-like compositions. Spectral modeling suggests these grains are Fe-rich [Mg/(Mg+Fe) 0.5], but it is not known whether the Fe is distributed within the silicate matrix or exists as metal inclusions. In contrast, the crystalline silicates are inferred to be extremely Mg-rich [Mg/(Mg+Fe) > 0.95]. The mineralogies and chemical compositions of dust in supernova (SN) remnants are not as well constrained, but abundant silicates of olivine-like and enstatite-like compositions have been fit to the infrared emission features. Silicates in the interstellar medium (ISM) are >99% amor-phous and Fe-bearing. The dearth of crystalline silicates in the ISM requires that some amorphization or destruction mechanisms process these grains.

  17. Determination of nucleoside analog mono-, di-, and tri-phosphates in cellular matrix by solid phase extraction and ultra-sensitive LC-MS/MS detection.

    Bushman, Lane R; Kiser, Jennifer J; Rower, Joseph E; Klein, Brandon; Zheng, Jia-Hua; Ray, Michelle L; Anderson, Peter L


    An ultra-sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS) assay was developed and validated to facilitate the assessment of clinical pharmacokinetics of nucleotide analogs from lysed intracellular matrix. The method utilized a strong anion exchange isolation of mono-(MP), di-(DP), and tri-phosphates (TP) from intracellular matrix. Each fraction was then dephosphorylated to the parent moiety yielding a molar equivalent to the original nucleotide analog intracellular concentration. The analytical portion of the methodology was optimized in specific nucleoside analog centric modes (i.e. tenofovir (TFV) centric, zidovudine (ZDV) centric), which included desalting/concentration by solid phase extraction and detection by LC-MS/MS. Nucleotide analog MP-, DP-, and TP-determined on the TFV centric mode of analysis include TFV, lamivudine (3TC), and emtricitibine (FTC). The quantifiable linear range for TFV was 2.5-2000 fmol/sample, and that for 3TC/FTC was 0.1 200 pmol/sample. Nucleoside analog MP-, DP-, and TP-determined on the ZDV centric mode of analysis included 3TC and ZDV. The quantifiable linear range for 3TC was 0.1 100 pmol/sample, and 5-2000 fmol/sample for ZDV. Stable labeled isotopic internal standards facilitated accuracy and precision in alternative cell matrices, which supported the intended use of the method for MP, DP, and TP determinations in various cell types. The method was successfully applied to clinical research samples generating novel intracellular information for TFV, FTC, ZDV, and 3TC nucleotides. This document outlines method development, validation, and application to clinical research.

  18. Simplified matrix solid phase dispersion procedure for the determination of parabens and benzophenone-ultraviolet filters in human placental tissue samples.

    Vela-Soria, F; Rodríguez, I; Ballesteros, O; Zafra-Gómez, A; Ballesteros, L; Cela, R; Navalón, A


    In recent decades, the industrial development has resulted in the appearance of a large amount of new chemicals that are able to produce disorders in the human endocrine system. These substances, so-called endocrine disrupting chemicals (EDCs), include many families of compounds, such as parabens and benzophenone-UV filters. Taking into account the demonstrated biological activity of these compounds, it is necessary to develop new analytical procedures to assess the exposure in order to establish, in an accurate way, relationships between EDCs and harmful health effects in population. In the present work, a new method based on a simplified sample treatment by matrix solid phase dispersion (MSPD) followed by ultrahigh performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis, is validated for the determination of four parabens (methyl-, ethyl-, propyl- and butylparaben) and six benzophenone-UV filters (benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-6, benzophenone-8 and 4-hydroxybenzophenone) in human placental tissue samples. The extraction parameters were accurately optimized using multivariate optimization strategies. Ethylparaben ring-13C6 and benzophenone-d10 were used as surrogates. The found limits of quantification ranged from 0.2 to 0.4 ng g(-1) and inter-day variability (evaluated as relative standard deviation) ranged from 5.4% to 12.8%. The method was validated using matrix-matched standard calibration followed by a recovery assay with spiked samples. Recovery rates ranged from 96% to 104%. The method was satisfactorily applied for the determination of compounds in human placental tissue samples collected at the moment of delivery from 10 randomly selected women. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Simultaneous analysis of 45 pharmaceuticals and personal care products in sludge by matrix solid-phase dispersion and liquid chromatography tandem mass spectrometry.

    Li, Mingyue; Sun, Qian; Li, Yan; Lv, Min; Lin, Lifeng; Wu, Yang; Ashfaq, Muhammad; Yu, Chang-Ping


    Pharmaceuticals and personal care products (PPCPs) are a class of emerging contaminants widely distributed in the wastewater treatment system. The simultaneous analysis of multiple PPCPs in the sludge, which is a complex matrix, is still not fully studied. In this study, a procedure based on matrix solid-phase dispersion (MSPD) for the extraction of PPCPs from the sludge with determination by liquid chromatography tandem mass spectrometry (LC-MS/MS) was investigated. Forty-five PPCPs, including antibiotics, nonsteroidal anti-inflammatory drugs, β-blockers, antidepressants, antimicrobial agents, preservatives, UV filters, and so on, were studied. MSPD parameters, including the sorbent materials, the ratio of sample to sorbent, the eluent composition, and the elution volumes, were sequentially optimized. Best results were achieved by 0.1 g of sludge homogenized with 0.4 g of C18-bonded silica sorbent and elution by 6 mL methanol and 10 mL acetonitrile/5 % oxalic acid (8/2, v/v). The method quantification limits for the 45 PPCPs ranged 0.117-5.55 μg/kg. The PPCP recoveries ranged from 50.3 to 107 % with relative standard deviation lower than 15 %. The proposed method was applied to analyze PPCPs in the sludge collected from a domestic wastewater treatment plant over 1 year. Thirteen PPCPs were detected, with the concentrations of ofloxacin and triclocarban more than 1000 μg/kg. Temporal variations of the PPCP levels were observed. Thus, MSPD-LC-MS/MS method could achieve good sensitivity and recovery for the target PPCP analysis in the sludge samples, while MSPD provided one-step sample preparation which was easier and faster to perform compared to the commonly used methods. Graphical abstract Workflow of MSPD and LC-MS/MS chromatograms for PPCP analysis.

  20. 21 CFR 872.6670 - Silicate protector.


    ... DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6670 Silicate protector. (a) Identification. A silicate protector is a device made of silicone intended to be applied with an absorbent tipped applicator to...

  1. Matrix solid-phase dispersion combined to liquid chromatography-tandem mass spectrometry for the determination of paraben preservatives in mollusks.

    Villaverde-de-Sáa, Eugenia; Rodil, Rosario; Quintana, José Benito; Cela, Rafael


    A method for the extraction and determination of seven parabens, esters of 4-hydroxybenzoic acid, widely used as preservatives in personal care products, pharmaceuticals, etc., and two chlorinated derivatives (mono- and di-chloro methyl paraben) from mollusk samples was developed by combining matrix solid-phase dispersion (MSPD) and liquid chromatography-tandem mass spectrometry. MSPD parameters, such as solvent, solid support and clean-up sorbent, were optimized. Besides, since blank problems were observed for some parabens, these were investigated and blanks were tackled by precleaning all sorbents prior to use. Under final conditions, 0.5g of freeze-dried mollusk were dispersed with 1.2g of silica and packed into a cartridge containing 3g of C18, as on-line clean-up sorbent. This cartridge was eluted with 10mL of acetonitrile, evaporated and reconstituted in methanol for analysis. In the validation stage, successful linearity (R(2)>0.999), recoveries (between 71 and 117% for most analytes), precision (RSD lower than 21%) and limits of detection and quantification (LOD and LOQ, lower than 0.4 and 1.4ngg(-1) dry weight respectively) levels were achieved. Finally, the new methodology was applied to mussel, clam and cockle samples. Methyl paraben was above the LOQ in five of the six samples (not found in one clam sample) at concentrations up to 7ngg(-1) dry weight. Ethyl paraben was found above the LOQ in mussel and cockle samples at a concentration level around 0.3ngg(-1). n-Propyl paraben was only above the LOQ in one mussel sample.

  2. Universal chemiluminescence flow-through device based on directed self-assembly of solid-state organic chromophores on layered double hydroxide matrix.

    Wang, Zhihua; Teng, Xu; Lu, Chao


    In this work, a universal chemiluminescence (CL) flow-through device suitable for various CL resonance energy transfer (CRET) systems has been successfully fabricated. Highly efficient CRET in solid-state photoactive organic molecules can be achieved by assembling them on the surface of layered double hydroxides (LDHs). We attribute these observations to the suppression of the intermolecular π-π stacking interactions among aromatic rings and the improvement of molecular orientation and planarity in the LDH matrix, enabling a remarkable increase in fluorescence lifetime and quantum yield of organic molecules. Under optimal conditions, using peroxynitrous acid-fluorescein dianion (FLUD) as a model CRET system, trace FLUD (10 μM) was assembled on the surface of LDHs. Peroxynitrous acid/nitrite could be assayed in the range of 1.0-500 μM, and the detection limit for peroxynitrous acid/nitrite (S/N = 3) was 0.6 μM. This CL flow-through device exhibited operational stability, high reproducibility, and long lifetime. While LDHs were immobilized in a flow-through device in the absence of FLUD, the detection limit for peroxynitrous acid/nitrite was 100 μM. On the other hand, FLUD at the same concentration can not enhance the CL intensity of peroxynitrous acid system. This fabricated CL flow-through column has been successfully applied to determine nitrite in sausage samples with recoveries of 98-102%. These satisfactory results demonstrated that our studies pave a novel way toward flow-through column-based CRET using solid-state organic molecules as acceptors for signal amplification.


    V. A. Aseev


    Full Text Available We created and synthesized luminescent composite of the "phosphor in glass" type, based on the lead-silicate matrix and fine-dispersed powder of cerium-activated yttrium-aluminum garnet crystal. Lead-silicate system (40SiO2- 20PbO-(40-x PbF2-xAlF3, x = 0-25 was chosen as the glassy matrix. Initial glass was reduced to powder (frit for "phosphor in glass" composite with a particle size about 50 µm. Glass frit and powder of commercial YAG:Ce3+ phosphor were mixed in a ratio of 30 to 70 (wt %. Then this composite was pressed in a tablet and sintered on a quartz substrate at 823 К for 30 minutes. Thus, the plane parallel sheet for composite of the "phosphor in glass" was obtained with a diameter equal to 10 mm. For the purpose to reduce the loss of light in the presence of dispersion at a glass-phosphor boundary, optimization of glass mixture was done by adjusting the refractive index. X-ray phase and spectral-luminescent analysis of the derived composite were done. The results of these studies showed that there was no degradation of YAG: Ce powder during sintering. Dependence of luminescence intensity from temperature in the range from room temperature to 473 К was studied. It was shown, that with the phosphor in glass usage thermal quenching of luminescence was reduced in comparison with the silicone. The model of white LED was created with the "phosphor in glass" composite based on lead-silicate glasses with low temperature of vitrifying. The derived LED emits white light with a color temperature of 4370 K, and the luminous efficiency is equal to 58 lm/W. The developed luminescent composite based on the lead-silicate matrix can be used for the production of high-power white light LED.

  4. Antibacterial Activity of Silicate Bioceramics

    HU Sheng; NING Congqin; ZHOU Yue; CHEN Lei; LIN Kaili; CHANG Jiang


    Four kinds of pure silicate ceramic particles, CaSiO3, Ca3SiO5, bredigite and akermanite were prepared and their bactericidal effects were systematically investigated. The phase compositions of these silicate ceramics were characterized by XRD. The ionic concentration meas urement revealed that the Calcium (Ca) ion concentration were relatively higher in Ca3SiO5 and bredigite, and much lower in CaSiO3 and akermanite. Accordingly, the pH values of the four silicate ceramics extracts showed a positive correlation with the particle concentrations. Meanwhile, by decreasing the particle size, higher Ca ion concentrations can be achieved, leading to the increase of aqueous pH value as well. In summary, all of the four silicate ceramics tested in our study showed antibacterial effect in a dose-dependent manner. Generally, the order of their antibacterial activity against E.coli from strong to weak is Ca3SiO5, bredigite, CaSiO3 and akermanite.

  5. Amended Silicated for Mercury Control

    James Butz; Thomas Broderick; Craig Turchi


    Amended Silicates{trademark}, a powdered, noncarbon mercury-control sorbent, was tested at Duke Energy's Miami Fort Station, Unit 6 during the first quarter of 2006. Unit 6 is a 175-MW boiler with a cold-side electrostatic precipitator (ESP). The plant burns run-of-the-river eastern bituminous coal with typical ash contents ranging from 8-15% and sulfur contents from 1.6-2.6% on an as-received basis. The performance of the Amended Silicates sorbent was compared with that for powdered activated carbon (PAC). The trial began with a period of baseline monitoring during which no sorbent was injected. Sampling during this and subsequent periods indicated mercury capture by the native fly ash was less than 10%. After the baseline period, Amended Silicates sorbent was injected at several different ratios, followed by a 30-day trial at a fixed injection ratio of 5-6 lb/MMACF. After this period, PAC was injected to provide a comparison. Approximately 40% mercury control was achieved for both the Amended Silicates sorbent and PAC at injection ratios of 5-6 lbs/MMACF. Higher injection ratios did not achieve significantly increased removal. Similar removal efficiencies have been reported for PAC injection trials at other plants with cold-side ESPs, most notably for plants using medium to high sulfur coal. Sorbent injection did not detrimentally impact plant operations and testing confirmed that the use of Amended Silicates sorbent does not degrade fly ash quality (unlike PAC). The cost for mercury control using either PAC or Amended Silicates sorbent was estimated to be equivalent if fly ash sales are not a consideration. However, if the plant did sell fly ash, the effective cost for mercury control could more than double if those sales were no longer possible, due to lost by-product sales and additional cost for waste disposal. Accordingly, the use of Amended Silicates sorbent could reduce the overall cost of mercury control by 50% or more versus PAC for locations where

  6. Immiscible silicate liquids and phosphoran olivine in Netschaëvo IIE silicate: Analogue for planetesimal core-mantle boundaries

    Van Roosbroek, Nadia; Hamann, Christopher; McKibbin, Seann; Greshake, Ansgar; Wirth, Richard; Pittarello, Lidia; Hecht, Lutz; Claeys, Philippe; Debaille, Vinciane


    We have investigated a piece of the Netschaëvo IIE iron meteorite containing a silicate inclusion by means of electron microprobe analysis (EMPA) and transmission electron microscopy (TEM). Netschaëvo contains chondrule-bearing clasts and impact melt rock clasts were also recently found. The examined inclusion belongs to the latter and is characterized by a porphyritic texture dominated by clusters of coarse-grained olivine and pyroxene, set in a fine-grained groundmass that consists of new crystals of olivine and a hyaline matrix. This matrix material has a quasi-basaltic composition in the inner part of the inclusion, whereas the edge of the inclusion has a lower SiO2 concentration and is enriched in MgO, P2O5, CaO, and FeO. Close to the metal host, the inclusion also contains euhedral Mg-chromite crystals and small (olivine crystallites containing up to 14 wt% P2O5, amorphous material, and interstitial Cl-apatite crystals. The Si-rich silicate glass globules show a second population of Fe-rich silicate glass droplets, indicating they formed by silicate liquid immiscibility. Together with the presence of phosphoran olivine and quenched Cl-apatite, these textures suggest rapid cooling and quenching as a consequence of an impact event. Moreover, the enrichment of phosphorus in the silicate inclusion close to the metal host (phosphoran olivine and Cl-apatite) indicates that phosphorus re-partitioned from the metal into the silicate phase upon cooling. This probably also took place in pallasite meteorites that contain late-crystallizing phases rich in phosphorus. Accordingly, our findings suggest that oxidation of phosphorus might be a general process in core-mantle environments, bearing on our understanding of planetesimal evolution. Thus, the Netschaëvo sample serves as a natural planetesimal core-mantle boundary experiment and based on our temperature estimates, the following sequence of events takes place: (i) precipitation of olivine (1400-1360 °C), (ii) re

  7. Determination of paraben preservatives in seafood using matrix solid-phase dispersion and on-line acetylation gas chromatography-mass spectrometry.

    Djatmika, Rosalina; Hsieh, Chih-Chung; Chen, Jhih-Ming; Ding, Wang-Hsien


    An effective method for determining four commonly detected paraben preservatives (methyl, ethyl, propyl and butyl paraben) in marketed seafood is presented. This method employs matrix solid-phase dispersion (MSPD) before identification and quantification of the paraben preservatives via on-line acetylation gas chromatography-mass spectrometry (GC-MS). Parameters affecting the extraction efficiency of MSPD were optimized through a Box-Behnken design method. Under optimal condition, 0.5-g of freeze-dried seafood was mixed with 0.5-g of anhydrous sodium sulfate, and dispersed with 1.0-g of Florisil using vortex. After that, the blend was transferred to a glass column containing 1.5-g of silica gel+C18 (w/w, 9:1), which acted as clean-up co-sorbents. Then, target analytes were eluted with 12mL of acetonitrile. The extract was then derivatized on-line in the GC injection-port through reaction with acetic anhydride, and the identity and quantity of the target analytes were determined by the GC-MS system. The limits of quantitation (LOQs) were 0.2 to 1.0ng/g (dry weight). Preliminary results showed that the total concentrations of four selected parabens ranged from 16.7 to 44.7ng/g (dry weight).

  8. Optimization of a method based on micro-matrix solid-phase dispersion (micro-MSPD for the determination of PCBs in mussel samples

    Nieves Carro


    Full Text Available This paper reports the development and optimization of micro-matrix solid-phase dispersion (micro-MSPD of nine polychlorinated biphenyls (PCBs in mussel samples (Mytilus galloprovincialis by using a two-level factorial design. Four variables (amount of sample, anhydrous sodium sulphate, Florisil and solvent volume were considered as factors in the optimization process. The results suggested that only the interaction between the amount of anhydrous sodium sulphate and the solvent volume was statistically significant for the overall recovery of a trichlorinated compound, CB 28. Generally most of the considered species exhibited a similar behaviour, the sample and Florisil amounts had a positive effect on PCBs extractions and solvent volume and sulphate amount had a negative effect. The analytical determination and confirmation of PCBs were carried out by using GC-ECD and GC-MS/MS, respectively. The method was validated having satisfactory precision and accuracy with RSD values below 6% and recoveries between 81 and 116% for all congeners. The optimized method was applied to the extraction of real mussel samples from two Galician Rías.

  9. Molecularly Imprinted Nanomicrospheres as Matrix Solid-Phase Dispersant Combined with Gas Chromatography for Determination of Four Phosphorothioate Pesticides in Carrot and Yacon

    Mengchun Zhou


    Full Text Available An efficient, rapid, and selective method for sample pretreatment, namely, molecularly imprinted matrix solid-phase dispersion (MI-MSPD coupled with gas chromatography (GC, was developed for the rapid isolation of four phosphorothioate organophosphorus pesticides (tolclofos-methyl, phoxim, chlorpyrifos, and parathion-methyl from carrot and yacon samples. New molecularly imprinted polymer nanomicrospheres were synthesized by using typical structural analogue tolclofos-methyl as a dummy template via surface grafting polymerization on nanosilica. Then, these four pesticides in carrot and yacon were extracted and adsorbed using the imprinted nanomicrospheres and further determined by gas chromatography. Under the optimized conditions, a good linearity of four pesticides was obtained in a range of 0.05–17.0 ng·g−1 with R varying from 0.9971 to 0.9996, and the detection limit of the method was 0.012~0.026 ng·g−1 in carrot and yacon samples. The recovery rates at two spiked levels were in the range of 85.4–105.6% with RSD ≤9.6%. The presented MI-MSPD method combined the advantages of MSPD for allowing the extraction, dispersion, and homogenization in two steps and the advantages of MIPs for high affinity and selectivity towards four phosphorothioate pesticides, which could be applied to the determination of pesticide residues in complicated vegetal samples.

  10. Simultaneous determination of fumonisins B1 and B2 in different types of maize by matrix solid phase dispersion and HPLC-MS/MS.

    de Oliveira, Gabriel Barros; de Castro Gomes Vieira, Carolyne Menezes; Orlando, Ricardo Mathias; Faria, Adriana Ferreira


    This work involved the optimization and validation of a method, according to Directive 2002/657/EC and the Analytical Quality Assurance Manual of Ministério da Agricultura, Pecuária e Abastecimento, Brazil, for simultaneous extraction and determination of fumonisins B1 and B2 in maize. The extraction procedure was based on a matrix solid phase dispersion approach, the optimization of which employed a sequence of different factorial designs. A liquid chromatography-tandem mass spectrometry method was developed for determining these analytes using the selected reaction monitoring mode. The optimized method employed only 1g of silica gel for dispersion and elution with 70% ammonium formate aqueous buffer (50mmolL(-1), pH 9), representing a simple, cheap and chemically friendly sample preparation method. Trueness (recoveries: 86-106%), precision (RSD ≤19%), decision limits, detection capabilities and measurement uncertainties were calculated for the validated method. The method scope was expanded to popcorn kernels, white maize kernels and yellow maize grits. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. In-Vial Micro-Matrix-Solid Phase Dispersion for the Analysis of Fragrance Allergens, Preservatives, Plasticizers, and Musks in Cosmetics

    Maria Celeiro


    Full Text Available Fragrance allergens, preservatives, plasticizers, and synthetic musks are usually present in cosmetic and personal care products formulations and many of them are subjected to use restrictions or labeling requirements. Matrix solid-phase dispersion (MSPD is a very suitable analytical technique for the extraction of these compounds providing a simple, low cost sample preparation, and the possibility of performing both extraction and clean-up in one step, reducing possible contamination and analyte losses. This extraction technique has been successfully applied to many cosmetics ingredients allowing obtaining quantitative recoveries. A new very simple micro-MSPD procedure performing the disruption step in a vial is proposed for the gas chromatography-mass spectrometry (GC-MS analysis of 66 chemicals usually present in cosmetics and personal care products. The method was validated showing general recoveries between 80% and 110%, relative standard deviation (RSD values lower than 15%, and limits of detection (LODs below 30 ng·g−1. The validated method was applied to a broad range of cosmetics and personal care products, including several products intended for baby care.

  12. Single "click" synthesis of a mixed-mode silica sorbent and application in matrix solid-phase dispersion extraction of β-agonists from porcine liver.

    Zhu, Yuling; Yang, Siwen; Chen, Gang; Xing, Jun


    A single "click" strategy is proposed for the preparation of a reversed-phase/weak cation-exchange mixed-mode silica-based sorbent (silica-WCX). Upon this strategy, both 1-dodecyne and 5-hexynoic acid were simultaneously immobilized onto azide-silica in varied ratio via Cu (I)-catalyzed azide-alkyne cycloaddition click reaction. The chemical compositions of silica-WCXs were characterized by elemental analysis, acid-base titration and Fourier transform-infrared spectroscopy. The results indicated that the actual mole ratio of n-dodecyl to carboxylic group on the sorbent is almost the same as the reactant ratio of 1-dodecyne to 5-hexynoic acid, and the repeatability of synthesis method is good. After that, two β-agonists, clenbuterol and ractopamine, were selected as model drug residues to evaluate the applicability of silica-WCX in matrix solid-phase dispersion extraction for the determination of basic drug residues in porcine liver by HPLC/UV. In comparison with some commercial sorbents, silica-WCX exhibited higher recoveries and better purification capability. Under the optimized conditions, linearity ranges were between 0.04 and 8.0μg/g for both analytes with coefficients of determination (R(2)) higher than 0.9997. The average recoveries at three spiked levels ranged from 92.5% to 105.0% with RSDs less than 6.6%.

  13. Application of matrix solid-phase dispersion to the propham and maleic hydrazide determination in potatoes by differential pulse voltammetry and HPLC.

    Arribas, Alberto Sánchez; Bermejo, Esperanza; Chicharro, Manuel; Zapardiel, Antonio


    The application of the matrix solid-phase dispersion (MSPD) process as sample treatment in connection with the electrochemical detection is studied for the first time. For this purpose, a novel methodology is introduced for the extraction of propham and maleic hydrazide herbicides from potatoes samples based in the MSPD process prior to their electrochemical detection. Potato samples disruption was done by blending them with C(8) bonded-phase and selective herbicide extraction was achieved by successive treatment of the blended with 50mM phosphate buffer pH 7.4 (for maleic hydrazide) and methanol (for propham). The extraction procedure efficiency was estimated using differential pulse voltammetry in potato samples spiked with the herbicides yielding recovery values of 98% and 68% for propham and maleic hydrazide, respectively. No significant adverse effect of the MSPD process was observed on the herbicides electrochemical signals. For comparison, recovery studies using HPLC with UV detection were carried out and a good correlation in the results obtained by using both techniques was observed.

  14. Electron stimulated hydroxylation of a metal supported silicate film.

    Yu, Xin; Emmez, Emre; Pan, Qiushi; Yang, Bing; Pomp, Sascha; Kaden, William E; Sterrer, Martin; Shaikhutdinov, Shamil; Freund, Hans-Joachim; Goikoetxea, Itziar; Wlodarczyk, Radoslaw; Sauer, Joachim


    Water adsorption on a double-layer silicate film was studied by using infrared reflection-absorption spectroscopy, thermal desorption spectroscopy and scanning tunneling microscopy. Under vacuum conditions, small amounts of silanols (Si-OH) could only be formed upon deposition of an ice-like (amorphous solid water, ASW) film and subsequent heating to room temperature. Silanol coverage is considerably enhanced by low-energy electron irradiation of an ASW pre-covered silicate film. The degree of hydroxylation can be tuned by the irradiation parameters (beam energy, exposure) and the ASW film thickness. The results are consistent with a generally accepted picture that hydroxylation occurs through hydrolysis of siloxane (Si-O-Si) bonds in the silica network. Calculations using density functional theory show that this may happen on Si-O-Si bonds, which are either parallel (i.e., in the topmost silicate layer) or vertical to the film surface (i.e., connecting two silicate layers). In the latter case, the mechanism may additionally involve the reaction with a metal support underneath. The observed vibrational spectra are dominated by terminal silanol groups (ν(OD) band at 2763 cm(-1)) formed by hydrolysis of vertical Si-O-Si linkages. Film dehydroxylation fully occurs only upon heating to very high temperatures (∼ 1200 K) and is accompanied by substantial film restructuring, and even film dewetting upon cycling hydroxylation/dehydroxylation treatment.

  15. Core formation in silicate bodies

    Nimmo, F.; O'Brien, D. P.; Kleine, T.


    Differentiation of a body into a metallic core and silicate mantle occurs most efficiently if temperatures are high enough to allow at least the metal to melt [1], and is enhanced if matrix deformation occurs [2]. Elevated temperatures may occur due to either decay of short-lived radio-isotopes, or gravitational energy release during accretion [3]. For bodies smaller than the Moon, core formation happens primarily due to radioactive decay. The Hf-W isotopic system may be used to date core formation; cores in some iron meteorites and the eucrite parent body (probably Vesta) formed within 1 My and 1-4~My of solar system formation, respectively [4]. These formation times are early enough to ensure widespread melting and differentiation by 26Al decay. Incorporation of Fe60 into the core, together with rapid early mantle solidification and cooling, may have driven early dynamo activity on some bodies [5]. Iron meteorites are typically depleted in sulphur relative to chondrites, for unknown reasons [6]. This depletion contrasts with the apparently higher sulphur contents of cores in larger planetary bodies, such as Mars [7], and also has a significant effect on the timing of core solidification. For bodies of Moon-size and larger, gravitational energy released during accretion is probably the primary cause of core formation [3]. The final stages of accretion involve large, stochastic collisions [8] between objects which are already differentiated. During each collision, the metallic cores of the colliding objects merge on timescales of a few hours [9]. Each collision will reset the Hf-W isotopic signature of both mantle and core, depending on the degree to which the impactor core re-equilibrates with the mantle of the target [10]. The re-equilibration efficiency depends mainly on the degree to which the impactor emulsifies [11], which is very uncertain. Results from N-body simulations [8,12] suggest that significant degrees of re- equilibration are required [4,10]. Re

  16. Effects of ionization on silicate glasses. [Silicate glasses

    Primak, W.


    This evaluation of radiation effects in silicate glasses caused by ionization is based on our own investigations, on material collected in our files (reports, articles, and notes), and on a computer literature search through recent issues of Physics Abstracts and Chemical Abstracts (and the apparently pertinent references which appeared). Some of our recent results, available heretofore only in internal correspondence, are presented in some detail. It is concluded that research into the behavior of silicate glasses generally will be required before the specific effects in the radioactive waste storage glasses can be properly understood and evaluated. Two particular neglected areas of investigation are targeted for immediate concern: a kinetic analysis of annealing data and the acquisition of data on effects of irradiation at controlled elevated temperatures.

  17. Measurement of the efficacy of calcium silicate for the protection and repair of dental enamel.

    Parker, Alexander S; Patel, Anisha N; Al Botros, Rehab; Snowden, Michael E; McKelvey, Kim; Unwin, Patrick R; Ashcroft, Alexander T; Carvell, Mel; Joiner, Andrew; Peruffo, Massimo


    To investigate the formation of hydroxyapatite (HAP) from calcium silicate and the deposition of calcium silicate onto sound and acid eroded enamel surfaces in order to investigate its repair and protective properties. Calcium silicate was mixed with phosphate buffer for seven days and the resulting solids analysed for crystalline phases by Raman spectroscopy. Deposition studies were conducted on bovine enamel surfaces. Acid etched regions were produced on the enamel surfaces using scanning electrochemical cell microscopy (SECCM) with acid filled pipettes and varying contact times. Following treatment with calcium silicate, the deposition was visualised with FE-SEM and etch pit volumes were measured by AFM. A second set of bovine enamel specimens were pre-treated with calcium silicate and fluoride, before acid exposure with the SECCM. The volumes of the resultant acid etched pits were measured using AFM and the intrinsic rate constant for calcium loss was calculated. Raman spectroscopy confirmed that HAP was formed from calcium silicate. Deposition studies demonstrated greater delivery of calcium silicate to acid eroded than sound enamel and that the volume of acid etched enamel pits was significantly reduced following one treatment (penamel was 0.092 ± 0.008 cm/s. This was significantly reduced, 0.056 ± 0.005 cm/s, for the calcium silicate treatments (penamel surfaces. Calcium silicate can provide significant protection of sound enamel from acid challenges. Calcium silicate is a material that has potential for a new approach to the repair of demineralised enamel and the protection of enamel from acid attacks, leading to significant dental hard tissue benefits. © 2014 Elsevier Ltd. All rights reserved.

  18. Silicate Composition of the Interstellar Medium

    Fogerty, Shane; Watson, Dan M; Sargent, Benjamin A; Koch, Ingrid


    The composition of silicate dust in the diffuse interstellar medium and in protoplanetary disks around young stars informs our understanding of the processing and evolution of the dust grains leading up to planet formation. Analysis of the well-known 9.7{\\mu}m feature indicates that small amorphous silicate grains represent a significant fraction of interstellar dust and are also major components of protoplanetary disks. However, this feature is typically modelled assuming amorphous silicate dust of olivine and pyroxene stoichiometries. Here, we analyze interstellar dust with models of silicate dust that include non-stoichiometric amorphous silicate grains. Modelling the optical depth along lines of sight toward the extinguished objects Cyg OB2 No. 12 and {\\zeta} Ophiuchi, we find evidence for interstellar amorphous silicate dust with stoichiometry intermediate between olivine and pyroxene, which we simply refer to as "polivene." Finally, we compare these results to models of silicate emission from the Trapez...

  19. Well-aligned polycrystalline lanthanum silicate oxyapatite grown by reactive diffusion between solid La{sub 2}SiO{sub 5} and gases [SiO+1/2O{sub 2}

    Fukuda, Koichiro, E-mail: [Department of Materials Science and Engineering, Nagoya Institute of Technology, Nagoya 466-8555 (Japan); Hasegawa, Ryo; Kitagawa, Takuya; Nakamori, Hiroshi; Asaka, Toru [Department of Materials Science and Engineering, Nagoya Institute of Technology, Nagoya 466-8555 (Japan); Berghout, Abid; Béchade, Emilie; Masson, Olivier; Jouin, Jenny; Thomas, Philippe [Science des Procédés Céramiques et de Traitements de Surface (SPCTS), UMR 7315 CNRS, Université de Limoges, Centre Européen de la Céramique, 12 Rue Atlantis, 87068 Limoges Cedex (France)


    The c-axis-oriented polycrystalline lanthanum silicate oxyapatite, La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} (□ denotes a vacancy in the Si site), was successfully prepared by the reactive diffusion between randomly grain-oriented La{sub 2}SiO{sub 5} polycrystal and [SiO+1/2O{sub 2}] gases at 1873 K in Ar atmosphere. The polycrystal was characterized using optical microscopy, scanning electron microscopy equipped with energy dispersive X-ray spectroscopy, micro-Raman spectroscopy, X-ray diffractometry, and impedance spectroscopy. The crystal structure (space group P6{sub 3}/m) showed the deficiency of Si site at ca. 1.9%. The bulk oxide-ion conductivity along the grain-alignment direction steadily increased from 9.2 × 10{sup −3} to 1.17 × 10{sup −2} S/cm with increasing temperature from 923 to 1073 K. The activation energy of conduction was 0.23(2) eV. - Graphical abstract: We have successfully prepared the highly c-axis-oriented polycrystalline La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} by the reactive diffusion between randomly grain-oriented La{sub 2}SiO{sub 5} polycrystal and [SiO + 1/2O{sub 2}] gases at 1873 K in Ar atmosphere. The crystal structure (space group P6{sub 3}/m) showed the deficiency of Si site of ca. 1.9%. - Highlights: • The c-axis-oriented polycrystalline La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} is successfully prepared. • Crystal structure of La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} is determined by single-crystal XRD. • The polycrystal shows relatively high oxide ion conductivity along the common c-axis. • Reactive diffusion is successfully used for the preparation of grain-aligned ceramics.

  20. Inorganic phosphors in lead-silicate glass for white LEDs

    Nikonorov, N. V.; Kolobkova, E. V.; Aseev, V. A.; Bibik, A. Yu.; Nekrasova, Ya. A.; Tuzova, Yu. V.; Novogran, A. I.


    Luminescent composites of the "phosphor-in-glass" type, based on a highly reflective lead-silicate matrix and fine-grained powders of YAG:Ce3+ and SiAlON:Eu2+ crystals, are developed and synthesized. Phosphor and glass powders are sintered at a temperature of 550°C to obtain phosphor samples for white LEDs. The composites are analyzed by X-ray diffraction and luminescence spectroscopy. The dependence of the light quantum yield on the SiAlON:Eu2+ content in the samples is investigated. A breadboard of a white LED is designed using a phosphor-in-glass composite based on lead-silicate glass with a low glasstransition temperature. The total emission spectra of a blue LED and glass-based composites are measured. The possibility of generating warm white light by choosing an appropriate composition is demonstrated.

  1. Surface characterization of silicate bioceramics.

    Cerruti, Marta


    The success of an implanted prosthetic material is determined by the early events occurring at the interface between the material and the body. These events depend on many surface properties, with the main ones including the surface's composition, porosity, roughness, topography, charge, functional groups and exposed area. This review will portray how our understanding of the surface reactivity of silicate bioceramics has emerged and evolved in the past four decades, owing to the adoption of many complementary surface characterization tools. The review is organized in sections dedicated to a specific surface property, each describing how the property influences the body's response to the material, and the tools that have been adopted to analyse it. The final section introduces the techniques that have yet to be applied extensively to silicate bioceramics, and the information that they could provide.

  2. Biogenic silicate accumulation in sediments, Jiaozhou Bay

    LI Xuegang; SONG Jinming; DAI Jicui; YUAN Huamao; LI Ning; LI Fengye; SUN Song


    It has been widely recognized that low silicate content in seawater is a major limiting factor to phytoplankton primary production in Jiaozhou Bay. However the reason of Si-limitation remains poorly understood. In the present study we measured the biogenic silicate content and discussed the accumulation of silicate in Jiaozhou Bay sediment. The results show that the biogenic silica content in the sediment of the Jiaozhou Bay is obviously much higher than those in the Yellow Sea and the Bohai Sea. The BSi:TN ratios and BSi:16P ratios in the sediment are > 1 and the OC:BSi ratio in sediment is lower than these of Redfield ratio (106:16), indicating that the decomposition rate of OC is much higher than that for BSi in similar conditions. Therefore, the majority of the biogenic silicate was buried and thus did not participate in silicate recycling. Silicate accumulation in sediment may explain why Si limits the phytoplankton growth in the Jiaozhou Bay. Comparing the flux of biogenic silicate from sediments with primary production rate, it can be concluded that only 15.5% of biogenic silicate is hydrolyzed during the journey from surface to bottom in seawater, thus approximate 84.5% of biogenic silicate could reach the bottom. The silicate releasing rate from the sediment to seawater is considerably lower than that of sedimentation of biogenic silicate, indicating silicate accumulation in sediment too. In a word, the silicate accumulation in sediment is the key reason of silicate limiting to phytoplankton growth in Jiaozhou Bay.

  3. Longevity of silicate ceramic restorations.

    Beier, Ulrike Stephanie; Dumfahrt, Herbert


    The demand for esthetic restorations has resulted in an increased use of dental ceramics as a biocompatible and functionally sufficient alternative to conventional restorative materials. Silicate ceramic restorations are widely used for veneers, inlays, onlays, and crowns in dentistry. Long-term data are of crucial importance to optimize clinical practice. The purpose of the present article is to summarize data of the Innsbruck ceramic evaluation up to 261 months with the focus on longevity and failure characteristics.

  4. Rapid Detection and Identification of Candidemia by Direct Blood Culturing on Solid Medium by Use of Lysis-Centrifugation Method Combined with Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS).

    Idelevich, Evgeny A; Grünastel, Barbara; Becker, Karsten


    Candida sepsis is a life-threatening condition with increasing prevalence. In this study, direct blood culturing on solid medium using a lysis-centrifugation procedure enabled successful Candida species identification by matrix-assisted laser desorption-ionization time of flight mass spectrometry on average 3.8 h (Sabouraud agar) or 7.4 h (chocolate agar) before the positivity signal for control samples in Bactec mycosis-IC/F or Bactec Plus aerobic/F bottles, respectively. Direct culturing on solid medium accelerated candidemia diagnostics compared to that with automated broth-based systems. Copyright © 2016 American Society for Microbiology.

  5. Confined Water in Layered Silicates: The Origin of Anomalous Thermal Expansion Behavior in Calcium-Silicate-Hydrates.

    Krishnan, N M Anoop; Wang, Bu; Falzone, Gabriel; Le Pape, Yann; Neithalath, Narayanan; Pilon, Laurent; Bauchy, Mathieu; Sant, Gaurav


    Water, under conditions of nanoscale confinement, exhibits anomalous dynamics, and enhanced thermal deformations, which may be further enhanced when such water is in contact with hydrophilic surfaces. Such heightened thermal deformations of water could control the volume stability of hydrated materials containing nanoconfined structural water. Understanding and predicting the thermal deformation coefficient (TDC, often referred to as the CTE, coefficient of thermal expansion), which represents volume changes induced in materials under conditions of changing temperature, is of critical importance for hydrated solids including: hydrogels, biological tissues, and calcium silicate hydrates, as changes in their volume can result in stress development, and cracking. By pioneering atomistic simulations, we examine the physical origin of thermal expansion in calcium-silicate-hydrates (C-S-H), the binding agent in concrete that is formed by the reaction of cement with water. We report that the TDC of C-S-H shows a sudden increase when the CaO/SiO2 (molar ratio; abbreviated as Ca/Si) exceeds 1.5. This anomalous behavior arises from a notable increase in the confinement of water contained in the C-S-H's nanostructure. We identify that confinement is dictated by the topology of the C-S-H's atomic network. Taken together, the results suggest that thermal deformations of hydrated silicates can be altered by inducing compositional changes, which in turn alter the atomic topology and the resultant volume stability of the solids.

  6. Analysis of multi-class preservatives in leave-on and rinse-off cosmetics by matrix solid-phase dispersion.

    Sanchez-Prado, Lucia; Alvarez-Rivera, Gerardo; Lamas, J Pablo; Lores, Marta; Garcia-Jares, Carmen; Llompart, Maria


    Matrix solid-phase extraction has been successfully applied for the determination of multi-class preservatives in a wide variety of cosmetic samples including rinse-off and leave-on products. After extraction, derivatization with acetic anhydride, and gas chromatography-mass spectrometry analysis were performed. Optimization studies were done on real non-spiked and spiked leave-on and rinse-off cosmetic samples. The selection of the most suitable extraction conditions was made using statistical tools such as ANOVA, as well as factorial experimental designs. The final optimized conditions were common for both groups of cosmetics and included the dispersion of the sample with Florisil (1:4), and the elution of the MSPD column with 5 mL of hexane/acetone (1:1). After derivatization, the extract was analyzed without any further clean-up or concentration step. Accuracy, precision, linearity and detection limits were evaluated to assess the performance of the proposed method. The recovery studies on leave-on and rinse-off cosmetics gave satisfactory values (>78% for all analytes in all the samples) with an average relative standard deviation value of 4.2%. The quantification limits were well below those set by the international cosmetic regulations, making this multi-component analytical method suitable for routine control. The analysis of a broad range of cosmetics including body milk, moisturizing creams, anti-stretch marks creams, hand creams, deodorant, shampoos, liquid soaps, makeup, sun milk, hand soaps, among others, demonstrated the high use of most of the target preservatives, especially butylated hydroxytoluene, methylparaben, propylparaben, and butylparaben.

  7. Determination of isothiazolinone preservatives in cosmetics and household products by matrix solid-phase dispersion followed by high-performance liquid chromatography-tandem mass spectrometry.

    Alvarez-Rivera, Gerardo; Dagnac, Thierry; Lores, Marta; Garcia-Jares, Carmen; Sanchez-Prado, Lucia; Lamas, J Pablo; Llompart, Maria


    In this work, the development of a new efficient methodology applying, for the first time, matrix solid phase dispersion (MSPD) for the determination of sensitizer isothiazolinone biocides in cosmetics and household products - 2-methyl-3-isothiazolinone (MI), 5-chloro-2-methyl-3-isothiazolinone (CMI), 1,2-benzisothiazolinone (BzI) and 2-octyl-3-isothiazolinone (OI) - is described. The main factors affecting the MSPD extraction procedure, the dispersive phase and the elution solvent, are assessed and optimized through a multicategorical experimental design, using a real cosmetic sample. The most suitable extraction conditions comprise the use of 2g of florisil as dispersive phase and 5 mL of methanol as elution solvent. Subsequently, the extract is readily analyzed by HPLC-MS/MS without any further clean-up or concentration steps. Method performance was evaluated demonstrating to have a broad linear range (R(2)>0.9980) and limits of detection (LOD) and quantification (LOQ) at the low nanogram per gram level, which are well below the required limits for UE regulation compliance. Satisfactory recoveries above 80%, except for MI (mean values close to 60%), were obtained. In all cases, the method precision (% RSD) was lower than 7%, making this low cost extraction method reliable for routine control. The validated methodology was finally applied to the analysis of a wide variety of cosmetics and household products. Most of the real samples analyzed have been shown to comply with the current European Cosmetic Regulation, although the results obtained for some rinse-off cosmetics (e.g. baby care products) revealed high isothiazolinone content.

  8. Multivariate optimisation of an ultrasound assisted-matrix solid-phase dispersion method combined with LC-fluorescence detection for simultaneous extraction and determination of aflatoxins in pistachio nut samples.

    Manoochehri, Mahboobeh; Asgharinezhad, Ali Akbar; Safaei, Mahdi


    This paper describes the application of ultrasound-assisted matrix solid-phase dispersion as an extraction and clean-up procedure for aflatoxins (B1, B2, G1 and G2) and subsequent determination by LC-fluorescence detection. A Box-Behnken design was used to determine the parameters influencing the extraction procedure through response surface methodology and experimental design. The influence of different variables including type of dispersing phase, sample-to-dispersing phase ratio, type and quantity of clean-up phase, ultrasonication time, ultrasonication temperature, nature and volume of the elution solvent were investigated in the optimisation study. C18, graphitic carbon black and acetonitrile were selected as dispersing phase, clean-up phase and elution solvent, respectively. The optimised values were sample-to-dispersing phase ratio of 1:1, 50 mg of graphitic carbon black, 11 min ultrasonication time, 30°C ultrasonication temperature and 3 ml acetonitrile. Under the optimal conditions the limits of detection (LODs) were ranged from 0.04-0.11 µg kg(-1) and the relative standard deviations (RSDs) of the extraction method were less than 8.6%. The recoveries of the matrix solid-phase dispersion process ranged from 74% to 78% with relative standard deviation lower than 9% in all cases. Finally, the matrix solid-phase dispersion was successfully applied to extraction of trace amounts of aflatoxins in pistachio samples.

  9. Cumulate Fragments in Silicic Ignimbrites

    Bachmann, O.; Ellis, B. S.; Wolff, J.


    Increasingly, studies are concluding that silicic ignimbrites are the result of the amalgamation of multiple discrete magma batches. Yet the existence of discrete batches presents a conundrum for magma generation and storage; if silicic magma batches are not generated nearly in situ in the upper crust, they must traverse, and reside within, a thermally hostile environment with large temperature gradients, resulting in low survivability in their shallow magmatic hearths. The Snake River Plain (Idaho, USA) is a type example of this 'multi-batch' assembly with ignimbrites containing multiple populations of pyroxene crystals, glass shards, and crystal aggregates. The ubiquitous crystal aggregates hint at a mechanism to facilitate the existence of multiple, relatively small batches of rhyolite in the upper crust. These aggregates contain the same plagioclase, pyroxene, and oxide mineral compositions as single phenocrysts of the same minerals in their host rocks, but they have significantly less silicic bulk compositions and lack quartz and sanidine, which occur as single phenocrysts in the deposits. This implies significant crystallization followed by melt extraction from mushy reservoir margins. The extracted melt then continues to evolve (crystallizing sanidine and quartz) while the melt-depleted margins provide an increasingly rigid and refractory network segregating the crystal-poor batches of magma. The hot, refractory, margins insulate the crystal-poor lenses, allowing (1) extended residence in the upper crust, and (2) preservation of chemical heterogeneities among batches. In contrast, systems that produce cumulates richer in low-temperature phases (quartz, K-feldspars, and/or biotite) favour remelting upon recharge, leading to less segregation of eruptible melt pockets and the formation of gradationally zoned ignimbrites. The occurrence of similar crystal aggregates from a variety of magmatic lineages suggests the generality of this process.

  10. Nanostructure of Er3+ doped silicates.

    Yao, Nan; Hou, Kirk; Haines, Christopher D; Etessami, Nathan; Ranganathan, Varadh; Halpern, Susan B; Kear, Bernard H; Klein, Lisa C; Sigel, George H


    We demonstrate nanostructural evolution resulting in highly increased photoluminescence in silicates doped with Er3+ ions. High-resolution transmission electron microscopy (HRTEM) imaging, nano-energy dispersed X-ray (NEDX) spectroscopy, X-ray diffraction (XRD) and photoluminescence analysis confirm the local composition and structure changes of the Er3+ ions upon thermal annealing. We studied two types of amorphous nanopowder: the first is of the composition SiO2/18Al2O3/2Er2O3 (SAE), synthesized by combustion flame-chemical vapor condensation, and the second is with a composition of SiO2/8Y2O3/2Er2O3 (SYE), synthesized by sol-gel synthesis (composition in mol%). Electron diffraction and HRTEM imaging clearly show the formation of nanocrystallites with an average diameter of approximately 8 nm in SAE samples annealed at 1000 degrees C and SYE samples annealed at 1200 degrees C. The volume fraction of the nanocrystalline phase increased with each heat treatment, eventually leading to complete devitrification at 1400 degrees C. Further XRD and NEDX analysis indicates that the nanocrystalline phase has the pyrochlore structure with the formula Er(x)Al(2-x)Si2O7 or Er(x)Y(2-x)Si2O7 and a surrounding silica matrix.

  11. Utilization of industrial solid wastes able to generate calcium trisulphoaluminate and silicate hydrates in stabilization processes and for the manufacture of building materials; Utilizzazione di residui solidi industriali in grado di generare trisolfoalluminato e silicato di calcio idrati nei processi di stabilizzazione e nella produzione di materiali da costruzione

    Santoro, L. [Naples, Univ. `Federico II` (Italy). Dipt. di Chimica; Cioffi, R. [Naples, Univ. `Federico II` (Italy). Ditp. di Ingegneria dei Materiali e della Produzione


    In this work the stabilization of hazardous solid wastes containing heavy metals has been studied by means of novel matrices able to generate calcium trisulphoaluminate and silicate hydrates. The process is based on the hydration of two different mixtures containing blast furnace slag, coal ashes, chemical gypsum and Portland cement. The stabilization capacity of the two mixtures has been checked with regard to both a residue from an incinerator of municipal solid wastes and model systems obtained by adding 5 and 10% of soluble nitrates of Cd, Cr, Cu, Ni, Pb and Zn. The stabilized products have been validated from the point of view of mechanical properties by determining the unconfined compressive strength, and from the environmental point of view by means of static and dynamic leaching tests. Both matrices have proved to have great potentiality for the stabilization of hazardous solid wastes, the one based on blast furnace slag being better. Finally, evidence is given that different leaching tests are necessary to fully understand the immobilization mechanism responsible for stabilization. [Italiano] In questo lavoro e` stata studiata la atbilizzazione di residui tossici e nocivi contenenti metalli pesanti per mezzo di matrici leganti innovative capaci di generare trisolfoalluminato e silicato di calcio idrati. Il processo e` basato sull`idratazione di due diverse miscele contenenti scoria d`alto forno, ceneri di carbone, gessi chimici e cemento Portland. Le capacita` stabilizzanti delle due miscele sono state verificate sia nei confronti di un residuo solido generato a seguito dell`incenerimento di RSU, che nei confronti di sistemi modello ottenuti aggiungendo singolarmente il 5 e 10% dei nitrati solubili di Cd, Cr, Cu, Ni, Pb e Zn. I prodotti solidi stabilizzati sono stati validati dal punto di vista delle prestazioni meccaniche mediante prove di resistenza a compressione, e dal punto di vista ambientale mediante test di rilascio sia statici che dinamici

  12. Mechanistic study and modeling of radionuclides retention by the hydrated calcium silicates (HCS) of cements; Etude mecanistique et modelisation de la retention de radionucleides par les silicates de calcium hydrates (CSH) des ciments

    Pointeau, I


    This work attempts to investigate the modelling of radioisotopes (Cs{sup +}, Pb{sup 2+}, Eu{sup 3+}) immobilization in cement matrix, in the frame of the design of engineered barrier of a deep radwaste repository. The model development concept consists of three major steps: - surface chemistry modelling of the calcium silicate hydrate CSH, used to simulate hydrated cement behaviour; - solid analysis of the batch sorption experiments: identification of the uptake mechanism; - both previous steps are used, with isotherm data, in the modelling of the radioisotopes immobilization in the CSH matrix. Final results: (all modelling are available for all the range of studied Ca/Si ratios and have been validated with predictive calculations). - A thermodynamic modelling of the CSH surface chemistry has been developed. The labile calcium and proton sorption constants on silanol sites (>SiOH) have been extracted. - Cs{sup +} is sorbed on two sites. The silanol site (weak site) has a high site density (10 sites.nm{sup -2}), which accounts for the CSH unsaturation in high [CS{sup +}]. A strong site is also identified. - Pb{sup 2+} immobilization in CSH matrix is modelled with surface equilibria and solubility equilibrium. - Eu{sup 3+} fixation has been investigated with solid analysis: Site-Selective anti Time-Resolved Luminescence Spectroscopy, XPS and SEM-EDS. Eu{sup 3+} thus does not precipitate in CSH water but is sorbed on the CSH surface (high hydroxylated environment). Europium is also (minority site) inserted in the CSH framework. (author)

  13. Nanoscale zinc silicate from phytoliths

    Qadri, S. B.; Gorzkowski, E. P.; Rath, B. B.; Feng, C. R.; Amarasinghe, R.; Freitas, J. A.; Culbertson, J. C.; Wollmershauser, J. A.


    We report a faster, less expensive method of producing zinc silicate nanoparticles. Such particles are used in high volume to make phosphors and anti-corrosion coatings. The approach makes use of phytoliths (plant rocks), which are microscopic, amorphous, and largely silicate particles embedded in plants, that lend themselves to being easily broken down into nanoparticles. Nanoparticles of Zn2SiO4 were produced in a two stage process. In the refinement stage, plant residue, mixed with an appropriate amount of ZnO, was heated in an argon atmosphere to a temperature exceeding 1400 °C for four to six hours and then heated in air at 650 °C to remove excess carbon. TEM shows 50-100 nm nanoparticles. Raman scattering indicates that only the -Zn2SiO4 crystalline phase was present. X-ray analysis indicated pure rhombohedral R 3 bar phase results from using rice/wheat husks. Both samples luminesced predominantly at 523 nm when illuminated with X-rays or UV laser light.

  14. Silicate condensation in Mira variables

    Gail, Hans-Peter; Pucci, Annemarie


    We study whether the condensation of silicate dust in Mira envelopes could be caused by cluster formation by the abundant SiO molecules. For a simplified model of the pulsational motions of matter in the the outer layers of a Mira variable which is guided by a numerical model for Mira pulsations, the equations of dust nucleation and growth are solved in the co-moving frame of a fixed mass element. It is assumed that seed particles form by clustering of SiO molecules. The calculation of the nucleation rate is based on the experimental data of Nuth and Donn (1982). The quantity of dust formed is calculated by a moment method and the calculation of radiation pressure on the dusty gas is based on a dirty silicate model. Dust nucleation occurs in the model at the upper culmination of the trajectory of a gas parcel where it stays for a considerable time at low temperatures while subsequent dust growth occurs during the descending part of the motion and continues after the next shock reversed motion. It is found tha...

  15. Structure and dynamics of iron doped and undoped silicate glasses

    Santos, Cristiane N.; Meneses, Domingos D. S.; Echegut, Patrick; Lecomte, Emmanuel


    The optical properties of common silicate glass compositions are well known at room temperature. However, their radiative properties and structural evolution of these glasses with temperature are still largely unexplored. In this work we have measured the emissivity of a set of iron doped and undoped silicate and borosilicate glasses over an unprecedented temperature (up to 1700 K) and spectral range (40 -- 20000 cm-1). This was achieved by means of a home-made apparatus composed of a CO2 laser as the heat source, a black-body reference and two spectrometers. The optical functions were assessed using a dielectric function model [1], and the structure and dynamics of the glassy network, as well the absorption of iron species in different redox states were evidenced. We believe that these new data will help to understand the heat transfer in molten silicates. [4pt] [1] D. D. S. Meneses, G. Gruener, M. Malki, and P. Echegut, J. Non-Cryst. Solids 351, 124 (2005)

  16. Observation directe de la croissance d'hydrosilicate de calcium sur des surfaces d'alité et de silice par microscopie à force atomique

    Gauffinet, Sandrine; Finot, Éric; Lesniewska, Eric; Nonat, André


    Direct observation of the growth of calcium silicate hydrates, the tricalcium silicate hydration products, at the solid-solution interface were performed by atomic force microscopy. The covering of the surface of alite or silica by a three-dimensional oriented aggregation of nano particles of calcium silicate hydrate is always observed whatever the sample. All observations and quantifications made on calcium silicate growth at the submicronic level are in agreement with the data deduced from the study of the system evolution at the macroscopic level.

  17. Silicates materials of high vacuum technology

    Espe, Werner


    Materials of High Vacuum Technology, Volume 2: Silicates covers silicate insulators of special importance to vacuum technology. The book discusses the manufacture, composition, and physical and chemical properties of technical glasses, quartz glass, quartzware, vycor glass, ceramic materials, mica, and asbestos.

  18. Removal of lead from cathode ray tube funnel glass by generating the sodium silicate.

    Hu, Biao; Zhao, Shuangshuang; Zhang, Shuhao


    In the disposal of electronic waste, cathode ray tube (CRT) funnel glass is an environmental problem of old television sets. Removal of the lead from CRT funnel glass can prevent its release into the environment and allow its reuse. In this research, we reference the dry progress productive technology of sodium silicate, the waste CRT glass was dealt with sodium silicate frit melted and sodium silicate frit dissolved. Adding a certain amount of Na ₂CO₃to the waste CRT glass bases on the material composition and content of it, then the specific modulus of sodium silicate frit is obtained by melting progress. The silicon, potassium and sodium compounds of the sodium silicate frit are dissolved under the conditions of high temperature and pressure by using water as solvent, which shows the tendency that different temperature, pressure, liquid-solid ratio and dissolving time have effect on the result of dissolving. At 175°C(0.75MPa), liquid-solid ratio is 1.5:1, the dissolving time is 1h, the dissolution rate of sodium silicate frit is 44.725%. By using sodium sulfide to separate hydrolysis solution and to collect lead compounds in the solution, the recovery rate of lead in dissolving reached 100% and we can get clean sodium silicate and high purity of lead compounds. The method presented in this research can recycle not only the lead but also the sodium, potassium and other inorganic minerals in CRT glass and can obtain the comprehensive utilization of leaded glass.

  19. Mesoporous Silicate Materials in Sensing

    Paul T. Charles


    Full Text Available Mesoporous silicas, especially those exhibiting ordered pore systems and uniform pore diameters, have shown great potential for sensing applications in recent years. Morphological control grants them versatility in the method of deployment whether as bulk powders, monoliths, thin films, or embedded in coatings. High surface areas and pore sizes greater than 2 nm make them effective as adsorbent coatings for humidity sensors. The pore networks also provide the potential for immobilization of enzymes within the materials. Functionalization of materials by silane grafting or through cocondensation of silicate precursors can be used to provide mesoporous materials with a variety of fluorescent probes as well as surface properties that aid in selective detection of specific analytes. This review will illustrate how mesoporous silicas have been applied to sensing changes in relative humidity, changes in pH, metal cations, toxic industrial compounds, volatile organic compounds, small molecules and ions, nitroenergetic compounds, and biologically relevant molecules.

  20. Mechanical Properties and Durability of Advanced Environmental Barrier Coatings in Calcium-Magnesium-Alumino-Silicate Environments

    Miladinovich, Daniel S.; Zhu, Dongming


    Environmental barrier coatings are being developed and tested for use with SiC/SiC ceramic matrix composite (CMC) gas turbine engine components. Several oxide and silicate based compositons are being studied for use as top-coat and intermediate layers in a three or more layer environmental barrier coating system. Specifically, the room temperature Vickers-indentation-fracture-toughness testing and high-temperature stability reaction studies with Calcium Magnesium Alumino-Silicate (CMAS or "sand") are being conducted using advanced testing techniques such as high pressure burner rig tests as well as high heat flux laser tests.

  1. Matriz de indicadores de sustentabilidade para a gestão de resíduos sólidos urbanos Matrix of sustainability indicatorsfor the urban solid waste management

    Leila Santos Santiago


    Full Text Available O artigo apresenta uma matriz de indicadores de sustentabilidade para a gestão de resíduos sólidos urbanos e a forma de sua construção. A construção foi realizada baseando-se em informações adquiridas em referências nacionais e internacionais. Os indicadores foram organizados em uma matriz preliminar, a qual passou por um processo de validação externa, com especialistas, por meio do método Delphi. Para a realização deste método foram necessárias duas rodadas. A matriz final possui 6 dimensões de sustentabilidade: política, tecnológica, econômica/financeira, ambiental/ecológica, conhecimento e inclusão social, contemplando 42 indicadores e 126 descritores. A matriz elaborada poderá ser utilizada como instrumento de avaliação e planejamento da gestão dos resíduos sólidos em municípios.This paper presents a matrix of Sustainability Indicators for the Urban Solid Waste Management and the way of its construction. The construction was performed based on information acquired in national and international references. The indicators were organized into a primary matrix, which has gone an external validation process, with experts through the Delphi method. To perform this method two rounds were necessary. The final matrix has 6 dimensions of sustainability: politics, technology, economic/financial, environmental/ecological, knowledge and social inclusion, comprising 42 indicators, 126 descriptors. The matrix produced can be used as a tool for evaluation and planning of the solid waste management in municipalities.

  2. Composite nanoparticles: A new way to siliceous materials and a model of biosilica synthesis

    Annenkov, Vadim V., E-mail: [Limnological Institute, Siberian Branch of the Russian Academy of Sciences, Irkutsk 664033 (Russian Federation); Pal' shin, Viktor A.; Verkhozina, Olga N. [Limnological Institute, Siberian Branch of the Russian Academy of Sciences, Irkutsk 664033 (Russian Federation); Larina, Lyudmila I. [A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk 664033 (Russian Federation); Danilovtseva, Elena N. [Limnological Institute, Siberian Branch of the Russian Academy of Sciences, Irkutsk 664033 (Russian Federation)


    A new polyampholyte based on poly (acrylic acid) which bears pendant polyamine oligomeric chains (average number of the nitrogen atoms is 11.2) is obtained. This polymer is a model of silaffins – proteins playing important role in formation of siliceous structures in diatom algae and sponges. The polymer catalyses condensation of silicic acid. The obtained solutions contain oligosilicates coordinated with the polymer chains. The action of 50,000 g gravity on this solution results in concentrating-induced condensation of the pre-condensed siliceous oligomers. The obtained solid silica contains 4% admixture of the organic polymer which is close to the silica from diatom frustules. These results confirm the hypothesis about formation of biosilica under the action of desiccation agent, e.g. aquaporins. The formation of solid substances during centrifugation of solutions containing soluble oligomers is a new promising approach to inorganic and composite materials which allows to work in aqueous medium and to reuse the organic polymer. - Highlights: • A polyampholyte with pendant polyamine chains is obtained. • The polymer catalyses condensation of silicic acid giving stable solutions. • Gravity-induced (50,000 g) formation of solid silica was observed in these solutions. • The obtained silica is close to biosilica from diatom frustules. • A new approach to inorganic and composite materials is proposed.

  3. Preparation of calcium silicate absorbent from iron blast furnace slag.

    Brodnax, L F; Rochelle, G T


    Calcium silicate hydrate (CSH) solids were prepared from hydrated lime and iron blast furnace slag in an aqueous agitated slurry at 92 degrees C. While it was hoped a minimal lime/slag ratio could be used to create near-amorphous CSH, the surface area of the product improved by increasing the lime/slag weight ratio to 2. The addition of gypsum to the lime/slag system dramatically improved the formation of surface area, creating solids with 139 m2/g after 30 hr of reaction when only a minimal amount of lime was present. The SO2 reactivity of solids prepared with gypsum greatly exceeded that of hydrated lime, achieving greater than 70-80% conversion of the alkalinity after 1 hr of reaction with SO2. The use of CaCl2 as an additive to the lime/slag system, in lieu of gypsum, also produced high-surface-area solids, 115 m2/g after 21 hr of reaction. However, the SO2 reactivity of these sorbents was relatively low given the high surface area. This emphasized that the correlation between surface area and SO2 reactivity was highly dependent on the solid phase, which was subsequently dependent on slurry composition.

  4. Development of Biomedical Polymer-Silicate Nanocomposites: A Materials Science Perspective

    Wu, Chia-Jung; Gaharwar, Akhilesh K.; Schexnailder, Patrick J.; Schmidt, Gudrun


    Biomedical polymer-silicate nanocomposites have potential to become critically important to the development of biomedical applications, ranging from diagnostic and therapeutic devices, tissue regeneration and drug delivery matrixes to various bio-technologies that are inspired by biology but have only indirect biomedical relation. The fundamental understanding of polymer-nanoparticle interactions is absolutely necessary to control structure-property relationships of materials that need to work within the chemical, physical and biological constraints required by an application. This review summarizes the most recent published strategies to design and develop polymer-silicate nanocomposites (including clay based silicate nanoparticles and bioactive glass nanoparticles) for a variety of biomedical applications. Emerging trends in bio-technological and biomedical nanocomposites are highlighted and potential new fields of applications are examined.

  5. Development of Biomedical Polymer-Silicate Nanocomposites: A Materials Science Perspective

    Chia-Jung Wu


    Full Text Available Biomedical polymer-silicate nanocomposites have potential to become critically important to the development of biomedical applications, ranging from diagnostic and therapeutic devices, tissue regeneration and drug delivery matrixes to various bio-technologies that are inspired by biology but have only indirect biomedical relation. The fundamental understanding of polymer-nanoparticle interactions is absolutely necessary to control structure-property relationships of materials that need to work within the chemical, physical and biological constraints required by an application. This review summarizes the most recent published strategies to design and develop polymer-silicate nanocomposites (including clay based silicate nanoparticles and bioactive glass nanoparticles for a variety of biomedical applications. Emerging trends in bio-technological and biomedical nanocomposites are highlighted and potential new fields of applications are examined.

  6. Effect of moisture and chitosan layered silicate on morphology and properties of chitosan/layered silicates films; Efeito do teor de quitosana e do silicato em camadas na morfologia e propriedades dos filmes quitosana/silicatos em camadas

    Silva, J.R.M.B. da; Santos, B.F.F. dos; Leite, I.F., E-mail: [Universidade Federal da Paraiba (UFPB), PB (Brazil). Centro de Tecnologia. Departamento de Engenharia de Materiais


    Thin chitosan films have been for some time an object of practical assessments. However, to obtain biopolymers capable of competing with common polymers a significant improvement in their properties is required. Currently, the technology of obtaining polymer/layered silicates nanocomposites has proven to be a good alternative. This work aims to evaluate the effect of chitosan content (CS) and layered silicates (AN) on the morphology and properties of chitosan/ layered silicate films. CS/AN bionanocomposites were prepared by the intercalation by solution in the proportion 1:1 and 5:1. Then were characterized by infrared spectroscopy (FTIR), diffraction (XRD) and X-ray thermogravimetry (TG). It is expected from the acquisition of films, based on different levels of chitosan and layered silicates, choose the best composition to serve as a matrix for packaging drugs and thus be used for future research. (author)

  7. Carbon Monoxide Silicate Reduction System Project

    National Aeronautics and Space Administration — The Carbon Monoxide Silicate Reduction System (COSRS) is a novel technology for producing large quantities of oxygen on the Moon. Oxygen yields of 15 kilograms per...

  8. Carbon Monoxide Silicate Reduction System Project

    National Aeronautics and Space Administration — The Carbon Monoxide Silicate Reduction System (COSRS) is an innovative method that for the first time uses the strong reductant carbon monoxide to both reduce iron...

  9. Intrinsic luminescence of alkali silicate glasses

    Arbuzov, V.I.; Grabovskis, V.Y.; Tolstoi, M.N.; Vitol, I.K.


    This study obtains additional information on L centers and their role in electron excitation and intrinsic luminescence of a whole series. (Li, Na, K, Rb, and Cs) of alkali silicate glasses. The authors compare the features of the interaction with radiation of specimens of glass and crystal of a similar chemical composition, since silicates of alkali metals can be obtained in both the glassy and crystalline states.

  10. The paleomagnetism of single silicate crystals: Recording geomagnetic field strength during mixed polarity intervals, superchrons, and inner core growth

    Tarduno, J. A.; Cottrell, R. D.; Smirnov, A. V.


    The basic features of the geomagnetic reversal chronology of the last 160 million years are well established. The relationship between this history and other features of the field, however, has been elusive. The determination of past field strength (paleointensity) is especially challenging. Commonly accepted results have come from analyses of bulk samples of lava. Historic lavas have been shown to faithfully record the past field strength when analyzed using the Thellier double-heating method. Data from older lavas, however, tend to show effects of in situ and laboratory-induced alteration. Here we review an alternative approach. Single plagioclase crystals can contain minute magnetic inclusions, 50-350 nm in size, that are potential high-fidelity field recorders. Thellier experiments using plagioclase feldspars from an historic lava on Hawaii provide a benchmark for the method. Rock magnetic data from older lavas indicate that the feldspars are less susceptible to experimental alteration than bulk samples. This resistance is likely related to the lack of clays. In addition, magnetic minerals are sheltered by the encasing silicate matrix from natural alteration that can otherwise transform the well-defined thermoremanent magnetization into an irresolute chemical remanent magnetization. If there is a relationship between geomagnetic reversal frequency and paleointensity, it should be best expressed during superchrons, intervals with few (or no) reversals. Thellier data sets based on single plagioclase crystals from lavas erupted during the Cretaceous Normal Polarity Superchron (~83-120 million years ago) suggest a strong (>12 × 1022 Am2), stable field, consistent with an inverse relationship between reversal frequency and paleointensity. Superchrons may represent times when the pattern of core-mantle boundary heat flux allows the geodynamo to operate at peak efficiency, as suggested in some numerical models. Thellier data from single plagioclase crystals formed

  11. Nano porous alkaline earth metal silicates as free fatty acid adsorbents from Crude Palm Oil (CPO)

    Masmur, Indra; Sembiring, Seri Bima; Bangun, Nimpan; Kaban, Jamaran; Putri, Nabila Karina


    Free fatty acids(FFA) from Crude Palm Oil (CPO) have been adsorbed by alkaline earth metal silicate (M-silicate : M = Mg, Ca, Sr and Ba) adsorbents in ethanol using batch method. The adsorbents were prepared from the chloride salts of alkaline metals and Na2SiO3. The resulting white solid of the alkaline earth metal silicates were then heated at 800°C for 3 hours to enlarge their porosities. All adsorbents were characterized by SEM-EDX, XRD and BET. The EDX spectrum of SEM-EDX showed the appearance of all elements in the adsorbents, and the XRD spectrum of all adsorbents showed that they have crystobalite structure. The porosity of the adsorbents calculated by BET method showed that the porosities of the adsorbents range from 2.0884 - 2.0969 nm. All the adsorbents were used to adsorb the FFA from CPO containing 4.79%, 7.3%, 10.37% and 13.34% of FFA. The ratio of adsorbent to CPO to be used in adsorption of FFA from CPO were made 1:1, 1:2 and 1:3, with adsorption time of 1 hour. We found that the maximum adsorption of FFA from CPO was given by Ca-Silicate adsorbent which was between 69.86 - 94.78%, while the lowest adsorption was shown by Mg-silicate adsorbent which was 49.32 -74.53%.

  12. First preparation of nanocrystalline zinc silicate by chemical vapor synthesis using an organometallic single-source precursor.

    Roy, A; Polarz, S; Rabe, S; Rellinghaus, B; Zähres, H; Kruis, F E; Driess, Matthias


    A method is presented to prepare nanocrystalline alpha-Zn(2)SiO(4) with the smallest crystal size reported so far for this system. Our approach combines the advantages of organometallic single-source precursor routes with aerosol processing techniques. The chemical design of the precursor enables the preferential formation of pure zinc silicates. Since gas-phase synthesis reduces intermolecular processes, and keeps the particles small, zinc silicate was synthesized from the volatile organometallic precursor [[MeZnOSiMe(3)](4)], possessing a Zn-methyl- and O-silyl-substituted Zn(4)O(4)-heterocubane framework (cubane), under oxidizing conditions, using the chemical vapor synthesis (CVS) method. The products obtained under different process conditions and their structural evolution after sintering were investigated by using various analytical techniques (powder X-ray diffraction, transmission electron microscopy, EDX analysis, solid-state NMR, IR, Raman, and UV/Vis spectroscopy). The deposited aerosol obtained first (processing temperature 750 degrees C) was amorphous, and contained agglomerates with primary particles of 12 nm in size. These primary particles can be described by a [Zn-O-Si] phase without long-range order. The deposit obtained at 900 degrees C contained particles with embedded nanocrystallites (3-5 nm) of beta-Zn(2)SiO(4), Zn(1.7)SiO(4), and ZnO in an amorphous matrix. On further ageing, the as-deposited particles obtained at 900 degrees C form alpha-Zn(2)SiO(4) imbedded in amorphous SiO(2). The crystallite sizes and primary particle sizes in the formed alpha-Zn(2)SiO(4) were found to be below approximately 50 nm and mainly spherical in morphology. A gas-phase mechanism for the particle formation is proposed. In addition, the solid-state reactions of the same precursor were studied in detail to investigate the fundamental differences between a gas-phase and a solid-state synthesis route.

  13. Zirconium silicate assisted removal of residual proteins after organic solvent deproteinization of human plasma, enhancing the stability of the LC–ESI-MS response for the bioanalysis of small molecules

    Hussain, Shah; Pezzei, Cornelia [Institute of Analytical Chemistry and Radiochemistry, CCB-Center for Chemistry and Biomedicine, Leopold-Franzens University, Innrain 80/82, 6020 Innsbruck (Austria); Güzel, Yüksel [Institute of Analytical Chemistry and Radiochemistry, CCB-Center for Chemistry and Biomedicine, Leopold-Franzens University, Innrain 80/82, 6020 Innsbruck (Austria); ADSI-Austrian Drug Screening Institute, Innrain 66a, 6020 Innsbruck (Austria); Rainer, Matthias [Institute of Analytical Chemistry and Radiochemistry, CCB-Center for Chemistry and Biomedicine, Leopold-Franzens University, Innrain 80/82, 6020 Innsbruck (Austria); Huck, Christian W., E-mail: [Institute of Analytical Chemistry and Radiochemistry, CCB-Center for Chemistry and Biomedicine, Leopold-Franzens University, Innrain 80/82, 6020 Innsbruck (Austria); Bonn, Günther K. [Institute of Analytical Chemistry and Radiochemistry, CCB-Center for Chemistry and Biomedicine, Leopold-Franzens University, Innrain 80/82, 6020 Innsbruck (Austria); ADSI-Austrian Drug Screening Institute, Innrain 66a, 6020 Innsbruck (Austria)


    Highlights: • A novel sample preparation technique for isolation of small molecules from human plasma. • Effectiveness of zirconium silicate for the removal of residual proteins after protein precipitation. • Abolishing the consumption of salts for the depletion of residual proteins after protein precipitation. • More than 99.6% removal of plasma proteins. - Abstract: An efficient blood plasma clean-up method was developed, where methanol protein precipitation was applied, followed by zirconium silicate assisted exclusion of residual proteins. A strong binding of zirconium (IV) silicate to the proteins enabled the elimination of remaining proteins after solvent deproteinization through a rapid solid-phase extraction (SPE) procedure. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI/TOF MS) was used for monitoring the proteins during clean-up practice applied to human plasma samples. The proteins were quantified by colorimetric detection using the bicinchoninic acid (BCA) assay. The presented analytical strategy resulted in the depletion of >99.6% proteins from human plasma samples. Furthermore, high-performance liquid chromatography hyphenated to diode-array and electrospray ionization mass spectrometric detection (HPLC–DAD/ESI MS) was applied for qualitative and quantitative analysis of the caffeoylquinic acids (CQAs) and their metabolites in human plasma. The procedure demonstrated high recoveries for the standard compounds spiked at different concentrations. Cynarin and chlorogenic acid were recovered in the range of 81–86% and 78–83%, respectively. Caffeic acid was extracted in the excess of 89–92%, while ferulic acid and dihydroxyhydrocinnamic acid showed a recovery of 87–91% and 92–95%, respectively. The method was partially validated in accordance with FDA-Industry Guidelines for Bioanalytical Method Validation (2001). The presented scheme improves the clean-up efficacy of the methanol deproteinization

  14. Multispin correlations and pseudo-thermalization of the transient density matrix in solid-state NMR: free induction decay and magic echo

    Morgan, Steven W.; Oganesyan, Vadim; Boutis, Gregory S.


    Quantum unitary evolution typically leads to thermalization of generic interacting many-body systems. There are very few known general methods for reversing this process, and we focus on the magic echo, a radio-frequency pulse sequence known to approximately “rewind” the time evolution of dipolar coupled homonuclear spin systems in a large magnetic field. By combining analytic, numerical, and experimental results we systematically investigate factors leading to the degradation of magic echoes, as observed in reduced revival of mean transverse magnetization. Going beyond the conventional analysis based on mean magnetization we use a phase encoding technique to measure the growth of spin correlations in the density matrix at different points in time following magic echoes of varied durations and compare the results to those obtained during a free induction decay (FID). While considerable differences are documented at short times, the long-time behavior of the density matrix appears to be remarkably universal among the types of initial states considered – simple low order multispin correlations are observed to decay exponentially at the same rate, seeding the onset of increasingly complex high order correlations. This manifestly athermal process is constrained by conservation of the second moment of the spectrum of the density matrix and proceeds indefinitely, assuming unitary dynamics. PMID:23710125

  15. IR spectrum of CH3CN-BF3 in solid neon: matrix effects on the structure of a Lewis acid-base complex.

    Eigner, Audrey A; Rohde, John A; Knutson, Christopher C; Phillips, James A


    We have observed several IR bands of CH3CN-BF3 in neon and nitrogen matrices. For the 11B isotopomer in neon matrices, we observed the BF3 symmetric deformation band (nu7) as a doublet at 600 and 603 cm(-1), the BF3 symmetric stretching band (nu6) as a doublet at 833 and 838 cm(-1), the BF3 asymmetric stretching mode (nu13) at 1281 cm(-1) (partially obscured), and the C-N stretching mode (nu2) as a doublet at 2352 and 2356 cm(-1). The nitrogen matrix data are largely consistent with those reported recently, though we do propose a refinement of one band assignment. Comparisons of the frequencies of a few key, structurally sensitive vibrational modes either observed in various condensed-phase environments or calculated for two minimum-energy gas-phase structures indicate that inert matrix media significantly alter the structural properties of CH3CN-BF3. Specifically, the B-N dative bond compresses relative to the gas phase and other concomitant changes occur as well. Furthermore, the frequency shifts depict structural changes that occur across the various matrix hosts in a manner that largely parallels the degree of stabilization offered by these inert media.

  16. Influence of silicate anions structure on desilication in silicate-bearing sodium aluminate solution

    刘桂华; 张闻; 齐天贵; 彭志宏; 周秋生; 李小斌


    The structural changes of silicate anions in the desilication process with the addition of calcium hydrate alumino-carbonate were studied by measuring Raman spectra, infrared spectra and corresponding second derivative spectra. The results show that the desilication ratio in the solution prepared by the addition of sodium silicate (solution-SS) is much greater than that in the solution by the addition of green liquor (solution-GL), and low alumina concentration in the sodium aluminate solutions facilitates the desilication process. It is also shown that alumino-silicate anions in the solution-GL, and Q3 polymeric silicate anions in solution-SS are predominant, respectively. In addition, increasing the concentration of silica favors respectively the formation of the alumino-silicate or the Q3 silicate anions in the solution-GL or the solution-SS. Therefore, it can be inferred that the low desilication ratio in the silicate-bearing aluminate solution is mainly attributed to the existence of alumino-silicate anions.

  17. Characterization of set Intermediate Restorative Material, Biodentine, Bioaggregate and a prototype calcium silicate cement for use as root-end filling materials.

    Grech, L; Mallia, B; Camilleri, J


    To investigate the composition of materials and leachate of a hydrated prototype cement composed of tricalcium silicate and radiopacifier and compare this to other tricalcium silicate-based cements (Biodentine and Bioaggregate) to assess whether the additives in the proprietary brand cements affect the hydration of the materials, using Intermediate Restorative Material (IRM), a standard root-end filling material as a control. The materials investigated included a prototype-radiopacified tricalcium silicate cement, Biodentine, Bioaggregate and Intermediate Restorative Material (IRM). The pH and calcium ion concentration of the leachate were investigated. The hydrated cements were characterized using scanning electron microscopy (SEM) and X-ray energy dispersive analysis (EDX), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). All the cements tested were alkaline. The tricalcium silicate-based cements leached calcium in solution. Scanning electron microscopy of the prototype-radiopacified tricalcium silicate cement, Biodentine and Bioaggregate displayed hydrating cement grains, surrounded by a matrix composed of calcium silicate hydrate and calcium hydroxide. The presence of calcium hydroxide was evident from the XRD plots. FT-IR indicated the occurrence of a poorly crystalline calcium silicate hydrate. Biodentine displayed the presence of calcium carbonate. Bioaggregate incorporated a phosphate-containing phase. IRM consisted of zinc oxide interspersed in an organic matrix. The hydration of prototype-radiopacified tricalcium silicate cement, Biodentine and Bioaggregate resulted in the formation of calcium silicate hydrate and calcium hydroxide, which was leached in solution. The hydrated materials were composed of a cementitous phase that was rich in calcium and silicon and a radiopacifying material. Biodentine included calcium carbonate, and Bioaggregate included silica and calcium phosphate in the powders. IRM was composed of zinc oxide

  18. Methodical evaluation and improvement of matrix compatible PDMS-overcoated coating for direct immersion solid phase microextraction gas chromatography (DI-SPME-GC)-based applications.

    Souza-Silva, Érica A; Gionfriddo, Emanuela; Shirey, Robert; Sidisky, Len; Pawliszyn, Janusz


    The main quest for the implementation of direct SPME to complex matrices has been the development of matrix compatible coatings that provide sufficient sensitivity towards the target analytes. In this context, we present here a thorough evaluation of PDMS-overcoated fibers suitable for simultaneous extraction of different polarities analytes, while maintaining adequate matrix compatibility. For this, eleven analytes were selected, from various application classes (pesticides, industrial chemicals and pharmaceuticals) and with a wide range of log P values (ranging from 1.43 to 6). The model matrix chosen was commercial Concord grape juice, which is rich in pigments such as anthocyanins, and contains approximately 20% of sugar (w/w). Two types of PDMS, as well as other intrinsic factors associated with the PDMS-overcoated fiber fabrication are studied. The evaluation showed that the PDMS-overcoated fibers considerably slowed down the coating fouling process during direct immersion in complex matrices of high sugar content. Longevity differences could be seen between the two types of PDMS tested, with a proprietary Sylgard(®) giving superior performance because of lesser amount of reactive groups and enhanced hydrophobicity. Conversely, the thickness of the outer layer did not seem to have a significant effect on the fiber lifetime. We also demonstrate that the uniformity of the overcoated PDMS layer is paramount to the achievement of reliable data and extended fiber lifetime. Employing the optimum overcoated fiber, limits of detection (LOD) in the range of 0.2-1.3 ng/g could be achieved. Additional improvement is attainable by introducing washing of the coatings after desorption, so that any carbon build-up (fouling) left on the coating surface after thermal desorption can be removed.

  19. Radiation damage induced by gamma irradiation on Ce sup 3 sup + doped phosphate and silicate scintillating glasses

    Baccaro, S; Mihoková, E; Nikl, M; Nitsch, K; Polato, P; Zanella, G; Zannoni, R


    The effect of gamma irradiation on the optical properties of Ce sup 3 sup + -doped phosphate and silicate glasses is studied in the 1-250 Gy dose range. Results are discussed by taking into account the possible dependence of radiation-induced effects on the composition of the glass matrix.

  20. Matrix theory

    Franklin, Joel N


    Mathematically rigorous introduction covers vector and matrix norms, the condition-number of a matrix, positive and irreducible matrices, much more. Only elementary algebra and calculus required. Includes problem-solving exercises. 1968 edition.

  1. Alginate-magnesium aluminum silicate composite films: effect of film thickness on physical characteristics and permeability.

    Pongjanyakul, Thaned; Puttipipatkhachorn, Satit


    The different film thicknesses of the sodium alginate-magnesium aluminum silicate (SA-MAS) microcomposite films were prepared by varying volumes of the composite dispersion for casting. Effect of film thickness on thermal behavior, solid-state crystallinity, mechanical properties, water uptake and erosion, and water vapor and drug permeability of the microcomposite films were investigated. The film thickness caused a small change in thermal behavior of the films when tested using DSC and TGA. The crystallinity of the thin films seemed to increase when compared with the thick films. The thin films gave higher tensile strength than the thick films, whereas % elongation of the films was on the contrary resulted in the lower Young's modulus of the films when the film thickness was increased. This was due to the weaker of the film bulk, suggesting that the microscopic matrix structure of the thick films was looser than that of the thin films. Consequently, water uptake and erosion, water vapor permeation and drug diffusion coefficient of the thick films were higher than those of the thin films. The different types of drug on permeability of the films also showed that a positive charge and large molecule of drug, propranolol HCl, had higher lag time and lower diffusion coefficient that acetaminophen, a non-electrolyte and small molecule. This was because of a higher affinity of positive charge drug on MAS in the films. The findings suggest that the evaporation rate of solvent in different volumes of the composite dispersion used in the preparation method could affect crystallinity and strength of the film surface and film bulk of the microcomposite films. This led to a change in water vapor and drug permeability of the films.

  2. Can matrix solid phase dispersion (MSPD) be more simplified? Application of solventless MSPD sample preparation method for GC-MS and GC-FID analysis of plant essential oil components.

    Wianowska, Dorota; Dawidowicz, Andrzej L


    This paper proposes and shows the analytical capabilities of a new variant of matrix solid phase dispersion (MSPD) with the solventless blending step in the chromatographic analysis of plant volatiles. The obtained results prove that the use of a solvent is redundant as the sorption ability of the octadecyl brush is sufficient for quantitative retention of volatiles from 9 plants differing in their essential oil composition. The extraction efficiency of the proposed simplified MSPD method is equivalent to the efficiency of the commonly applied variant of MSPD with the organic dispersing liquid and pressurized liquid extraction, which is a much more complex, technically advanced and highly efficient technique of plant extraction. The equivalency of these methods is confirmed by the variance analysis. The proposed solventless MSPD method is precise, accurate, and reproducible. The recovery of essential oil components estimated by the MSPD method exceeds 98%, which is satisfactory for analytical purposes.

  3. Matrix-assisted laser desorption/ionization mass spectrometric analysis of poly(3,4-ethylenedioxythiophene) in solid-state dye-sensitized solar cells: comparison of in situ photoelectrochemical polymerization in aqueous micellar and organic media.

    Zhang, Jinbao; Ellis, Hanna; Yang, Lei; Johansson, Erik M J; Boschloo, Gerrit; Vlachopoulos, Nick; Hagfeldt, Anders; Bergquist, Jonas; Shevchenko, Denys


    Solid-state dye-sensitized solar cells (sDSCs) are devoid of such issues as electrolyte evaporation or leakage and electrode corrosion, which are typical for traditional liquid electrolyte-based DSCs. Poly(3,4-ethylenedioxythiophene) (PEDOT) is one of the most popular and efficient p-type conducting polymers that are used in sDSCs as a solid-state hole-transporting material. The most convenient way to deposit this insoluble polymer into the dye-sensitized mesoporous working electrode is in situ photoelectrochemical polymerization. Apparently, the structure and the physicochemical properties of the generated conducting polymer, which determine the photovoltaic performance of the corresponding solar cell, can be significantly affected by the preparation conditions. Therefore, a simple and fast analytical method that can reveal information on polymer chain length, possible chemical modifications, and impurities is strongly required for the rapid development of efficient solar energy-converting devices. In this contribution, we applied matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) for the analysis of PEDOT directly on sDSCs. It was found that the PEDOT generated in aqueous micellar medium possesses relatively shorter polymeric chains than the PEDOT deposited from an organic medium. Furthermore, the micellar electrolyte promotes a transformation of one of the thiophene terminal units to thiophenone. The introduction of a carbonyl group into the PEDOT molecule impedes the growth of the polymer chain and reduces the conductivity of the final polymer film. Both the simplicity of sample preparation (only application of the organic matrix onto the solar cell is needed) and the rapidity of analysis hold the promise of making MALDI MS an essential tool for the physicochemical characterization of conducting polymer-based sDSCs.

  4. The stability of non-ionic surfactants and linear alkylbenzene sulfonates in a water matrix and on solid-phase extraction cartridges.

    Petrović, M; Barceló, D


    The stability of nonylphenol ethoxylates (NPEO), alcohol ethoxylates (AEO), coconut diethanol amides (CDEA) and linear alkylbenzene sulfonates (LAS) in a water matrix and preconcentrated on SPE cartridges was studied. A stability study was carried out in a water matrix (spiked ground water and real-world waste water) comparing different pretreatment procedures (addition of sulfuric acid to pH = 3, preservation with 1% and 3% of formaldehyde). When stored in a water matrix serious qualitative and quantitative changes occurred in waste water during the period of time studied (30 days). The losses of C12-C14 alcohol ethoxylates ranged from 72% to 88% when the sample was preserved with acid and from 17% to 86% when the sample was preserved with formaldehyde (3%). Simultaneously, an enrichment of the shorter alkyl chain homologues (C7EO and C10EO) was observed. The losses of NPEO were from 45% (sample preserved by acidification or by addition of 3% of formaldehyde) to 85% (sample preserved with 1% of formaldehyde). Additionally, an increase in concentration of polyethylene glycols (PEGs) and formation of different acidic forms, such as monocarboxylated (MCPEGs) and dicarboxylated polyethylene glycols (DCPEGs) were observed. The stability of surfactants preconcentrated on SPE cartridges was studied as a function of storage time and storage conditions (room temperature, 4 degrees C and -20 degrees C). The results indicate that disposable SPE cartridges can be recommended for the stabilization of non-ionic surfactants and LAS. Storage at -20 degrees C is feasible for long periods (up to 3 months for ground water and up to 2 months for waste water), while storage at 4 C can be recommended for a maximum of 1 month. When cartridges were kept at -20 degrees C the losses of AEOs (n = 12, 13 and 14), preconcentrated from waste water, ranged from 17 to 29% (after 60 days) and other compounds suffered small losses (maximum of 14% for C13LAS). At room temperature, after 7 days, the

  5. Multiresidue LC-MS/MS analysis of cephalosporins and quinolones in milk following ultrasound-assisted matrix solid-phase dispersive extraction combined with the quick, easy, cheap, effective, rugged, and safe methodology.

    Karageorgou, Eftichia; Myridakis, Antonis; Stephanou, Euripides G; Samanidou, Victoria


    A sensitive and selective confirmatory method for milk-residue analysis of ten quinolones and eight cephalosporins by LC-MS/MS has been developed herein. For the chromatographic separation of target analytes, a Perfectsil ODS-2 (250 × 4 mm, 5 μm) analytical column was used and gradient elution was applied, using a mobile phase of 0.1% w/w TFA in water and 0.1% w/w TFA in ACN. Ultrasound-assisted matrix solid-phase dispersion procedure was applied for the extraction and clean-up procedure of antimicrobials agents from milk matrix using a mixture of Bond Elut Plexa sorbent and QuEChERS. The method was validated meeting the European Legislation determining selectivity, linearity response, trueness, precision (repeatability and between-day reproducibility), decision limit, detection capability, and ruggedness following the Youden approach. Recoveries of all antibiotics ranged from 81.7 to 117.9%, while RSD values were lower than 13.7%. Limits of quantification for all examined compounds ranged from 2.4 to 15.0 μg/kg, substantially lower than the maximum residue limits established by the European Union (30-100 μg/kg).

  6. Determination of polybrominated diphenyl ethers in fish tissues by matrix solid-phase dispersion and gas chromatography coupled to triple quadrupole mass spectrometry: case study on European eel (Anguilla anguilla) from Mediterranean coastal lagoons.

    Labadie, Pierre; Alliot, Fabrice; Bourges, Catherine; Desportes, Annie; Chevreuil, Marc


    This paper describes the development and validation of an analytical methodology to determine 28 polybrominated diphenyl ethers (PBDEs) in European eel (Anguilla anguilla) tissues using matrix solid-phase dispersion (MSPD) and gas chromatography coupled to triple quadrupole mass spectrometry (GC-QQQ-MS/MS). A total of 28 PBDEs were targeted, including tri- to deca-brominated congeners. The robustness and effectiveness of the proposed sample preparation procedure was demonstrated in lipid-rich eel tissues. The use of batch MSPD with activated silica gel and H(2)SO(4)-impregnated silica gel, followed by H(2)SO(4) digestion and multilayer cartridge clean-up allowed for complete lipid removal and eliminated matrix effects during GC-QQQ-MS/MS analysis. The average PBDE recoveries from eel muscle samples spiked with PBDEs at two levels were in the range 56.2-119.0%. Precision was satisfactory since relative standard deviations were lower than 19.6%, regardless of spike level, and method quantification limits ranged between 1 and 170 pg g(-1) (wet weight). The method demonstrated its successful application for the analysis of eel samples from two coastal lagoons located on the western French Mediterranean coast. All samples tested positive, but for tri- to hexa-brominated congeners only and total PBDE levels observed in this study were in the range 0.08-1.80 ng g(-1) wet weight.

  7. A combination of solid-phase extraction and dispersive solid-phase extraction effectively reduces the matrix interference in liquid chromatography-ultraviolet detection during pyraclostrobin analysis in perilla leaves.

    Farha, Waziha; Rahman, Md Musfiqur; Abd El-Aty, A M; Jung, Da-I; Kabir, Md Humayun; Choi, Jeong-Heui; Kim, Sung-Woo; Im, So Jeong; Lee, Young-Jun; Shin, Ho-Chul; Kwon, Chan-Hyeok; Son, Young-Wook; Lee, Kang-Bong; Shim, Jae-Han


    Perilla leaves contain many interfering substances; thus, it is difficult to protect the analytes during identification and integration. Furthermore, increasing the amount of sample to lower the detection limit worsens the situation. To overcome this problem, we established a new method using a combination of solid-phase extraction and dispersive solid-phase extraction to analyze pyraclostrobin in perilla leaves by liquid chromatography with ultraviolet absorbance detection. The target compound was quantitated by external calibration with a good determination coefficient (R(2) = 0.997). The method was validated (in triplicate) with three fortification levels, and 79.06- 89.10% of the target compound was recovered with a relative standard deviation <4. The limits of detection and quantification were 0.0033 and 0.01 mg/kg, respectively. The method was successfully applied to field samples collected from two different areas at Gwangju and Muan. The decline in the resiudue concentrations was best ascribed to a first-order kinetic model with half-lives of 5.7 and 4.6 days. The variation between the patterns was attributed to humidity.

  8. Novel molecularly imprinted polymers with carbon nanotube as matrix for selective solid-phase extraction of emodin from kiwi fruit root.

    Yang, Xiao; Zhang, Zhaohui; Li, Jiaxing; Chen, Xing; Zhang, Minlei; Luo, Lijuan; Yao, Shouzhuo


    In this paper, we present a novel surface imprinting technique for the preparation of molecularly imprinted polymers/multi-walled carbon nanotubes (MIPs/MWNTs) for extraction of emodin from kiwi fruit root. The MIPs/MWNTs were characterised by scanning electron microscopy (SEM) and Fourier transform-infrared spectroscopy (FT-IR). The properties involving adsorption dynamics, static adsorption, and selective recognition capacity were evaluated. The MIPs/MWNTs exhibited good site accessibility in which it only took 60 min to achieve adsorption equilibrium and highly selective recognition for the template emodin. Furthermore, the performance of the MIPs/MWNTs as solid phase extraction (SPE) material was investigated in detail. The proposed MIPs/MWNTs-SPE procedure for emodin exhibited satisfactory recoveries ranging from 89.2% to 93.8% for real samples. It was used for the purification and enrichment of emodin from kiwi fruit root successfully.

  9. Simplified miniaturized ultrasound-assisted matrix solid phase dispersion extraction and high performance liquid chromatographic determination of seven flavonoids in citrus fruit juice and human fluid samples: hesperetin and naringenin as biomarkers.

    Barfi, Behruz; Asghari, Alireza; Rajabi, Maryam; Barfi, Azadeh; Saeidi, Iman


    In the present study, for the first time, a simplified miniaturized ultrasound-assisted matrix solid-phase dispersion (SM-USA-MSPD) method with a different application for liquid matrices was developed to extract different flavonoids (hesperidin, diosmin, eriocitrin, narirutin, naringin, hesperetin and naringenin) from citrus fruit juice and human fluid samples prior to their determination using high performance liquid chromatography (HPLC). Different effective parameters were studied and under the optimum conditions (including sample volume: 150μL; solid phase: silica-based C18, 200mg; eluting solvent: methanol, 500μL; pH: 4; and sonication: 6min; at room temperature), limits of detection and limits of quantification were ranged from 23.3 to 46.8ngmL(-1) and 74.8 to 141.5ngmL(-1), respectively. Once optimized, analytical performance of the method was studied in terms of linearity (0.074-198.5μgmL(-1), r(2)>0.991), accuracy (recovery=84.6-101.5%), and precision (repeatability: intra-day precisionjuices- and the obtained results confirmed that these compounds could be used as good biomarkers of citrus fruit juice intake.

  10. Microcrystalline cellulose based matrix solid phase dispersion microextration for isomeric triterpenoid acids in loquat leaves by ultrahigh-performance liquid chromatography and quadrupole time-of-flight mass spectrometry.

    Cao, Jun; Peng, Li-Qing; Xu, Jing-Jing


    An analytical procedure based on matrix solid phase dispersion (MSPD) microextration and ultrahigh-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry was developed for the determination of isomeric triterpenoid acids (maslinic acid, corosolic acid, oleanolic acid and ursolic acid) in loquat leaves. Microcrystalline cellulose was used for the first time as a solid sorbent in MSPD microextration. Compared with the traditional extraction methods, the proposed method possessed the advantages of shorter extraction time, and lower consumption of sample, sorbent and organic solvent. The MSPD parameters that influenced the extraction efficiency of isomeric analytes were investigated and optimized in detail. Under the optimized conditions, good linearity was obtained with correlation coefficients higher than 0.9990. The limits of detection and quantification were 19.6-51.6μg/kg and 65.3-171.8μg/kg, respectively. Meanwhile, the recoveries obtained for all the analytes were ranging from 90.1% to 107.5%. Finally, the optimized method was successfully applied for analyzing these isomeric acids in loquat leaves samples obtained from different cultivated areas.

  11. Rheocasting Al Matrix Composites

    Girot, F. A.; Albingre, L.; Quenisset, J. M.; Naslain, R.


    Aluminum alloy matrix composites reinforced by SiC short fibers (or whiskers) can be prepared by rheocasting, a process which consists of the incorporation and homogeneous distribution of the reinforcement by stirring within a semi-solid alloy. Using this technique, composites containing fiber volume fractions in the range of 8-15%, have been obtained for various fibers lengths (i.e., 1 mm, 3 mm and 6 mm for SiC fibers). This paper attempts to delineate the best compocasting conditions for aluminum matrix composites reinforced by short SiC (e.g Nicalon) or SiC whiskers (e.g., Tokamax) and characterize the resulting microstructures.

  12. Novel Transparent Phosphor Conversion Matrix with High Thermal Conductivity for Next Generation Phosphor-Converted LED-based Solid State Lighting

    Bockstaller, Michael [Carnegie Mellon Univ., Pittsburgh, PA (United States)


    The low thermal conductivity of state-of-the-art polymer encapsulants (k ~ 0.15 Wm-1K-1) limits the efficiency and power density of current phosphor conversion light emitting diodes (pc-LEDs). The technical objective of this project was to demonstrate synthesis and processing schemes for the fabrication of polymer hybrid encapsulants with a thermal conductivity exceeding k = 0.4 Wm-1K-1 for LED applications. The ‘hybrid polymer’ approach encompasses the dispersion of high thermal conductivity particle fillers (zinc oxide, ZnO as well as the alpha-polymorph of alumina, Al2O3) within a polysiloxane matrix (poly(dimethylsiloxane), PDMS as well as poly(phenyl methyl siloxane), PPMS) to increase the thermal conductivity while maintaining optical transparency and photothermal stability at levels consistent with LED applications. To accomplish this goal, a novel synthesis method for the fabrication of nanosized ZnO particles was developed and a novel surface chemistry was established to modify the surface of zinc oxide particle fillers and thus to enable their dispersion in poly(dimethyl siloxane) (PDMS) matrix polymers. Molecular dynamics and Mie simulations were used to optimize ligand structure and to enable the concurrent mixing of particles in PDMS/PPMS embedding media while also minimizing the thermal boundary resistance as well as optical scattering of particle fillers. Using this approach the synthesis of PDMS/ZnO hybrid encapsulants exhibiting a thermal conductivity of 0.64 Wm-1K-1 and optical transparency > 0.7 mm-1 was demonstrated. A forming process based on micromolding was developed to demonstrate the forming of particle filled PDMS into film and lens shapes. Photothermal stability testing revealed stability of the materials for approximately 4000 min when exposed to blue light LED (450 nm, 30 W/cm2). One postgraduate and seven graduate students were supported by the project. The research performed within this project led to fifteen publications in peer

  13. 21 CFR 172.410 - Calcium silicate.


    ... CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Anticaking... agent in food in an amount not in excess of that reasonably required to produce its intended effect. (b... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Calcium silicate. 172.410 Section 172.410 Food...

  14. Stability of calcium silicate in basic solution

    刘桂华; 李小斌; 彭志宏; 周秋生


    Mixture of CaO and SiO2 was sintered at 1 200 or 1 400 ℃ according to the mole ratio of CaO/SiO2 of 1 or 2, and then calcium silicate was leached in pure caustic or soda solution. The results indicated that calcium silicate exists much more stably in caustic solution than that in soda solution, and CaO*SiO2 is more stable than β-2CaO*SiO2 whether in caustic solution or in soda solution. The increase of sintering temperature favored the stability of calcium silicate in the leaching process. When β-2CaO*SiO2 was leached in soda solution, the increase of leaching temperature and time resulted in decomposing of more calcium silicate. And when β-2CaO*SiO2 was leached in caustic solution at high temperature, much 2CaO*SiO2*H2O but little CaO*SiO2*H2O appeared in slag.



    The objective of the submitted work was to prepare and to characterize two types of silicate coatings prepared by the sol-gel method using the dip-coating technique on a titanium substrate. Efforts have been made to use mechanical properties of bio-inert titanium and bioactive properties of a silicate layer enriched with an admixture of compounds identified below. The first group consisted of silicate coatings containing silver, brushite and monetite. The other group of silicate coatings cont...

  16. The fatty acids and alkanes of Satureja adamovicii Silic and Satureja fukarekii Silic (NOTE



    Full Text Available The content and composition of fatty acids and alkanes of Satureja adamovicii Silic and Satureja fukarekii Silic were analized by GC. It was found that unsaturated acids prevailed and that the major components were palmitic, oleic, linoleic and linolenic acids. The hydrocarbon fractions of pentane extracts were shown to consist of the alkane homologues (C17 to C34 with nonacosane and hentriacontane being prevailing compounds.

  17. 40 CFR 721.9513 - Modified magnesium silicate polymer (generic).


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified magnesium silicate polymer... Specific Chemical Substances § 721.9513 Modified magnesium silicate polymer (generic). (a) Chemical... as modified magnesium silicate polymer (PMN P-98-604) is subject to reporting under this section for...

  18. Multi-residue analysis of pharmaceuticals in aqueous environmental samples by online solid-phase extraction-ultra-high-performance liquid chromatography-tandem mass spectrometry: optimisation and matrix effects reduction by quick, easy, cheap, effective, rugged and safe extraction.

    Bourdat-Deschamps, Marjolaine; Leang, Sokha; Bernet, Nathalie; Daudin, Jean-Jacques; Nélieu, Sylvie


    The aim of this study was to develop and optimise an analytical method for the quantification of a bactericide and 13 pharmaceutical products, including 8 antibiotics (fluoroquinolones, tetracyclines, sulfonamides, macrolide), in various aqueous environmental samples: soil water and aqueous fractions of pig slurry, digested pig slurry and sewage sludge. The analysis was performed by online solid-phase extraction coupled to ultra-high performance liquid chromatography with tandem mass spectrometry (online SPE-UHPLC-MS-MS). The main challenge was to minimize the matrix effects observed in mass spectrometry, mostly due to ion suppression. They depended on the dissolved organic carbon (DOC) content and its origin, and ranged between -22% and +20% and between -38% and -93% of the signal obtained without matrix, in soil water and slurry supernatant, respectively. The very variable levels of these matrix effects suggested DOC content cut-offs above which sample purification was required. These cut-offs depended on compounds, with concentrations ranging from 30 to 290mgC/L for antibiotics (except tylosine) up to 600-6400mgC/L for the most apolar compounds. A modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction procedure was therefore optimised using an experimental design methodology, in order to purify samples with high DOC contents. Its performance led to a compromise, allowing fluoroquinolone and tetracycline analysis. The QuEChERS extraction salts consisted therefore of sodium acetate, sodium sulfate instead of magnesium sulfate, and sodium ethylenediaminetetraacetate (EDTA) as a ligand of divalent cations. The modified QuEChERS procedure employed for the extraction of pharmaceuticals in slurry and digested slurry liquid phases reduced the matrix effects for almost all the compounds, with extraction recoveries generally above 75%. The performance characteristics of the method were evaluated in terms of linearity, intra-day and inter

  19. Dust in the wind: Crystalline silicates, corundum and periclase in PG 2112+059

    Markwick-Kemper, F; Hines, D C; Bouwman, J


    We have determined the mineralogical composition of dust in the Broad Absorption Line (BAL) quasar PG 2112+059 using mid-infrared spectroscopy obtained with the Spitzer Space Telescope. From spectral fitting of the solid state features, we find evidence for Mg-rich amorphous silicates with olivine stoichiometry, as well as the first detection of corundum (Al_2O_3) and periclase (MgO) in quasars. This mixed composition provides the first direct evidence for a clumpy density structure of the grain forming region. The silicates in total encompass 56.5% of the identified dust mass, while corundum takes up 38 wt.%. Depending on the choice of continuum, a range of mass fractions is observed for periclase ranging from 2.7% in the most conservative case to 9% in a less constrained continuum. In addition, we identify a feature at 11.2 micron as the crystalline silicate forsterite, with only a minor contribution from polycyclic aromatic hydrocarbons. The 5% crystalline silicate fraction requires high temperatures such ...

  20. Core Formation on Asteroid 4 Vesta: Iron Rain in a Silicate Magma Ocean

    Kiefer, Walter S.; Mittlefehldt, David W.


    Geochemical observations of the eucrite and diogenite meteorites, together with observations made by NASA's Dawn spacecraft, suggest that Vesta resembles H chondrites in bulk chemical composition, possibly with about 25% of a CM-chondrite like composition added in. For this model, the core is 15% by mass (or 8 volume %) of the asteroid. The abundances of moderately siderophile elements (Ni, Co, Mo, W, and P) in eucrites require that essentially all of the metallic phase in Vesta segregated to form a core prior to eucrite solidification. Melting in the Fe-Ni-S system begins at a cotectic temperature of 940 deg. C. Only about 40% of the total metal phase, or 3-4 volume % of Vesta, melts prior to the onset of silicate melting. Liquid iron in solid silicate initially forms isolated pockets of melt; connected melt channels, which are necessary if the metal is to segregate from the silicate, are only possible when the metal phase exceeds about 5 volume %. Thus, metal segregation to form a core does not occur prior to the onset of silicate melting.

  1. Determination of solid solubility level of Ho nanoparticles in Y-123 superconducting matrix and strong Cu{sub 1} site preference of nanoparticles

    Sarıtekin, N.K. [Abant Izzet Baysal University, Department of Physics, Bolu 14280 (Turkey); Zalaoglu, Y., E-mail: [Abant Izzet Baysal University, Department of Physics, Bolu 14280 (Turkey); Osmaniye Korkut Ata University, Department of Physics, Osmaniye 80000 (Turkey); Yildirim, G. [Abant Izzet Baysal University, Department of Mechanical Engineering, Bolu 14280 (Turkey); Doğruer, M.; Terzioglu, C.; Varilci, A.; Gorur, O. [Abant Izzet Baysal University, Department of Physics, Bolu 14280 (Turkey)


    Graphical abstract: The excess Ho particles inserted in the Y-123 superconducting matrix not only damage the crystal plane alignments and crystallinity of poly-crystallized Y-123 bulk samples but also lead to the phase transition from optimally doped state to the underdoped position in the crystal structure. - Highlights: • Identification of Y-123 ceramics by ρ–T, J{sub c}, XRD, SEM, EDX, H{sub V} and density measurements. • Optimum dopant level of x = 0.100 for Ho concentration in the Y-123 crystal structure. • Phase transition from optimally doped to the underdoped position with excess Ho impurities (x > 0.100). • Improvement of mechanical behavior with increase in strength of interaction between grains. • Superiority of IIC model to HK approach for the description of the real microhardness values. - Abstract: This comprehensive study reports the effect of the Ho inclusions on the microstructural, electrical, mechanical and superconducting characteristics of YBa{sub 2}Cu{sub 3}O{sub 7−δ} ceramic superconductors with the aid of standard characterization methods including the bulk density, dc resistivity (ρ–T), transport critical current density (J{sub c}), X-ray diffraction (XRD), electron dispersive X-ray (EDX), scanning electron microscopy (SEM) and Vickers microhardness (H{sub V}) investigations. The experimental results such as the degree of granularity, hole (filling) localization effect, room temperature resistivity, onset–offset critical transition temperature, degree of the broadening, thermodynamic fluctuations (spin-gap opening temperature), crystallinity, crystal plane alignments (texturing), crystal structure, grain size, phase purity and lattice parameters, appearance of flux pinning centers, grain boundary weak-links (interaction between the superconducting grains), surface morphologies (grain size distribution), real (load independent) microhardness values, elemental compositions and distributions belonging to the pure and Y

  2. Apatite bone cement reinforced with calcium silicate fibers.

    Motisuke, Mariana; Santos, Verônica R; Bazanini, Naiana C; Bertran, Celso A


    Several research efforts have been made in the attempt to reinforce calcium phosphate cements (CPCs) with polymeric and carbon fibers. Due to their low compatibility with the cement matrix, results were not satisfactory. In this context, calcium silicate fibers (CaSiO3) may be an alternative material to overcome the main drawback of reinforced CPCs since, despite of their good mechanical properties, they may interact chemically with the CPC matrix. In this work CaSiO3 fibers, with aspect ratio of 9.6, were synthesized by a reactive molten salt synthesis and used as reinforcement in apatite cement. 5 wt.% of reinforcement addition has increased the compressive strength of the CPC by 250% (from 14.5 to 50.4 MPa) without preventing the cement to set. Ca and Si release in samples containing fibers could be explained by CaSiO3 partial hydrolysis which leads to a quick increase in Ca concentration and in silica gel precipitation. The latter may be responsible for apatite precipitation in needle like form during cement setting reaction. The material developed presents potential properties to be employed in bone repair treatment.

  3. In matrix derivatization of trichloroethylene metabolites in human plasma with methyl chloroformate and their determination by solid-phase microextraction-gas chromatography-electron capture detector.

    Mudiam, Mohana Krishna Reddy; Jain, Rajeev; Varshney, Meenu; Ch, Ratnasekhar; Chauhan, Abhishek; Goyal, Sudhir Kumar; Khan, Haider A; Murthy, R C


    Trichloroethylene (TCE) is a common industrial chemical that has been widely used as metal degreaser and for many industrial purposes. In humans, TCE is metabolized into dichloroacetic acid (DCA), trichloroacetic acid (TCA) and trichloroethanol (TCOH). A simple and rapid method has been developed for the quantitative determination of TCE metabolites. The procedure involves the in situ derivatization of TCE metabolites with methyl chloroformate (MCF) directly in diluted plasma samples followed by extraction and analysis with solid-phase microextraction (SPME) coupled to gas chromatography-electron capture detector (GC-ECD). Factors which can influence the efficiency of derivatization such as amount of MCF and pyridine (PYR), ratio of water/methanol were optimized. The factors which can affect the extraction efficiencies of SPME were screened using 2(7-4) Placket-Burman Design (PBD). A central composite design (CCD) was then applied to further optimize the most significant factors for optimum SPME extraction. The optimum factors for the SPME extraction were found to be 562.5mg of NaCl, pH at 1 and an extraction time of 22 min. Recoveries and detection limits of all three analytes in plasma were found to be in the range of 92.69-97.55% and 0.036-0.068 μg mL(-1) of plasma, respectively. The correlation coefficients were found to be in the range of 0.990-0.995. The intra- and inter-day precisions for TCE metabolites were found to be in the range of 2.37-4.81% and 5.13-7.61%, respectively. The major advantage of this method is that MCF derivatization allows conversion of TCE metabolites into their methyl esters in very short time (≤30 s) at room temperature directly in the plasma samples, thus makes it a solventless analysis. The method developed was successfully applied to the plasma samples of humans exposed to TCE.

  4. Calcic, gypsic, and siliceous soil chronosequences in arid and semiarid environments

    Harden, J.W.; Taylor, E.M.; Reheis, M.C.; McFadden, L.D.; ,


    We studied three soil chronosequences in the western USA to compare the development of calcic, gypsic, and siliceous soils through time. We compared calcic soils from the Silver Lake playa, southeastern California, gypsic-calcic soils from the Kane Fans in Big Horn County, Wyoming, and siliceous-calcic soils from Forty-mile Wash in southwestern Nevada. In these areas, carbonate, gypsum, and opaline silica appear to be derived primarily from eolian additions and, in advanced stages typical of old soils, are dissolved and precipitated as diagnostic calcic or petrocalcic, gypsic or petrogypsic, and duripan soil horizons. These three precipitates produce somewhat similar morphologic characteristics through time. Morphological stages progress from discrete coatings under clasts, to matrix and around clasts, to significant coatings of clasts and cementation of matrix, to laminar caps above plugged horizons in cases of carbonate and silica. Significant differences among the three soil types include development of color, change of pH, and the depth to which the precipitates begin to accumulate. The tops of gypsic horizons occur below the tops of calcic horizons in simple leaching regimes; the depth to the tops of siliceous horizons is more closely related to the presence and development of argillic horizons.

  5. Modified tricalcium silicate cement formulations with added zirconium oxide.

    Li, Xin; Yoshihara, Kumiko; De Munck, Jan; Cokic, Stevan; Pongprueksa, Pong; Putzeys, Eveline; Pedano, Mariano; Chen, Zhi; Van Landuyt, Kirsten; Van Meerbeek, Bart


    This study aims to investigate the effect of modifying tricalcium silicate (TCS) cements on three key properties by adding ZrO2. TCS powders were prepared by adding ZrO2 at six different concentrations. The powders were mixed with 1 M CaCl2 solution at a 3:1 weight ratio. Biodentine (contains 5 wt.% ZrO2) served as control. To evaluate the potential effect on mechanical properties, the mini-fracture toughness (mini-FT) was measured. Regarding bioactivity, Ca release was assessed using ICP-AES. The component distribution within the cement matrix was evaluated by Feg-SEM/EPMA. Cytotoxicity was assessed using an XTT assay. Adding ZrO2 to TCS did not alter the mini-FT (p = 0.52), which remained in range of that of Biodentine (p = 0.31). Ca release from TSC cements was slightly lower than that from Biodentine at 1 day (p > 0.05). After 1 week, Ca release from TCS 30 and TCS 50 increased to a level that was significantly higher than that from Biodentine (p  0.05). EPMA revealed a more even distribution of ZrO2 within the TCS cements. Particles with an un-reacted core were surrounded by a hydration zone. The 24-, 48-, and 72-h extracts of TCS 50 were the least cytotoxic. ZrO2 can be added to TCS without affecting the mini-FT; Ca release was reduced initially, to reach a prolonged release thereafter; adding ZrO2 made TCS cements more biocompatible. TCS 50 is a promising cement formulation to serve as a biocompatible hydraulic calcium silicate cement.

  6. Matrix Factorization and Matrix Concentration

    Mackey, Lester


    Motivated by the constrained factorization problems of sparse principal components analysis (PCA) for gene expression modeling, low-rank matrix completion for recommender systems, and robust matrix factorization for video surveillance, this dissertation explores the modeling, methodology, and theory of matrix factorization.We begin by exposing the theoretical and empirical shortcomings of standard deflation techniques for sparse PCA and developing alternative methodology more suitable for def...

  7. Preparation of magnetic graphene/mesoporous silica composites with phenyl-functionalized pore-walls as the restricted access matrix solid phase extraction adsorbent for the rapid extraction of parabens from water-based skin toners.

    Feng, Jianan; He, Xinying; Liu, Xiaodan; Sun, Xueni; Li, Yan


    In this work, phenyl-functionalized magnetic graphene/mesoporous silica composites (MG-mSiO2-Ph) were prepared and applied as restricted access matrix solid phase extraction (RAM-SPE) adsorbents to determine the parabens in commercially available retail cosmetics. MG-mSiO2-Ph composites were synthesized by a surfactant-mediated co-condensation reaction in which mesoporous silica with phenyl-functionalized pore-walls was coated on a magnetic graphene sheet. The obtained nano-composites were proven to be of sufficient quality for an ideal RAM-SPE adsorbent with a large specific surface area of 369m(2)g(-1), uniform mesopores of 2.8nm, and special phenyl-functionalized pore-walls. Parabens, such as methyl paraben, ethyl paraben and propyl paraben, were extracted from water-based skin toners using one step of the RAM-SPE and were then analysed by a HPLC-DAD system. The SPE conditions were optimized by studying the parameters, such as the adsorbent amount, elution solvent type, adsorption time and desorption time, that influence the extraction efficiency. For each analyte, there were good linearities of approximately 0.10-120μgmL(-1) with determination coefficients (R(2))>0.995. The sensitivity was as low as 0.01-0.025μgmL(-1) for the LOD, and the percent recoveries were 98.37-105.84%. The intra-day and inter-day RSDs were 1.44-6.11% (n=6) and 3.12-11.70% (n=6), respectively. The results indicated that this method with novel RAM-SPE adsorbents is sensitive and convenient. The results also offered an attractive alternative for the extraction and determination of paraben preservatives in a complex matrix, such as cosmetics. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Dynamic Strengthening During High Velocity Shear Experiments with Siliceous Rocks

    Liao, Z.; Chang, J. C.; Boneh, Y.; Chen, X.; Reches, Z.


    It is generally accepted that dynamic-weakening is essential for earthquake instability, and many experimental works have documented this weakening. Recent observations revealed also opposite trends of dynamic-strengthening in experiments (Reches & Lockner, 2010). We present here our experimental results of this dynamic-strengthening and discuss possible implications to earthquake behavior. We ran hundreds of experiments on experimental faults made of siliceous rock including granite, syenite, diorite, and quartzite. The experimental fault is comprised of two solid cylindrical blocks with a raised-ring contact of 7 cm diameter and 1 cm width. We recognized general, three regimes of strength-velocity relations: (I) Dynamic weakening (drop of 20-60% of static strength) as slip velocity increased from ~0.0003 m/s (lowest experimental velocity) to a critical velocity, Vc=0.008-0.16 m/s; (II) Abrupt transition to dynamic strengthening regime during which the fault strength almost regains its static strength; and (III) Quasi-constant strength with further possible drops as velocity approaches ~1 m/s. The critical velocity depends on the sample lithology: Vc is ~0.06 m/s for granite, ~0.008 m/s for syenite, ~0.01 m/s for diorite, and ~0.16 m/s for quartzite. The strengthening stage is associated with temperature increase, wear-rate increase, and the occurrence of intense, high frequency stick-slip events (Reches & Lockner, 2010). Sammis et al., (this meeting) attributed this strengthening to dehydration of the thin water layer that covers the gouge particles as the temperature increases. On the other hand, we note that tens of experiments with dolomite samples (non-siliceous), which were deformed under similar conditions, did not exhibit the velocity strengthening (unpublished). Based on the analyses by Andrews (2004, 2005), we speculate that velocity strengthening may bound the slip velocity. The numerical models of Andrews show that the slip velocity along a slip

  9. Seebeck effect influence on joule heat evolution in electrically conductive silicate materials

    Fiala, Lukáš; Medved, Igor; Maděra, Jiří; Černý, Robert


    In general, silicate building materials are non-conductive matters that are not able to evolve heat when they are subjected to an external voltage. However, the electrical conductivity can be increased by addition of electrically conductive admixtures in appropriate amount which leads to generation of conductive paths in materials matrix. Such enhanced materials can evolve Joule heat and are utilizable as a core of self-heating or snow-melting systems. In this paper, Joule heat evolution together with Seebeck effect in electrically conductive silicate materials was taken into consideration and the model based on heat equation with included influence of DC electric field was proposed. Besides, a modeling example of heating element was carried out on FEM basis and time development of temperature in chosen surface points was expressed in order to declare ability of such system to be applicable.

  10. Thermogravimetric analysis of phase transitions in cement compositions mixed by sodium silicate solution

    Fedosov Sergey Viktorovich


    Full Text Available This paper presents a study of the capability to modify cement by mechanical activation of sodium silicate water solution. Admixtures or blends of binding agents were employed for modifying concrete properties. The liquid glass is applied to protect from chemically or physically unfavorable environmental impacts, such as acidic medium and high temperature. The sodium silicate is a high-capacity setting accelerator. The increasing of the liquid glass proportion in the mix leads to the degradation of the cement paste plasticity and for this reason it is necessary to reduce the amount of liquid glass in the cement paste. The activation of dilute water solution of sodium silicate into rotary pulsating apparatus directly before tempering of the cement paste is an effective way to decrease mass fraction of liquid glass in the cement paste. The results of the combined influence of liquid glass and mechanical activation on physicochemical processes taking place in cement stone are represented in this research. Thermogravimetric analysis was used in order to study cement blends. Thermogravimetric analysis of modified cement stone assays was performed by thermo analyzer SETARAM TGA 92-24. The results of the analysis of phase transition taking place under high-temperature heating of cement stone modified by the mechanical activation of the water solution of the sodium silicate were introduced. Thermograms of cement stone assays were obtained at different hardening age. The comparison of these thermograms allows us to come to a conclusion on the formation and the retention during long time of a more dense structure of the composite matrix mixed by the mechanical activation of sodium silicate water solution. The relation between the concrete composition and its strength properties was stated. Perhaps, the capability of modified concrete to keep calcium ions in sparingly soluble hydrosilicates leads to the increase in its durability and corrosion resistance.

  11. Transesterification of palm oil using sodium silicate base catalyst from geothermal sludge

    Perdana, I.; Nugrahanti, N.; Sofiyah; Bendiyasa, I. M.


    The use of solid base catalysts in biodiesel synthesis is becoming more preferable because of their superiority over homogeneous catalysts. In the present work, a strong base catalyst of sodium silicate synthesized from silica-rich geothermal sludge was used in a transesterification of palm oil with methanol. The catalyst was calcined at 400°C for three hours with a temperature ramp of 20°C/min. The transesterification was carried out at varying temperature in the range of 50 - 70°C for 60 minutes with a methanol-palm oil molar ratio of 8.8:1. The catalyst-palm oil ratio was varied in the range of 1 - 5% (w/w). In order to investigate kinetics of reaction, at a certain interval of time samples were taken consecutively during the reaction. Experimental results showed that the sodium silicate was very active in the transesterification of palm oil with methanol. Reaction temperature at 60°C was sufficient to reach a conversion level as high as 93% in a relatively short reaction period. Meanwhile, the high conversion was still achievable with the use of 1 % (w/w) catalyst. In addition, a lumped model of reaction kinetics was adequate to approach the experimental data with a calculated activation energy of 15.73 kcal/mole. Results of the present work suggested that sodium silicate synthesized from local resources of geothermal sludge would become potential solid base catalyst in biodiesel synthesis.

  12. Development of a new laboratory technique for high-temperature thermal emission spectroscopy of silicate melts

    Lee, Rachel J.; Ramsey, Michael S.; King, Penelope L.


    the prevalence of glass and molten silicates in volcanic environments, and the important role of surface emissivity in thermal infrared (TIR) measurements, it is imperative to characterize accurately the spectral features associated with silicate glasses and melts. A microfurnace has been developed specifically for use with a laboratory Fourier transform infrared (FTIR) spectrometer to collect the first in situ TIR emission spectra of actively melting and cooling silicate glasses. The construction, implementation, and calibration of the microfurnace spectrometer system are presented here. Initial testing of the microfurnace is also discussed, which includes acquisition of thermal emission spectra of a quartz powder (unmelted), a melted and cooled oligoclase feldspar, and glassy melt of rhyolitic composition. Unlike a solid material, which may only have bending and stretching vibrations within its molecular structure, a fully molten material will exhibit several more degrees of freedom in structural movement, thus changing its spectral character. Differences in spectral behavior and morphology are observed between a glass in a solid state and its molten counterpart, confirming previous field measurements of lower emissivity upon melting. This laboratory microfurnace system has been designed to quantify the TIR emission spectral behavior of glassy materials in various physical states. Ultimately, it is hoped that the microfurnace data will help improve the ability of field-based, airborne, and spaceborne TIR data to characterize glassy volcanic terranes.

  13. Cooling rate calculations for silicate glasses.

    Birnie, D. P., III; Dyar, M. D.


    Series solution calculations of cooling rates are applied to a variety of samples with different thermal properties, including an analog of an Apollo 15 green glass and a hypothetical silicate melt. Cooling rates for the well-studied green glass and a generalized silicate melt are tabulated for different sample sizes, equilibration temperatures and quench media. Results suggest that cooling rates are heavily dependent on sample size and quench medium and are less dependent on values of physical properties. Thus cooling histories for glasses from planetary surfaces can be estimated on the basis of size distributions alone. In addition, the variation of cooling rate with sample size and quench medium can be used to control quench rate.

  14. Tracking bubble evolution inside a silicic dike

    Álvarez-Valero, Antonio M.; Okumura, Satoshi; Arzilli, Fabio; Borrajo, Javier; Recio, Clemente; Ban, Masao; Gonzalo, Juan C.; Benítez, José M.; Douglas, Madison; Sasaki, Osamu; Franco, Piedad; Gómez-Barreiro, Juan; Carnicero, Asunción


    Pressure estimates from rapidly erupted crustal xenoliths constrain the depth of intrusion of the silicic lavas hosting them. This represents an opportunity for tracking magmatic bubble's evolution and quantifying the variation in bubble volume during rapid magma ascent through a volcanic dike just prior to eruption. The petrology, stable-isotope geochemistry and X-ray micro-tomography of dacites containing crustal xenoliths, erupted from a Neogene volcano in SE Spain, showed an increase in porosity from ~ 1.7 to 6.4% from ~ 19 to 13 km depth, at nearly constant groundmass and crystal volumes. This result provides additional constraints for experimental and numerical simulations of subvolcanic magma-crust degassing processes in silicic systems, and may allow the characterization of volcanic eruptive styles based on volatile content.

  15. Recycle of silicate waste into mesoporous materials.

    Kim, Jung Ho; Kim, Minwoo; Yu, Jong-Sung


    Template synthesis of porous carbon materials usually requires selective removal of template silica from the carbon/silica composites. It not only involves waste of valuable chemicals, but also poses significant environmental concerns including high waste treatment cost. Recycling of silicates released from such nanocasting methods is successfully performed for the first time to regenerate valuable mesoporous MCM and SBA type silica materials, which will not only help in saving valuable chemicals, but also in decreasing chemical waste, contributing in improvement of our environmental standards. This approach can thus improve cost effectiveness for the mass production of nanostructured carbon and others utilizing silica directed nanocasting method by recycling otherwise silicate waste into highly desirable valuable mesoporous silica.

  16. Biomimetic Mineralization on a Macroporous Cellulose-Based Matrix for Bone Regeneration


    The aim of this study is to investigate the biomimetic mineralization on a cellulose-based porous matrix with an improved biological profile. The cellulose matrix was precalcified using three methods: (i) cellulose samples were treated with a solution of calcium chloride and diammonium hydrogen phosphate; (ii) the carboxymethylated cellulose matrix was stored in a saturated calcium hydroxide solution; (iii) the cellulose matrix was mixed with a calcium silicate solution in order to introduce ...

  17. Adsorption of dimeric surfactants in lamellar silicates

    Balcerzak, Mateusz; Pietralik, Zuzanna [Department of Macromolecular Physics, Faculty of Physics, A. Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland); Domka, Ludwik [Department of Metalorganic Chemistry, Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznań (Poland); Skrzypczak, Andrzej [Institute of Chemical Technology, Poznań University of Technology, Berdychowo 4, 60-965 Poznań (Poland); Kozak, Maciej, E-mail: [Department of Macromolecular Physics, Faculty of Physics, A. Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland)


    Highlights: • The intercalation of dimeric surfactants changed the morphology of MMT samples. • XRD indicated structures formed by surfactant molecules in interlayer space. • The four-step thermal decomposition of dimeric surfactant, confirms intercalation. - Abstract: The adsorption of different types of cationic surfactants in lamellar silicates changes their surface character from hydrophilic to hydrophobic. This study was undertaken to obtain lamellar silicates modified by a series of novel dimeric (gemini) surfactants of different length alkyl chains and to characterise these organophilised materials. Synthetic sodium montmorillonite SOMASIF® ME 100 (M) and enriched bentonite of natural origin (Nanoclay – hydrophilic bentonite®) were organophilised with dimeric (gemini) surfactants (1,1′-(1,4-butanediyl)bis(alkoxymethyl)imidazolium dichlorides). As a result of surfactant molecule adsorption in interlamellar space, the d-spacing (d{sub 001}) increased from 0.97 nm (for the anhydrous structure) to 2.04 nm. A Fourier transform infrared spectroscopy (FTIR) analysis of the modified systems reveals bands assigned to the stretching vibrations of the CH{sub 2} and CH{sub 3} groups and the scissoring vibrations of the NH group from the structure of the dimeric surfactants. Thermogravimetric (TG) and derivative thermogravimetric (DTG) studies imply a four-stage process of surfactant decomposition. Scanning electron microscopy (SEM) images provide information on the influence of dimeric surfactant intercalation into the silicate structures. Particles of the modified systems show a tendency toward the formation of irregularly shaped agglomerates.

  18. Hard X-ray irradiation of cosmic silicate analogs: structural evolution and astrophysical implications

    Gavilan, L.; Jäger, C.; Simionovici, A.; Lemaire, J. L.; Sabri, T.; Foy, E.; Yagoubi, S.; Henning, T.; Salomon, D.; Martinez-Criado, G.


    Context. Protoplanetary disks, interstellar clouds, and active galactic nuclei contain X-ray-dominated regions. X-rays interact with the dust and gas present in such environments. While a few laboratory X-ray irradiation experiments have been performed on ices, X-ray irradiation experiments on bare cosmic dust analogs have been scarce up to now. Aims: Our goal is to study the effects of hard X-rays on cosmic dust analogs via in situ X-ray diffraction. By using a hard X-ray synchrotron nanobeam, we seek to simulate cumulative X-ray exposure on dust grains during their lifetime in these astrophysical environments and provide an upper limit on the effect of hard X-rays on dust grain structure. Methods: We prepared enstatite (MgSiO3) nanograins, which are analogs to cosmic silicates, via the melting-quenching technique. These amorphous grains were then annealed to obtain polycrystalline grains. These were characterized via scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) before irradiation. Powder samples were prepared in X-ray transparent substrates and were irradiated with hard X-rays nanobeams (29.4 keV) provided by beamline ID16B of the European Synchrotron Radiation Facility (Grenoble). X-ray diffraction images were recorded in transmission mode, and the ensuing diffractograms were analyzed as a function of the total X-ray exposure time. Results: We detected the amorphization of polycrystalline silicates embedded in an organic matrix after an accumulated X-ray exposure of 6.4 × 1027 eV cm-2. Pure crystalline silicate grains (without resin) do not exhibit amorphization. None of the amorphous silicate samples (pure and embedded in resin) underwent crystallization. We analyze the evolution of the polycrystalline sample embedded in an organic matrix as a function of X-ray exposure. Conclusions: Loss of diffraction peak intensity, peak broadening, and the disappearance of discrete spots and arcs reveal the amorphization

  19. Matrix calculus

    Bodewig, E


    Matrix Calculus, Second Revised and Enlarged Edition focuses on systematic calculation with the building blocks of a matrix and rows and columns, shunning the use of individual elements. The publication first offers information on vectors, matrices, further applications, measures of the magnitude of a matrix, and forms. The text then examines eigenvalues and exact solutions, including the characteristic equation, eigenrows, extremum properties of the eigenvalues, bounds for the eigenvalues, elementary divisors, and bounds for the determinant. The text ponders on approximate solutions, as well

  20. The sealing of excavation damaged zones in salt formations using sodium silicate solutions

    Engelhardt, Hans-Joachim; Schmidt, Holger; Borstel, Lieselotte von [DBE TECHNOLOGY GmbH, Peine (Germany). Dept. of Repository Safety


    Since many decades, pressure grouting is an effective technique of civil engineering for sealing and stabilization purposes. Due to the potential contamination of fluids, grouting is of particular importance in repositories of radioactive waste. Traditional grouts for the sealing of fine fractures are sodium silicate solutions. Laboratory and field investigations prove that the particle-free solutions can be used to permanently seal excavation damaged zones (EDZ) in salt formations, because the solid reaction products are inert or almost insoluble. EDZ permeabilities of 10{sup -17} m{sup 2} can be achieved and were determined on the basis of the injection pressures and flow rates. High grouting pressures were realized as local test loadings. Laboratory tests show the fixation of Co{sup 2+}, Ni{sup 2+}, Sr{sup 2+}, Ba{sup 2+}, [UO{sub 2}]{sup 2+} and illustrate that sodium silicates may act additionally as a chemical barrier.

  1. [Broad excitation band alkaline-earth silicate luminescent materials activated by rare earth and its applications].

    Xia, Wei; Lei, Ming-Kai; Luo, Xi-Xian; Xiao, Zhi-Guo


    Series of novel broad excitation band phosphors M2 MgSis O7 : Eu, Dy(M = Ca, Sr) were prepared by a high temperature solid-state reaction method. The crystal structure of compound was characterized. And the effects of part substitution of alkaline-earth on crystal structure, photoluminescence spectra and luminescence properties were also investigated. It is found that the excitation band of silicate luminescent materials extend to visible region and they exhibit yellow, green and blue long after-glow luminescence after excited by ultraviolet or visible light. Ca MgSi O7 : Eu, Dy luminescent materials can be excited effectively under the 450-480 nm range and exhibit a strong emission at 536 nm, nicely combining with blue light emitted by InGaN chips to produce white light. This promises the silicate luminescent materials a potential yellow phosphor for white LED.

  2. Formation of a low-crystalline Zn-silicate in a stream in SW Sardinia, Italy

    Wanty, Richard B.; De Giudici, G.; Onnis, P.; Rutherford, D.; Kimball, B.A.; Podda, F.; Cidu, R.; Lattanzi, P.; Medas, D.


    n southwestern Sardinia, Italy, the Rio Naracauli drains a catchment that includes several abandoned mines. The drainage from the mines and associated waste rocks has led to extreme concentrations of dissolved Zn, but because of the near-neutral pH, concentrations of other metals remain low. In the reach from approximately 2300 to 3000 m downstream from the headwaters area, an amorphous Zn-silicate precipitates from the water. In this reach, concentrations of both Zn and silica remain nearly constant, but the loads (measured in mass/time) of both increase, suggesting that new Zn and silica are supplied to the stream, likely from emerging groundwater. Zinc isotope signatures of the solid are heavier than the dissolved Zn by about 0.5 permil in 66/64Zn, suggesting that an extracellular biologically mediated adsorption process may be involved in the formation of the Zn-silicate.

  3. Graphene/TiO2 nanocomposite based solid-phase extraction and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for lipidomic profiling of avocado (Persea americana Mill.).

    Shen, Qing; Yang, Mei; Li, Linqiu; Cheung, Hon-Yeung


    Phospholipids possess important physiological, structural and nutritional functions in biological systems. This study described a solid-phase extraction (SPE) method, employing graphene and titanium dioxide (G/TiO2) nanocomposite as sorbent, for the selective isolation and enrichment of phospholipids from avocado (Persea americana Mill.). Based on the principal that the phosphoryl group in the phospholipid can interact with TiO2 via a bridging bidentate mode, an optimum condition was established for SPE, and was successfully applied to prepare avocado samples. The extracts were monitored by matrix-assisted laser desorption ionization time-of-flight/tandem mass spectrometry (MALDI-TOF/MS) in both positive-ion and negative-ion modes. Results showed that phospholipids could be efficiently extracted in a clean manner by G/TiO2 based SPE. In addition, the signals of phospholipids were enhanced while the noise was reduced. Some minor peaks became more obvious. In conclusion, the nanocomposite material of G/TiO2 was proved to be a promising sorbent for selective separation of phospholipids from crude lipid extract.

  4. Importance of the coupling between the sign of the mean stress and the third invariant on the rate of void growth and collapse in porous solids with a von Mises matrix

    Alves, J. L.; Revil-Baudard, Benoit; Cazacu, Oana


    Recently, Cazacu et al (2013a J. Appl. Mech. 80 64501) demonstrated that the plastic potential of porous solids with a von Mises matrix containing randomly distributed spherical cavities should involve a very specific coupling between the mean stress and J_{3}^{\\Sigma} , the third invariant of the stress deviator. In this paper, the effects of this coupling on void evolution are investigated. It is shown that the new analytical model predicts that for axisymmetric stress states, void growth is faster for loading histories corresponding to J_{3}^{\\Sigma} \\ge 0 than for those corresponding to J_{3}^{\\Sigma} \\le 0 . However, void collapse occurs faster for loadings where J_{3}^{\\Sigma} \\le 0 than for those characterized by J_{3}^{\\Sigma} \\ge 0 . Finite-element (FE) results also confirm these trends. Furthermore, comparisons between FE results and corresponding predictions of yielding and void evolution show the improvements provided by the new model with respect to Gurson's. Irrespective of the loading history, the predicted rate of void growth is much faster than that according to Gurson's criterion.

  5. Direct analysis of 18 flavonol glycosides, aglycones and terpene trilactones in Ginkgo biloba tablets by matrix solid phase dispersion coupled with ultra-high performance liquid chromatography tandem triple quadrupole mass spectrometry.

    Liu, Xin-Guang; Yang, Hua; Cheng, Xiao-Lan; Liu, Lei; Qin, Yong; Wang, Qi; Qi, Lian-Wen; Li, Ping


    Analysis and quality control of Ginkgo biloba have been comprehensively studied. However, little attention has been devoted to the simultaneous extraction and analysis of flavonols and terpene trilactones, especially for direct quantification of flavonol glycosides. This work described a rapid strategy for one-step extraction and quantification of the components. A matrix solid phase dispersion (MSPD) method was designed for the extraction of ginkgo ingredients and compared with the heat-reflux and ultrasonic extraction methods. An ultra-high performance liquid chromatography (UHPLC)-tandem-triple-quadrupole-mass spectrometry (QQQ-MS) method was developed for detection of the 18 components, including 10 original flavonol glycosides, 3 aglycones, and 5 lactones. Subsequently, the proposed strategy was used for the analysis of 12 G. biloba tablets. Results showed that MSPD produced comparable extraction efficiency but consumed less time and required lower solvent volumes compared with conventional methods. Without hydrolysis, the concentration detected was much closer to the original in the sample. The total flavonol glycoside contents in ginkgo tablets ranged from 3.59 to 125.21μgmg(-1), and the terpene trilactone varied from 3.45 to 57.8μgmg(-1) among different manufacturers. In conclusion, the proposed MSPD and UHPLC-QQQ-MS is rapid and sensitive in providing comprehensive profile of chemical constituents especially the genuine flavonol glycosides for improved quality control of ginkgo products.

  6. Effect of silicate solutions on metakaolinite based cementitious material

    XIAO Xue-jun; LI Hua-jian; SUN Heng-hu


    High performance metakaolinite based cementitious materials were prepared with metakaolinite as main component, and the different modules of Na and Na-K silicate solutions as diagenetic agent. The results show that the mechanical properties are affected by different silicate solutions, compressive strengths of pastes hydrated for 3 d and 28 d with Na-K silicate solution (The modulus is 1) are about 43.68 and 78.52 MPa respectively. By analyzing the mechanical properties of Metakaolinite based cementitious materials, the diagenetic effect of lower module is better than higher module, and Na-K silicate solution is better than Na silicate solution. The structure of the Na and Na-K silicate solutions is studied with IR and 29Si NMR, the reason of the lower module and Na-K silicate solution improving the mechanical properties is that the low module silicate solution has lower polymeric degree of silicon dioxide, and the higher polymeric degree of silicon oxide tetrahedron(Q4) in Na-K silicate solution is less than Na silicate solution.

  7. Diseases associated with exposure to silica and nonfibrous silicate minerals. Silicosis and Silicate Disease Committee


    Silicosis, a disease of historical importance, continues to occur cryptically today. Its pathogenesis is under ongoing study as new concepts of pathobiology evolve. In this article, the gross and microscopic features of the disease in the lungs and the lesions in lymph nodes and other viscera are described. These tissue changes are then discussed in the context of clinical disease and other possible or established complications of silica exposure (ie, scleroderma and rheumatoid arthritis, glomerulonephritis, and bronchogenic carcinoma). Silicates are members of a large family of common minerals, some of which have commercial importance. Silicates are less fibrogenic than silica when inhaled into the lungs, but cause characteristic lesions after heavy prolonged exposure. The features of these disease conditions are described herein. Various aspects of the mineralogy and tissue diagnosis of silicosis and lung disease due to silicates are reviewed. An overview of contemporary regulatory considerations is provided.204 references.

  8. Zirconium silicate assisted removal of residual proteins after organic solvent deproteinization of human plasma, enhancing the stability of the LC-ESI-MS response for the bioanalysis of small molecules.

    Hussain, Shah; Pezzei, Cornelia; Güzel, Yüksel; Rainer, Matthias; Huck, Christian W; Bonn, Günther K


    An efficient blood plasma clean-up method was developed, where methanol protein precipitation was applied, followed by zirconium silicate assisted exclusion of residual proteins. A strong binding of zirconium (IV) silicate to the proteins enabled the elimination of remaining proteins after solvent deproteinization through a rapid solid-phase extraction (SPE) procedure. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI/TOF MS) was used for monitoring the proteins during clean-up practice applied to human plasma samples. The proteins were quantified by colorimetric detection using the bicinchoninic acid (BCA) assay. The presented analytical strategy resulted in the depletion of >99.6% proteins from human plasma samples. Furthermore, high-performance liquid chromatography hyphenated to diode-array and electrospray ionization mass spectrometric detection (HPLC-DAD/ESI MS) was applied for qualitative and quantitative analysis of the caffeoylquinic acids (CQAs) and their metabolites in human plasma. The procedure demonstrated high recoveries for the standard compounds spiked at different concentrations. Cynarin and chlorogenic acid were recovered in the range of 81-86% and 78-83%, respectively. Caffeic acid was extracted in the excess of 89-92%, while ferulic acid and dihydroxyhydrocinnamic acid showed a recovery of 87-91% and 92-95%, respectively. The method was partially validated in accordance with FDA-Industry Guidelines for Bioanalytical Method Validation (2001). The presented scheme improves the clean-up efficacy of the methanol deproteinization, significantly reduces the matrix effects and provides a great analytical tool for the isolation of small molecules from human plasma.

  9. Discrete dipole approximation models of chrystalline forsterite: Applications to cometary crystalline silicates

    Lindsay, Sean Stephen

    The shape, size, and composition of crystalline silicates observed in comet comae and external proto-planetary disks are indicative of the formation and evolution of the dust grains during the processes of planetary formation. In this dissertation, I present the 3 -- 40 mum absorption efficiencies( Qabs) of irregularly shaped forsterite crystals computed with the discrete dipole approximation (DDA) code DDSCAT developed by Draine and Flatau and run on the NASA Advanced Supercomputing facility Pleiades. An investigation of grain shapes ranging from spheroidal to irregular indicate that the strong spectral features from forsterite are sensitive to grain shape and are potentially degenerate with the effects of crystal solid state composition (Mg-content). The 10, 11, 18, 23, and 33.5 mum features are found to be the most crystal shape sensitive and should be avoided in determining Mg-content. The distinct spectral features for the three shape classes are connected with crystal formation environment using a condensation experiment by (Kobatake et al., 2008). The condensation experiment demonstrates that condensed forsterite crystal shapes are dependent on the condensation environmental temperature. I generate DDSCAT target analog shapes to the condensed crystal shapes. These analog shapes are represented by the three shape classes: 1) equant, 2) a, c-columns, and 3) b-shortened platelets. Each of these shape classes exhibit distinct spectral features that can be used to interpret grain shape characteristics from 8 --- 40 mum spectroscopy of astronomical objects containing crystalline silicates. Synthetic spectral energy distributions (SEDs) of the coma of Hale-Bopp at rh = 2.8 AU are generated by thermally modeling the flux contributions of 5 mineral species present in comets. The synthetic SEDs are constrained using a chi2- minimization technique. The mineral species are amorphous carbon, amorphous pyroxene, amorphous olivine, crystalline enstatite, and crystalline

  10. Correlative spectroscopy of silicates in mineralised nodules formed from osteoblasts

    Boonrungsiman, Suwimon; Fearn, Sarah; Gentleman, Eileen; Spillane, Liam; Carzaniga, Raffaella; McComb, David W.; Stevens, Molly M.; Porter, Alexandra E.


    Silicon supplementation has been shown to play an important role in skeleton development, however, the potential role that silicon plays in mediating bone formation, and an understanding of where it might localise in the resulting bone tissue remain elusive. An improved understanding of these processes could have important implications for treating pathological mineralisation. A key aspect of defining the role of silicon in bone is to characterise its distribution and coordination environment, however, there is currently almost no information available on either. We have combined a sample-preparation method that simultaneously preserved mineral, ions, and the extracellular matrix (ECM) with secondary ion mass spectroscopy (SIMS) and electron energy-loss spectroscopy (EELS) to examine the distribution and coordination environment of silicon in murine osteoblasts (OBs) in an in vitro model of bone formation. SIMS analysis showed a high level of surface contamination from polydimethysiloxane (PDMS) resulting from sample preparation. When the PDMS was removed, silicon compounds could not be detected within the nodules either by SIMS or by energy dispersive X-ray spectroscopy (EDX) analysis. In comparison, electron energy-loss spectroscopy (EELS) provided a powerful and potentially widely applicable means to define the coordination environment and localisation of silicon in mineralising tissues. We show that trace levels of silicon were only detectable from the mineral deposits located on the collagen and in the peripheral region of mineralised matrix, possibly the newly mineralised regions of the OB nodules. Taken together our results suggest that silicon plays a biological role in bone formation, however, the precise mechanism by which silicon exerts its physicochemical effects remains uncertain. Our analytical results open the door for compelling new sets of EELS experiments that can provide detailed and specific information about the role that silicates play in bone

  11. Sintering and foaming of barium silicate glass powder compacts

    Mueller, Ralf; Reinsch, Stefan; Agea-Blanco, Boris


    The manufacture of sintered glasses and glass-ceramics, glass matrix composites and glass-bounded ceramics or pastes is often affected by gas bubble formation. Against this background, we studied sintering and foaming of barium silicate glass powders used as SOFC sealants using different powder milling procedures. Sintering was measured by means of heating microscopy backed up by XPD, DTA, Vacuum Hot Extraction (VHE) and optical and electron microscopy. Foaming increased significantly as milling progressed. For moderately milled glass powders, subsequent storage in air could also promote foaming. Although the powder compacts were uniaxially pressed and sintered in air, the milling atmosphere sig¬ni¬ficantly affected foaming. The strength of this effect increased in the order Ar ? N2 encapsulated CO2, even for powders milled in Ar and N2. Results of this study thus indicate that foaming is caused by carbonaceous species trapped on the glass powder surface. Foaming could be substantially reduced by milling in water and 10 wt% HCl.

  12. Sintering and foaming of barium silicate glass powder compacts

    Ralf Mueller


    Full Text Available The manufacture of sintered glasses and glass-ceramics, glass matrix composites and glass-bounded ceramics or pastes is often affected by gas bubble formation. Against this background, we studied sintering and foaming of barium silicate glass powders used as SOFC sealants using different powder milling procedures. Sintering was measured by means of heating microscopy backed up by XPD, DTA, Vacuum Hot Extraction (VHE and optical and electron microscopy. Foaming increased significantly as milling progressed. For moderately milled glass powders, subsequent storage in air could also promote foaming. Although the powder compacts were uniaxially pressed and sintered in air, the milling atmosphere sig¬ni¬ficantly affected foaming. The strength of this effect increased in the order Ar  N2 < air < CO2. Conformingly, VHE studies revealed that the pores of foamed samples predominantly encapsulated CO2, even for powders milled in Ar and N2. Results of this study thus indicate that foaming is caused by carbonaceous species trapped on the glass powder surface. Foaming could be substantially reduced by milling in water and 10 wt% HCl.

  13. Determination of chlorine in silicate rocks

    Peck, L.C.


    In a rapid accurate method for the determination of chlorine in silicate rocks, the rock powder is sintered with a sodium carbonate flux containing zinc oxide and magnesium carbonate. The sinter cake is leached with water, the resulting solution is filtered, and the filtrate is acidified with nitric acid. Chlorine is determined by titrating this solution with mercuric nitrate solution using sodium nitroprusside as the indicator. The titration is made in the dark with a beam of light shining through the solution. The end point of the titration is found by visually comparing the intensity of this beam of light with that of a similar beam of light in a reference solution.

  14. Nitridosilicates - a significant extension of silicate chemistry

    Schnick, W.; Huppertz, H. [Bayreuth Univ. (Germany). Lab. fuer Anorganische Chemie


    A new dimension in silicate chemistry becomes accessible through substitution of oxygen by nitrogen. Multinary nitridosilicates, such as Ln{sub 3}Si{sub 6}N{sub 11} (Ln = La, Ce, Pr, Nd, Sm) shown on the right, are built up from SiN{sub 4} tetrahedra into network structures. Owing to the stability of the covalent Si-N bonds and the high degree of condensation, the nitridosilicates show remarkable chemical and thermal stabilities, similar to Si{sub 3}N{sub 4}. (orig.) 22 refs.

  15. Microbial dissolution of silicate materials. Final report

    Schwartzman, D. [Howard Univ., Washington, DC (United States). Dept. of Biology


    The objective of this research was to better understand the role of selected thermophilic bacteria in the colonization and dissolution of silicate minerals, with potential applications to the HDR Project. The demonstration of enhanced dissolution from microbial effects is critically dependent on providing a mineral bait within a media deficient in the critical nutrient found in the mineral (e.g., Fe). Reproducible experimental conditions in batch experiments require agitation to expose mineral powders, as well as nearly similar initial conditions for both inoculated cultures and controls. It is difficult, but not impossible to ensure reproducible conditions with microbes favoring filamentous growth habits.

  16. Identification of Highly Fractionated (18)O-Rich Silicate Grains in the Queen Alexandra Range 99177 CR3 Chondrite

    Nguyen, A. N.; Keller, L. P.; Messenger, S.; Rahman, Z.


    Carbonaceous chondrites contain a mixture of solar system condensates, presolar grains, and primitive organic matter. The CR3 chondrite QUE 99177 has undergone minimal al-teration [1], exemplified by abundant presolar silicates [2, 3] and anomalous organic matter [4]. Oxygen isotopic imaging studies of this meteorite have focused on finding submicrometer anomalous grains in fine-grained regions of thin sections. Here we present re-sults of an O isotopic survey of larger matrix grains.

  17. Matrix Thermalization

    Craps, Ben; Nguyen, Kévin


    Matrix quantum mechanics offers an attractive environment for discussing gravitational holography, in which both sides of the holographic duality are well-defined. Similarly to higher-dimensional implementations of holography, collapsing shell solutions in the gravitational bulk correspond in this setting to thermalization processes in the dual quantum mechanical theory. We construct an explicit, fully nonlinear supergravity solution describing a generic collapsing dilaton shell, specify the holographic renormalization prescriptions necessary for computing the relevant boundary observables, and apply them to evaluating thermalizing two-point correlation functions in the dual matrix theory.

  18. Single-Drop Solution Electrode Discharge-Induced Cold Vapor Generation Coupling to Matrix Solid-Phase Dispersion: A Robust Approach for Sensitive Quantification of Total Mercury Distribution in Fish.

    Chen, Qian; Lin, Yao; Tian, Yunfei; Wu, Li; Yang, Lu; Hou, Xiandeng; Zheng, Chengbin


    Sensitive quantification of mercury distribution in fish is challenging because of insufficient sensitivities of conventional analytical methods, the limited mass of organs (tens of micrograms to several milligrams), and dilution of analyte concentration from sample digestion. In this work, a simple and robust approach coupling multiwall carbon nanotubes assisted matrix solid-phase dispersion (MWCNTs-MSPD) to single-drop solution electrode glow discharge-induced cold vapor generation (SD-SEGD-CVG) was developed for the sensitive determination of mercury in limited amount of sample. Mercury species contained in a limited amount of sample can be efficiently extracted into a 100 μL of eluent by MWCNTs-MSPD, which are conveniently converted to Hg(0) by SD-SEGD-CVG and further transported to atomic fluorescence spectrometry for their determination. Therefore, analyte dilution resulted from sample preparation is avoided and sensitivity is significantly improved. On the basis of consumption of 1 mg of sample, a limit of detection of 0.01 μg L(-1) (0.2 pg) was obtained with relative standard deviations (RSDs) of 5.2% and 4.6% for 2 and 20 μg L(-1), respectively. The accuracy of the proposed method was validated by analysis of three Certified Reference Materials with satisfying results. To confirm that SD-SEGD-CVG-AFS coupling to MWCNTs-MSPD is a promising method to quantify mercury distribution in fish, this method was successfully applied for the sensitive determination of mercury in seven organs of common carps (muscle, gill, intestine, liver, gallbladder, brain, and eye) after dietary of mercury species. The proposed method provides advantages of minimum sample dilution, low blank, high sample introduction efficiency, high sensitivity, and minimum toxic chemicals and sample consumption.

  19. Changes in Global Silicate Weathering Feedbacks over Phanerozoic Time

    West, A. J.


    The release of carbon from the solid Earth exerts a first-order control on the evolution of the planetary environment. This basic climate forcing is modulated by a host of chemical reactions at the Earth's surface, the pace of which are in turn regulated by tectonic forces. Together, these various pieces in the puzzle of the global carbon cycle have been identified for decades, but understanding of how they fit together has remained elusive and continues to be much debated. In particular, we now know the climate-dependence of silicate mineral weathering may vary as a function of denudation rate, which is related to tectonic drivers. This variation suggests that the strength of the weathering feedback may have varied in the past, with consequent implications for the past state of global climate. This work will survey and synthesize approaches to representing changes in the weathering feedback, showing that relatively simple parameterizations yield similar results as recently developed reactive transport approaches. This similarity gives confidence in applying the simple parameterizations to reconstructing changes in feedback strength in the geologic past, at least over Phanerozoic timescales, and allows inclusion of this effect explicitly in carbon cycle models.

  20. Structure characterization for the geopolymer of sodium silicate and metakaolin

    CAO De-guang; SU Da-gen


    Geopolymers of metakaolin and sodium silicate were synthesized respectively with the ratios of the amount of SiO2 in the sodium silica solution to that of Al2O3 in metakaolinite equal to 1.0, and 0.66. The geopolymeric structures of the products were investigated by 27Al and 29Si solid-state nuclear magnetic resonances with magic-angle spinning (MAS NMR), Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), differential scanning colorimetry (DSC) and scanning electron microscopy (SEM). The reaction of the Al-O sheet in meakaolinite with low-order polymerized Si-O tetrahedral units such as monomer of SiO4 yields three-dimensional structures with the Q3 Si-O tetrahedral structure and the coordination of Al(IV) in the Al-O tetrahedral structure. The geopolymers are essentially X-ray amorphous. The assays by 27Al and 29Si NMR, FTIR confirm that the active structure in the metakaolinite is the sheet of Al-O with three coordination states.

  1. A New Biphasic Dicalcium Silicate Bone Cement Implant

    Fausto Zuleta


    Full Text Available This study aimed to investigate the processing parameters and biocompatibility of a novel biphasic dicalcium silicate (C2S cement. Biphasic α´L + β-C2Sss was synthesized by solid-state processing, and was used as a raw material to prepare the cement. In vitro bioactivity and biocompatibility studies were assessed by soaking the cement samples in simulated body fluid (SBF and human adipose stem cell cultures. Two critical-sized defects of 6 mm Ø were created in 15 NZ tibias. A porous cement made of the high temperature forms of C2S, with a low phosphorous substitution level, was produced. An apatite-like layer covered the cement’s surface after soaking in SBF. The cell attachment test showed that α´L + β-C2Sss supported cells sticking and spreading after 24 h of culture. The cement paste (55.86 ± 0.23 obtained higher bone-to-implant contact (BIC percentage values (better quality, closer contact in the histomorphometric analysis, and defect closure was significant compared to the control group (plastic. The residual material volume of the porous cement was 35.42 ± 2.08% of the initial value. The highest BIC and bone formation percentages were obtained on day 60. These results suggest that the cement paste is advantageous for initial bone regeneration.

  2. Stability of foams in silicate melts

    Proussevitch, Alexander A.; Sahagian, Dork L.; Kutolin, Vladislav A.


    Bubble coalescence and the spontaneous disruption of high-porosity foams in silicate melts are the result of physical expulsion of interpore melt (syneresis) leading to bubble coalescence, and diffusive gas exchange between bubbles. Melt expulsion can be achieved either along films between pairs of bubbles, or along Plateau borders which represent the contacts between 3 or more bubbles. Theoretical evaluation of these mechanisms is confirmed by experimental results, enabling us to quantify the relevant parameters and determine stable bubble size and critical film thickness in a foam as a function of melt viscosity, surface tension, and time. Foam stability is controlled primarily by melt viscosity and time. Melt transport leading to coalescence of bubbles proceeds along inter-bubble films for smaller bubbles, and along Plateau borders for larger bubbles. Thus the average bubble size accelerates with time. In silicate melts, the diffusive gas expulsion out of a region of foam is effective only for water (and even then, only at small length scales), as the diffusion of CO 2 is negligible. The results of our analyses are applicable to studies of vesicularity of lavas, melt degassing, and eruption mechanisms.

  3. Research drilling in young silicic volcanoes

    Eichelberger, J.C.


    Magmatic activity, and particularly silicic magmatic activity, is the fundamental process by which continental crust forms and evolves. The transport of magma from deep crustal reservoirs to the surface is a neglected but important aspect of magmatic phenomena. It encompasses problems of eruptive behavior, hydrothermal circulation, and ore deposition, and must be understood in order to properly interpret deeper processes. Drilling provides a means for determining the relationship of shallow intrusive processes to eruption processes at young volcanoes where eruptions are best understood. Drilling also provides a means for directly observing the processes of heat and mass transfer by which recently emplaced intrusions approach equilibrium with their new environment. Drilling in the Inyo Chain, a 600-year-old chain of volcanic vents in California, has shown the close relationship of silicic eruption to shallow dike emplacement, the control of eruptive style by shallow porous-flow degassing, the origin of obsidian by welding, the development of igneous zonation by viscosity segregation, and the character and size of conduits in relation to well-understood magmatic and phreatic eruptions. 36 refs., 9 figs.

  4. Stability constants for silicate adsorbed to ferrihydrite

    Hansen, Hans Christian Bruun; Wetche, T.P.; Raulund-Rasmussen, Karsten


    experiments in 0.01 m NaNO3 electrolyte (pH 3-6). The surface equilibrium constants were calculated according to the two-layer model by Dzombak & Morel (1990). Near equilibrium between protons/hydroxyls in solution and the ferrihydrite surface was obtained within minutes while equilibration with silicate...... required days-weeks, both reactions probably being diffusion controlled. Applying the values for specific surface area and site densities for ferrihydrite used by Dzombak & Morel (1990) (600 m2 g-1, 3.4 mumole m-2) the constants pK(al)intr 6.93 +/- 0.12, pK(a2)intr = 8.72 +/- 0.17 and log K(Si) = 3.62 were...... calculated by using the FITEQL optimization routine. Use of the specific surface area actually measured (269 m2 g-1) gave a poorer fit of the experimental data. Due to the slow adsorption of silicate and hence long shaking times, changes in the surface characteristics of the ferrihydrite seem to take place...

  5. Seed particle formation for silicate dust condensation by SiO nucleation

    Gail, H -P; Pucci, A; Tamanai, A


    Clustering of the abundant SiO molecules has been discussed as a possible mechanism of seed particle formation for silicate dust in stellar outflows with an oxygen rich element mixture. Previous results indicated that condensation temperatures based on this mechanism are significant lower than what is really observed. This negative result strongly rests on experimental data on vapour pressure of SiO. New determinations show the older data to be seriously in error. Here we aim to check with improved data the possibility that SiO nucleation triggers the cosmic silicate dust formation. First we present results of our measurements of vapour pressure of solid SiO. Second, we use the improved vapour pressure data to re-calibrate existing experimental data on SiO nucleation from the literature. Third, we use the re-calibrated data on SiO nucleation in a simple model for dust-driven winds to determine the condensation temperature of silicate in stellar outflows from AGB stars. We show that onset of nucleation under c...

  6. Petrophysical Analysis of Siliceous Ooze Sediments, Ormen Lange Field, Norway

    Awedalkarim, Ahmed; Fabricius, Ida Lykke

    Skeletal remains of siliceous algae form biogenic fine grained highly porous pelagic siliceous ooze sediments that were found above the reservoir of the Ormen Lange gas field which is located in the southern part of the Norwegian Sea (Figure 1a). The Palaeocene sandstone of the “Egga” Formation i...

  7. Silicate Adsorption in Paddy Soils of Guangdong Province, China

    HUANG Li-Yuan; LI Hua-Xing; ZHANG Xin-Ming; LU Wei-Sheng; LIU Yuan-Jin


    Silicate adsorption in eight paddy soils developed from four different parent materials in Guangdong Province, China was examined to obtain fundamental knowledge of silicate adsorption to improve the efficacy of silicate fertilizer use in these areas. A correlation analysis showed that silicate adsorption did not obey the Langmuir equation (r = -0.664-0.301) but did obey the Freundlich and Temkin equations (P ≤ 0.01, r = 0.885-0.990). When the equilibrium silicate concentration (Ci) was less than 45 mg SiO2 kg-1, the adsorption capacity was in the following decreasing order of paddy soils: basalt-derived > Pearl River Delta sediment-derived > granite-derived > sand-shale-derived. Stepwise regression and path analysis showed that for the investigated paddy soils amorphous MnO and Al2O3 were the two most important materials that affected silicate adsorption. Moreover, as Ci increased, amorphous Al2O3 tended to play a more important role in silicate adsorption, while the effects of amorphous MnO on silicate adsorption tended to decrease.

  8. Crystalline silicates in AGB and post-AGB stars

    Waters, LBFM; Molster, FJ; LeBertre, T; Lebre, A; Waelkens, C


    We discuss ISO spectroscopy of oxygen-rich dust shells surrounding evolved stars. The dust that condenses in the outflows of stars on the Asymptotic Giant Branch consists mainly of amorphous silicates and simple oxides. For high mass loss rates, crystalline silicates begin to appear at modest abunda

  9. The shape and composition of interstellar silicate grains

    Min, M.; Waters, L.B.F.M.; de Koter, A.; Hovenier, J.W.; Keller, L.P.; Markwick-Kemper, F.


    We investigate the composition and shape distribution of silicate dust grains in the interstellar medium. The effects of the amount of magnesium and iron in the silicate lattice are studied in detail. We fit the spectral shape of the interstellar 10 mu m extinction feature as observed towards the ga

  10. The shape and composition of interstellar silicate grains

    Min, M.; Waters, L.B.F.M.; de Koter, A.; Hovenier, J.W.; Keller, L.P.; Markwick-Kemper, F.


    We investigate the composition and shape distribution of silicate dust grains in the interstellar medium. The effects of the amount of magnesium and iron in the silicate lattice are studied in detail. We fit the spectral shape of the interstellar 10 mu m extinction feature as observed towards the

  11. Crystallisation mechanism of a multicomponent lithium alumino-silicate glass

    Wurth, R. [Otto-Schott-Institut, Jena University, Fraunhoferstr. 6, 07743 Jena (Germany); Pascual, M.J., E-mail: [Instituto de Ceramica y Vidrio, CSIC, Kelsen 5, 28049 Madrid (Spain); Mather, G.C.; Pablos-Martin, A.; Munoz, F.; Duran, A. [Instituto de Ceramica y Vidrio, CSIC, Kelsen 5, 28049 Madrid (Spain); Cuello, G.J. [Institut Laue-Langevin, Boite Postale 156, 38042 Grenoble Cedex 9 (France); Ruessel, C. [Otto-Schott-Institut, Jena University, Fraunhoferstr. 6, 07743 Jena (Germany)


    A base glass of composition 3.5 Li{sub 2}O Bullet-Operator 0.15 Na{sub 2}O Bullet-Operator 0.2 K{sub 2}O Bullet-Operator 1.15 MgO Bullet-Operator 0.8 BaO Bullet-Operator 1.5 ZnO Bullet-Operator 20 Al{sub 2}O{sub 3} Bullet-Operator 67.2 SiO{sub 2} Bullet-Operator 2.6 TiO{sub 2} Bullet-Operator 1.7 ZrO{sub 2} Bullet-Operator 1.2 As{sub 2}O{sub 3} (in wt.%), melted and provided by SCHOTT AG (Mainz), was used to study the crystallisation mechanism of lithium alumino-silicate glass employing X-ray diffraction combined with neutron diffraction and non-isothermal differential scanning calorimetry (DSC). A high-quartz solid solution of LiAlSi{sub 2}O{sub 6} with nanoscaled crystals forms at 750 Degree-Sign C. Quantitative Rietveld refinement of samples annealed at 750 Degree-Sign C for 8 h determined a crystallised fraction of around 59 wt.%. The room temperature crystallised phase adopts an ordered, {beta}-eucryptite-like structure (2 Multiplication-Sign 2 Multiplication-Sign 2 cell) with Li ordered in the structural channels. The Avrami parameter (n {approx} 4), calculated from DSC data using different theoretical approaches, indicates that bulk crystallisation occurs and that the number of nuclei increases during annealing. The activation energy of the crystallisation is 531 {+-} 20 kJ mol{sup -1}. - Highlights: Black-Right-Pointing-Pointer Nanoscaled high-quartz crystals from a multicomponent lithium alumino-silicate glass. Black-Right-Pointing-Pointer Combined X-ray and neutron diffraction structural refinement. Black-Right-Pointing-Pointer {beta}-Eucryptite-like structure (2 Multiplication-Sign 2 Multiplication-Sign 2 cell) with Li ordered in the structural channels. Black-Right-Pointing-Pointer 3-Dimensional bulk crystallisation mechanism with an increasing number of nuclei. Black-Right-Pointing-Pointer Usage and validation of an alternative approach to calculate the Avrami parameter.

  12. TiO{sub 2} on magnesium silicate monolith: effects of different preparation techniques on the photocatalytic oxidation of chlorinated hydrocarbons

    Cardona, Ana I.; Candal, Roberto; Sanchez, Benigno; Avila, Pedro; Rebollar, Moises


    In this article, the comparative results of the photocatalytic oxidation of trichloroethylene (TCE) alone and a mixture of chlorinated hydrocarbons (trichloroethylene, perchloroethylene and chloroform) in gas phase, obtained with three different monolithic catalysts in a flat reactor frontally illuminated with a Xenon lamp are presented. The three catalysts incorporate titanium dioxide (TiO{sub 2}) as active phase on a magnesium silicate support, by means of different procedures: (i) incorporation of commercial TiO{sub 2} powder into the silicate matrix ('massic monolith'); (ii) sol-gel coating of the silicate support; (iii) impregnation with a commercial TiO{sub 2} aqueous suspension of the same silicate support. In the first case, the massic monolith was made from a 50:50 w/w mixture of magnesium silicate and 'Titafrance G5' TiO{sub 2} powder. In the second case, a magnesium silicate monolith was coated with several layers of an aqueous TiO{sub 2} sol prepared from hydrolysis and condensation of titanium tetra-isopropoxide (Ti(OC{sub 3}H{sub 7}){sub 4}) in excess of acidified water (acid catalysis). The third catalyst was prepared by impregnating the same silicate support with several layers of 'Titafrance G5' TiO{sub 2} powder water suspension. All the catalysts were thermal treated under comparable conditions in order to fix the TiO{sub 2} active phase to the silicate support. Although the performance of the massic monolith was better than the sol-gel monolith, the latter is of great interest because this technique allows the chemical composition of the active films to be easily modified.

  13. Intercalation of Layered Silicates, Layered Double Hydroxides, and Lead Iodide: Synthesis, Characterization and Properties.

    Mehrotra, Vivek

    Layered silicates, layered double hydroxides, and lead iodide are lamellar solids that can incorporate guest species into the galleries between their layers. Various intercalated forms of these layered materials have been synthesized and their properties studied. The dielectric behavior of pristine fluorohectorite, a typical layered silicate, and Zn-Al layered double hydroxide is explained by considering the structural ordering and mobility of the intercalated water molecules, as well as models invoking fractal time processes and fractal structure. Intercalative polymerization of aniline and pyrrole into fluorohectorite leads to a multilayered structure consisting of single polymer chains alternately stacked with the 9.6 A thick silicate layers. The polymer chains are confined to the quasi two-dimensional interlayer space between the rigid host layers. The hybrid films exhibit highly anisotropic properties. The optical, electrical and mechanical behavior is discussed in terms of the molecular confinement of the polymer chains. Ethylenediamine functionalized C _{60} clusters have also been intercalated into fluorohectorite via an ion-exchange procedure. Intercalation results in an improved thermal stability of the functionalized C_{60} clusters. Rutherford backscattering spectrometry has been used to elucidate the mechanism of intercalative ion exchange of silver in muscovite mica, a layered silicate with a layer charge density of 2e per unit cell. It is proposed that ion-exchange progresses by intercalating successive galleries through the edges of the mica layers. Guest-host interactions have been studied in the system aniline-PbI_2. The optical and structural effects of aniline intercalation in lead iodide thin films is discussed. Intercalation leads to a large shift in the optical band gap of PbI_2. The observed change in band gap is not only due to the increased separation between the PbI_2 layers but also because of an electrostatic interaction between the


    Suyanta Suyanta


    Full Text Available The research about synthesis and characterization of MCM-41 from rice husk has been done. Silica (SiO2 was extracted from rice husk by refluxing with 3M hydrochloric solution at 80 °C for 3 h. The acid-leached rice husk was filtered, washed, dried and calcined at 650 °C for 6 h lead the rough powder of rice husk silica with light brown in color. Characterization was carried out by X-ray diffraction (XRD and FTIR spectroscopy method. Rice husk silica was dissolved into the sodium hydroxide solution leading to the solution of sodium silicate, and used as silica source for the synthesis of MCM-41. MCM-41 was synthesized by hydrothermal process to the mixture prepared from 29 g of distilled water, 8.67 g of cetyltrimethyl ammonium bromide (CTMAB, 9.31 g of sodium silicate solution, and amount mL of 1 M H2SO4. Hydrothermal process was carried out at 100 °C in a teflon-lined stainless steel autoclave heated in the oven for 36 h. The solid phase was filtered, then washed with deionised water, and dried in the oven at 100 °C for 2 h. The surfactant CTMAB was removed by calcination at 550 °C for 10 h with heating rate 2 °C/min. The as-synthesized and calcined crystals were characterized by using FTIR spectroscopy, X-ray diffraction and N2 physisorption methods. In order to investigate the effect of silica source, the same procedure was carried out by using pure sodium silicate as silica source. It was concluded that silica extracted from rice husk can be used as raw materials in the synthesis of MCM-41, there is no significant difference in crystallinity and pore properties when was compared to material produced from commercial sodium silicate.

  15. Optical Properties of Astronomical Silicates in the Far-infrared

    Rinehart, Stephen A,; Benford, Dominic J.; Dwek, Eli; Henry, Ross M.; Nuth, Joseph A., III; Silverberg, Robert f.; Wollack, Edward J.


    Correct interpretation of a vast array of astronomical data relies heavily on understanding the properties of silicate dust as a function of wavelength, temperature, and crystallinity. We introduce the QPASI-T (Optical Properties of Astronomical Silicates with Infrared Techniques) project to address the need for high fidelity optical characterization data on the various forms of astronomical dust. We use two spectrometers to provide extinction data for silicate samples across a wide wavelength range (from the near infrared to the millimeter). New experiments are in development that will provide complementary information on the emissivity of our samples, allowing us to complete the optical characterization of these dust materials. In this paper, we present initial results from several materials including amorphous iron silicate, magnesium silicate and silica smokes, over a wide range of temperatures, and discuss the design and operation of our new experiments.

  16. Matrix inequalities

    Zhan, Xingzhi


    The main purpose of this monograph is to report on recent developments in the field of matrix inequalities, with emphasis on useful techniques and ingenious ideas. Among other results this book contains the affirmative solutions of eight conjectures. Many theorems unify or sharpen previous inequalities. The author's aim is to streamline the ideas in the literature. The book can be read by research workers, graduate students and advanced undergraduates.

  17. Organic modification of layered silicates. Structural and thermal characterizations

    Prado, L.A.S. de A.; Schulte, K. [Polymer Composites, Denickstrasse 15, TU Hamburg-Harburg, D-21073 Hamburg (Germany); Karthikeyan, C.S.; Nunes, S.P. [Institute of Chemistry, GKSS Research Centre, Max-Planck Strasse 1, D-21502 Geesthacht (Germany); De Torriani, Iris L. [Instituto de Fisica Gleb Wataghin, Universidade Estadual de Campinas, Cidade Universitaria Zeferino Vaz, CEP 13083-970, Campinas-SP (Brazil)


    Organic modification of natural and synthetic layered silicates namely montmorillonite and laponite is reported in this work. The modified silicates are being subsequently used in the preparation of nano-composite membranes based on ionomers for fuel cells application. Laponite, an entirely synthetic silicate, was modified using organosiloxanes containing imidazole groups. Two different strategies were adopted for modification: (a) swelling of the silicate in 2-butanone followed by functionalization using the siloxane at room temperature, (b) direct reaction between laponite and the organosiloxane in xylene at 120{sup o}C. Montmorillonite, a natural silicate, was supplied in the alkyl-ammonium form containing -OH groups. The modification of this silicate was conducted following the procedure (b). The structures of both plain and modified silicates were investigated by XRD showing that the interlayer distance (around 17A) was not affected during the functionalization of laponite. However, a noticeable increase in the interlayer distance from 18.0A to 24.5A was observed for the modified montmorillonite. This clearly shows the presence of polysiloxane chains in between the silicate layers. Further characterization showed that the modification of these silicates was in the range between 16% and 23% (molar percentage). TGA was done between 25 and 300{sup o}C in order to study the thermal degradation pattern of the silicates. The amount of adsorbed water could be determined from the results. The functionalization reduced the adsorption of water from 13.5% to 6.8% for laponite and from 8.5% to 4% for montmorillonite.

  18. The incorporation of an organically modified layered silicate in monolithic polymeric matrices produced using hot melt extrusion

    Lyons, John G. [Centre for Biopolymer and Biomolecular Research, Athlone Institute of Technology, Dublin Road, Athlone, Co. Westmeath (Ireland)]. E-mail:; Holehonnur, Harshad [Centre for Biopolymer and Biomolecular Research, Athlone Institute of Technology, Dublin Road, Athlone, Co. Westmeath (Ireland)]. E-mail:; Devine, Declan M. [Centre for Biopolymer and Biomolecular Research, Athlone Institute of Technology, Dublin Road, Athlone, Co. Westmeath (Ireland)]. E-mail:; Kennedy, James E. [Centre for Biopolymer and Biomolecular Research, Athlone Institute of Technology, Dublin Road, Athlone, Co. Westmeath (Ireland)]. E-mail:; Geever, Luke M. [Centre for Biopolymer and Biomolecular Research, Athlone Institute of Technology, Dublin Road, Athlone, Co. Westmeath (Ireland)]. E-mail:; Blackie, Paul [Centre for Biopolymer and Biomolecular Research, Athlone Institute of Technology, Dublin Road, Athlone, Co. Westmeath (Ireland)]. E-mail:; Higginbotham, Clement L. [Centre for Biopolymer and Biomolecular Research, Athlone Institute of Technology, Dublin Road, Athlone, Co. Westmeath (Ireland)]. E-mail:


    The body of work described in this research paper outlines the use of nanoclay particles as a novel filler material in a hot melt extruded monolithic polymer matrix for oral drug delivery. Several batches of matrix material were prepared with Carvedilol used as the active pharmaceutical ingredient. An organically modified layered silicate was used as the filler material at various levels of inclusion. The resultant matrices were characterised using steady state parallel plate rheometry, differential scanning calorimetry (DSC), atomic force microscopy (AFM), mechanical testing, and dissolution testing. The mechanical analysis indicated that the nanoclay filler incorporation resulted in an increase in all of the mechanical properties of the matrix. Dissolution analysis showed that the presence of the filler particles resulted in a slower release rate of API than for the matrix alone. The results detailed within this paper indicate that nanoclay materials are an interesting prospect for use as filler materials for extended release hot melt produced dosage forms.

  19. Disordered Silicates in Space: a Study of Laboratory Spectra of "Amorphous" Silicates

    Speck, Angela K; Hofmeister, Anne M


    We present a laboratory study of silicate glasses of astrophysically relevant compositions including olivines, pyroxenes and melilites. With emphasis on the classic Si-O stretching feature near 10 microns, we compare infrared spectra of our new samples with laboratory spectra on ostensibly similar compositions, and also with synthetic silicate spectral data commonly used in dust modeling. Several different factors affect spectral features including sample chemistry (e.g., polymerization, Mg/Fe ratio, oxidation state and Al-content) and different sample preparation techniques lead to variations in porosity, density and water content. The convolution of chemical and physical effects makes it difficult to attribute changes in spectral parameters to any given variable. It is important that detailed chemical and structural characterization be provided along with laboratory spectra. In addition to composition and density, we measured the glass transition temperatures for the samples which place upper limits on the ...

  20. Microstructure and optical properties of Pr3+-doped hafnium silicate films


    In this study, we report on the evolution of the microstructure and photoluminescence properties of Pr3+-doped hafnium silicate thin films as a function of annealing temperature (TA). The composition and microstructure of the films were characterized by means of Rutherford backscattering spectrometry, spectroscopic ellipsometry, Fourier transform infrared absorption, and X-ray diffraction, while the emission properties have been studied by means of photoluminescence (PL) and PL excitation (PLE) spectroscopies. It was observed that a post-annealing treatment favors the phase separation in hafnium silicate matrix being more evident at 950°C. The HfO2 phase demonstrates a pronounced crystallization in tetragonal phase upon 950°C annealing. Pr3+ emission appeared at TA = 950°C, and the highest efficiency of Pr3+ ion emission was detected upon a thermal treatment at 1,000°C. Analysis of the PLE spectra reveals an efficient energy transfer from matrix defects towards Pr3+ ions. It is considered that oxygen vacancies act as effective Pr3+ sensitizer. Finally, a PL study of undoped HfO2 and HfSiOx matrices is performed to evidence the energy transfer. PMID:23336520

  1. Interstellar Silicate Dust in the z=0.89 Absorber Towards PKS 1830-211: Crystalline Silicates at High Redshift?

    Aller, Monique C; York, Donald G; Vladilo, Giovanni; Welty, Daniel E; Som, Debopam


    We present evidence of a >10-sigma detection of the 10 micron silicate dust absorption feature in the spectrum of the gravitationally lensed quasar PKS 1830-211, produced by a foreground absorption system at redshift 0.886. We have examined more than 100 optical depth templates, derived from both observations of Galactic and extragalactic sources and laboratory measurements, in order to constrain the chemical structure of the silicate dust. We find that the best fit to the observed absorption profile is produced by laboratory crystalline olivine, with a corresponding peak optical depth of tau_10=0.27+/-0.05. The fit is slightly improved upon by including small contributions from additional materials such as silica, enstatite, or serpentine, which suggests that the dust composition may consist of a blend of crystalline silicates. Combining templates for amorphous and crystalline silicates, we find that the fraction of crystalline silicates needs to be at least 95%. Given the rarity of extragalactic sources wit...

  2. Synthesis and application of Fe3O4@SiO2@TiO2 for photocatalytic decomposition of organic matrix simultaneously with magnetic solid phase extraction of heavy metals prior to ICP-MS analysis.

    Habila, Mohamed A; ALOthman, Zeid A; El-Toni, Ahmed Mohamed; Labis, Joselito Puzon; Soylak, Mustafa


    Interference of organic compounds in the matrix of heavy metal solution could suppress their pre-concentration and detection processes. Therefore, this work aimed to develop simple and facile methods for separation of heavy metals before ICP-MS analysis. Fe3O4@SiO2@TiO2 core-double shell magnetic adsorbent was prepared and characterized by TEM, SEM, FTIR, XRD and surface area, and tested for Magnetic Solid Phase Extraction (MSPE) of Cu(II), Zn(II), Cd(II) and Pb(II). TEM micrograph of Fe3O4@SiO2@TiO2 reveals the uniform coating of TiO2 layer of about 20nm onto the Fe3O4@SiO2 nanoparticles and indicates that all nanoparticles are monodispersed and uniform. The saturation magnetization from the room-temperature hysteresis loops of Fe3O4 and Fe3O4@SiO2@TiO2 was found to be 72 and 40emug(-1), respectively, suggesting good separability of the nanoparticles. The Fe3O4@SiO2@TiO2 showed maximum adsorption capacity of 125, 137, 148 and 160mgg(-1) for Cu(II), Zn(II), Cd(II) and Pb(II) respectively, and the process was found to fit with the second order kinetic model and Langmuir isotherm. Fe3O4@SiO2@TiO2 showed efficient photocatalytic decomposition for tartrazine and sunset yellow (consider as Interfering organic compounds) in aqueous solution under the irradiation of UV light. The maximum recovery% was achieved at pH 5, by elution with 10mL of 2M nitric acid solution. The LODs were found to be 0.066, 0.049, 0.041 and 0.082µgL(-1) for Cu(II), Zn(II), Cd(II) and Pb(II), respectively while the LOQs were found to be 0.20, 0.15, 0.12 and 0.25µgL(-1) for Cu(II), Zn(II), Cd(II) and Pb(II), respectively. Copyright © 2016 Elsevier B.V. All rights reserved.


    Aller, Monique C.; Kulkarni, Varsha P.; Som, Debopam [Department of Physics and Astronomy, University of South Carolina, 712 Main Street, Columbia, SC 29208 (United States); York, Donald G.; Welty, Daniel E. [Department of Astronomy and Astrophysics, University of Chicago, 5640 S. Ellis Ave., Chicago, IL 60637 (United States); Vladilo, Giovanni, E-mail: [Osservatorio Astonomico di Trieste, Via Tiepolo 11, 34143 Trieste (Italy)


    We present evidence of a >10{sigma} detection of the 10 {mu}m silicate dust absorption feature in the spectrum of the gravitationally lensed quasar PKS 1830-211, produced by a foreground absorption system at redshift 0.886. We have examined more than 100 optical depth templates, derived from both observations of Galactic and extragalactic sources and laboratory measurements, in order to constrain the chemical structure of the silicate dust. We find that the best fit to the observed absorption profile is produced by laboratory crystalline olivine, with a corresponding peak optical depth of {tau}{sub 10} = 0.27 {+-} 0.05. The fit is slightly improved upon by including small contributions from additional materials, such as silica, enstatite, or serpentine, which suggests that the dust composition may consist of a blend of crystalline silicates. Combining templates for amorphous and crystalline silicates, we find that the fraction of crystalline silicates needs to be at least 95%. Given the rarity of extragalactic sources with such a high degree of silicate crystallinity, we also explore the possibility that the observed spectral features are produced by amorphous silicates in combination with other molecular or atomic transitions, or by foreground source contamination. While we cannot rule out these latter possibilities, they lead to much poorer profile fits than for the crystalline olivine templates. If the presence of crystalline interstellar silicates in this distant galaxy is real, it would be highly unusual, given that the Milky Way interstellar matter contains essentially only amorphous silicates. It is possible that the z = 0.886 absorber toward PKS 1830-211, well known for its high molecular content, has a unique star-forming environment that enables crystalline silicates to form and prevail.

  4. Behavior of calcium silicate hydrate in aluminate solution

    LI Xiao-bin; ZHAO Zhuo; LIU Gui-hua; ZHOU Qiu-sheng; PENG Zhi-hong


    Using calcium hydroxide and sodium silicate as starting materials, two kinds of calcium silicate hydrates, CaO · SiO2 · H2O and 2CaO · SiO2 · 1.17H2O, were hydro-thermally synthesized at 120 ℃. The reaction rule of calcium silicate hydrate in aluminate solution was investigated. The result shows that CaO · SiO2 · H2O is more stable than 2CaO · SiO2 · 1.17H2 O in aluminate solution and its stability increases with the increase of reaction temperature but decreases with the increase of caustic concentration. The reaction between calcium silicate hydrate and aluminate solution is mainly through two routes. In the first case, Al replaces partial Si in calcium silicate hydrate, meanwhile 3CaO · Al2 O3 · xSiO2 · (6-2x) H2 O (hydro-garnet) is formed and some SiO2 enters the solution. In the second case, calcium silicate hydrate can react directly with aluminate solution, forming hydro-garnet and Na2O · Al2O3 · 2SiO2 · nH2O (DSP). The desilication reaction of aluminate solution containing silicate could contribute partially to forming DSP.

  5. Deep ocean biogeochemistry of silicic acid and nitrate

    Sarmiento, J. L.; Simeon, J.; Gnanadesikan, A.; Gruber, N.; Key, R. M.; Schlitzer, R.


    Observations of silicic acid and nitrate along the lower branch of the global conveyor belt circulation show that silicic acid accumulation by diatom opal dissolution occurs at 6.4 times the rate of nitrate addition by organic matter remineralization. The export of opal and organic matter from the surface ocean occurs at a Si:N mole ratio that is much smaller than this almost everywhere (cf. Sarmiento et al., 2004). The preferential increase of silicic acid over nitrate as the deep circulation progresses from the North Atlantic to the North Pacific is generally interpreted as requiring deep dissolution of opal together with shallow remineralization of organic matter (Broecker, 1991). However, Sarmiento et al. (2004) showed that the primary reason for the low silicic acid concentration of the upper ocean is that the waters feeding the main thermocline from the surface Southern Ocean are depleted in silicic acid relative to nitrate. By implication, the same Southern Ocean processes that deplete the silicic acid in the surface Southern Ocean must also be responsible for the enhanced silicic acid concentration of the deep ocean. We use observations and results from an updated version of the adjoint model of Schlitzer (2000) to confirm that this indeed the case.

  6. The shape and composition of interstellar silicate grains

    Min, M; De Koter, A; Hovenier, J W; Keller, L P; Markwick-Kemper, F


    We investigate the composition and shape distribution of silicate dust grains in the interstellar medium. The effect of the amount of magnesium in the silicate lattice is studied. We fit the spectral shape of the interstellar 10 mu extinction feature as observed towards the galactic center. We use very irregularly shaped coated and non-coated porous Gaussian Random Field particles as well as a statistical approach to model shape effects. For the dust materials we use amorphous and crystalline silicates with various composition and SiC. The results of our analysis of the 10 mu feature are used to compute the shape of the 20 mu silicate feature and to compare this with observations. By using realistic particle shapes we are, for the first time, able to derive the magnesium fraction in interstellar silicates. We find that the interstellar silicates are highly magnesium rich (Mg/(Fe+Mg)>0.9) and that the stoichiometry lies between pyroxene and olivine type silicates. This composition is not consistent with that o...

  7. Reagentless and calibrationless silicate measurement in oceanic waters.

    Giraud, William; Lesven, Ludovic; Jońca, Justyna; Barus, Carole; Gourdal, Margaux; Thouron, Danièle; Garçon, Véronique; Comtat, Maurice


    Determination of silicate concentration in seawater without addition of liquid reagents was the key prerequisite for developing an autonomous in situ electrochemical silicate sensor (Lacombe et al., 2007) [11]. The present challenge is to address the issue of calibrationless determination. To achieve such an objective, we chose chronoamperometry performed successively on planar microelectrode (ME) and ultramicroelectrode (UME) among the various possibilities. This analytical method allows estimating simultaneously the diffusion coefficient and the concentration of the studied species. Results obtained with ferrocyanide are in excellent agreement with values of the imposed concentration and diffusion coefficient found in the literature. For the silicate reagentless method, successive chronoamperometric measurements have been performed using a pair of gold disk electrodes for both UME and ME. Our calibrationless method was tested with different concentrations of silicate in artificial seawater from 55 to 140×10(-6) mol L(-1). The average value obtained for the diffusion coefficient of the silicomolybdic complex is 2.2±0.4×10(-6) cm(2) s(-1), consistent with diffusion coefficient values of molecules in liquid media. Good results were observed when comparing known concentration of silicate with experimentally derived ones. Further work is underway to explore silicate determination within the lower range of oceanic silicate concentration, down to 0.1×10(-6) mol L(-1). Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Matrix analysis

    Bhatia, Rajendra


    A good part of matrix theory is functional analytic in spirit. This statement can be turned around. There are many problems in operator theory, where most of the complexities and subtleties are present in the finite-dimensional case. My purpose in writing this book is to present a systematic treatment of methods that are useful in the study of such problems. This book is intended for use as a text for upper division and gradu­ ate courses. Courses based on parts of the material have been given by me at the Indian Statistical Institute and at the University of Toronto (in collaboration with Chandler Davis). The book should also be useful as a reference for research workers in linear algebra, operator theory, mathe­ matical physics and numerical analysis. A possible subtitle of this book could be Matrix Inequalities. A reader who works through the book should expect to become proficient in the art of deriving such inequalities. Other authors have compared this art to that of cutting diamonds. One first has to...

  9. Resolving the stellar sources of isotopically rare presolar silicate grains through Mg and Fe isotopic analyses

    Nguyen, Ann N.; Messenger, Scott, E-mail: [Robert M. Walker Laboratory for Space Science, Astromaterials Research and Exploration Science Directorate, NASA Johnson Space Center, Houston, TX 77058 (United States)


    We conducted multi-element isotopic analyses of 11 presolar silicate grains from the Acfer 094 meteorite having unusual O isotopic compositions. Eight grains are {sup 18}O-rich, one is {sup 16}O-rich, and two are extremely {sup 17}O-rich. We constrained the grains' stellar sources by measuring their Si and Mg isotopic ratios, and also the {sup 54}Fe/{sup 56}Fe and {sup 57}Fe/{sup 56}Fe ratios for five grains. The Mg and Fe isotopic measurements were conducted after surrounding matrix grains were removed for more accurate ratios. Most of the {sup 18}O-rich silicates had anomalous Mg isotopic ratios, and their combined isotopic constraints are consistent with origins in low-mass Type II supernovae (SNe II) rather than high-metallicity stars. The isotopic ratios of the {sup 16}O-rich silicate are also consistent with an SN origin. Mixing small amounts of interior stellar material with the stellar envelope replicated all measured isotopic ratios except for {sup 29}Si/{sup 28}Si and {sup 54}Fe/{sup 56}Fe in some grains. The {sup 29}Si/{sup 28}Si ratios of all SN-derived grains are matched by doubling the {sup 29}Si yield in the Ne- and Si-burning zones. The {sup 54}Fe/{sup 56}Fe ratios of the grains imply elemental fractionation in the Si/S zone, or introduction of isotopically solar Fe by secondary processing. The two highly {sup 17}O-rich silicates exhibited significant {sup 25}Mg and/or {sup 26}Mg enrichments and their isotopic ratios are best explained by strong dilution of 1.15 M {sub ☉} CO nova matter. We estimate that ∼12% and 1% of presolar silicates have SN and nova origins, respectively, similar to presolar SiC and oxides. This implies that asymptotic giant branch stars are the dominant dust producers in the galaxy.

  10. Contact fatigue mechanisms as a function of crystal aspect ratio in baria-silicate glass ceramics

    Suputtamongkol, Kallaya


    Ceramic materials are potentially useful for dental applications because of their esthetic potential and biocompatibility. However, the existence of fatigue damage in ceramics raises considerable concern regarding its effect on the life prediction of dental prostheses. During normal mastication, dental restorations are subjected to repeated loading more than a thousand times per day and relatively high clinical failure rates for ceramic prostheses have been reported. To simulate the intraoral loads, Hertzian indentation loading was used in this study to characterize the fatigue failure mechanisms of ceramic materials using clinically relevant parameters. The baria-silicate system was chosen because of the nearly identical composition between the crystal and the glass matrix. Little or no residual stress is expected from the elastic modulus and thermal expansion mismatches between the two phases. Crystallites with different aspect ratios can also be produced by controlled heat treatment schedules. The objective of this study was to characterize the effect of crystal morphology on the fatigue mechanisms of bariasilicate glass-ceramics under clinically relevant conditions. The results show that the failure of materials with a low toughness such as baria-silicate glass (0.7 MPa•m1/2) and glass-ceramic with an aspect ratio of 3/1 (1.3 MPa•m1/2) initiated from a cone crack developed during cyclic loading for 103 to 105 cycles. The mean strength values of baria-silicate glass and glass-ceramic with an aspect ratio of 3/1 decreased significantly as a result of the presence of a cone crack. Failure of baria-silicate glass-ceramics with an aspect ratio of 8/1 (Kc = 2.1 MPa•m1/2) was initiated from surface flaws caused by either polishing or cyclic loading. The gradual decrease of fracture stress was observed in specimens with an aspect ratio of 8/1 after loading in air for 103 to 10 5 cycles. A reduction of approximately 50% in fracture stress levels was found for

  11. Functional substitution of coordination polyhedron in crystal structure of silicates

    叶大年; 马哲生; 赫伟; 李哲; 施倪承; D.Pushcharovsky


    On the bases of the study of comparative crystal chemistry of silicates it has been concluded that the octahedra and square pyramids of Ti-0 and Zr-O play functional role of tetrahedra of Si-O in the construction of crystal structures. Therefore, those silicates may be named titano-and zircono-silicates. Because of the functional similarity of coordination polyhedra, the structures of cristobalite and feldspar have been compared with those of perovskite and garnet, respectively. As a new concept, the functional replacement of tetrahedra by octahedra and/or pyramids is defined by the authors of this paper for favorable comparison of relative crystal structures.

  12. Sensitized photoluminescence of erbium silicate synthesized on porous silicon framework

    Shen, Hao; Xu, Lingbo; Li, Dongsheng; Yang, Deren


    Er silicate/porous silicon (PS) composites with effective sensitized erbium emission at 1.53 μm have been synthesized on the PS framework. Cross-sectional scanning electron microscopy and X-ray diffraction reveal that the PS is coated by Er silicate in composites. Indirect excitation of Er3+ ion luminescence via energy transfer from PS is confirmed. The temperature dependence of Er-related photoluminescence intensity and lifetime is investigated, which concludes a phonon-mediated energy transfer process. The combination of the PS framework and Er silicate provides a possible strategy for practical silicon-based light sources.

  13. Fire Resistance of Wood Impregnated with Soluble Alkaline Silicates

    Carlos Alberto Giudice


    Full Text Available The aim of this paper is to determine the fire performance of wood panels (Araucaria angustifolia impregnated with soluble alkaline silicates. Commercial silicates based on sodium and potassium with 2.5/1.0 and 3.0/1.0 silica/alkali molar ratios were selected; solutions and glasses were previously characterized. Experimental panels were tested in a limiting oxygen chamber and in a two-foot tunnel. Results displayed a high fire-retardant efficiency using some soluble silicates.

  14. Journal of the Chinese Silicate Society (Selected Articles).



  15. Core-shell Au/Ag nanoparticles embedded in silicate sol-gel network for sensor application towards hydrogen peroxide

    Shanmugam Manivannan; Ramasamy Ramaraj


    The electrocatalytic activity of core-shell Au100-Ag ( = 15, 27, 46, and 60) bimetallic nanoparticles embedded in methyl functionalized silicate MTMOS network towards the reduction of hydrogen peroxide was investigated by using cyclic voltammetry and chronoamperometric techniques. Core-shell Au/Ag bimetallic nanoparticles were characterized by absorption spectra and HRTEM. The MTMOS silicate sol-gel embedded Au73Ag27 core-shell nanoparticles modified electrode showed better synergistic electrocatalytic effect towards the reduction of hydrogen peroxide when compared to monometal MTMOS-Aunps and MTMOS-Agnps modified electrodes. These modified electrodes were studied without immobilizing any enzyme in the MTMOS sol-gel matrix. The present study highlights the influence of molar composition of Ag nanoparticles in the Au/Ag bimetallic composition towards the electrocatalytic reduction and sensing of hydrogen peroxide in comparison to monometal Au and Ag nanoparticles.

  16. Matrix pentagons

    Belitsky, A V


    The Operator Product Expansion for null polygonal Wilson loop in planar maximally supersymmetric Yang-Mills theory runs systematically in terms of multiparticle pentagon transitions which encode the physics of excitations propagating on the color flux tube ending on the sides of the four-dimensional contour. Their dynamics was unravelled in the past several years and culminated in a complete description of pentagons as an exact function of the 't Hooft coupling. In this paper we provide a solution for the last building block in this program, the SU(4) matrix structure arising from internal symmetry indices of scalars and fermions. This is achieved by a recursive solution of the Mirror and Watson equations obeyed by the so-called singlet pentagons and fixing the form of the twisted component in their tensor decomposition. The non-singlet, or charged, pentagons are deduced from these by a limiting procedure.

  17. Viscosity model for fully liquid silicate melt

    Zhang Guo-Hua


    Full Text Available A model for estimating the viscosity of silicate melt as derived in our previous paper is extended to the system containing MgO, CaO, SrO, BaO, Li2O, Na2O, K2O, which can express the nonlinear variation of activation energy of viscosity with the composition. It is found that the optimized parameters of model which characterize the deforming ability of bonds around non-bridging oxygen decrease with increasing the bond strength of M-O bond expressed by I=2Q/RMz+ + rO2-2 (where Q is the valence of cation M; r is the radius. It is pointed out that viscosity is not only determined by the bond strength, but also by the radius of cation which is defined as the size effect. The radius of cation plays paradox roles in the two factors: smaller radius leads to a stronger bond, thus a higher viscosity; while cations with smaller radius are easier to diffuse when neglecting the interaction force, thus a lower viscosity will be.

  18. Hardness and incipient plasticity in silicate glasses

    Kjeldsen, Jonas; Smedskjær, Morten Mattrup; Mauro, John C.;


    The scaling of Vickers hardness (Hv) in oxide glasses with varying network modifier/modifier ratio is manifested as either a positive or negative deviation from linearity with a maximum deviation at the ratio of about 1:1. In an earlier study [J. Kjeldsen et al., J. Non-Cryst. Solids 369,61(2013)......The scaling of Vickers hardness (Hv) in oxide glasses with varying network modifier/modifier ratio is manifested as either a positive or negative deviation from linearity with a maximum deviation at the ratio of about 1:1. In an earlier study [J. Kjeldsen et al., J. Non-Cryst. Solids 369...

  19. Silicate Urolithiasis during Long-Term Treatment with Zonisamide

    Satoru Taguchi


    Full Text Available Silicate urinary calculi are rare in humans, with an incidence of 0.2% of all urinary calculi. Most cases were related to excess ingestion of silicate, typically by taking magnesium trisilicate as an antacid for peptic ulcers over a long period of time; however, there also existed unrelated cases, whose mechanism of development remains unclear. On the other hand, zonisamide, a newer antiepileptic drug, is one of the important causing agents of iatrogenic urinary stones in patients with epilepsy. The supposed mechanism is that zonisamide induces urine alkalinization and then promotes crystallization of urine components such as calcium phosphate by inhibition of carbonate dehydratase in renal tubular epithelial cells. Here, we report a case of silicate urolithiasis during long-term treatment with zonisamide without magnesium trisilicate intake and discuss the etiology of the disease by examining the silicate concentration in his urine.

  20. Properties of sodium silicate bonded sand hardened by microwave heating

    Wang Jina; Fan Zitian; Zan Xiaolei; Pan Di


    The sodium silicate bonded sand hardened by microwave heating has many advantages,such as low sodium silicate adding quantity,fast hardening speed,high room temperature strength,good collapsibility and certain surface stability. However,it has big moisture absorbability in the air,which would lead to the compression strength and the surface stability of the sand molds being sharply reduced. In this study,the moisture absorbability of the sodium silicate bonded sand hardened by microwave heating in different humidity conditions and the effect factors were investigated. Meanwhile,the reasons for the big moisture absorbability of the sand were analyzed.Some measures to overcome the problems of high moisture absorbability,bad surface stability and sharply reducing strength in the air were discussed. The results of this study establish the foundation of green and clean foundry technology based on the microwave heating hardening sodium silicate sand process.

  1. Polymer/layered silicates nanocomposites for barrier technology

    Labuschagne, Philip W


    Full Text Available -1 Intelligent Nanomaterials: Processes, Properties, and Applications February 2012/Chapter 13 Polymer/layered silicates nanocomposites for barrier technology Labuschagne, PW, Moolman, S and Maity, A. Corresponding author: PLabusch...

  2. Characterization of iron-phosphate-silicate chemical garden structures.

    Barge, Laura M; Doloboff, Ivria J; White, Lauren M; Stucky, Galen D; Russell, Michael J; Kanik, Isik


    Chemical gardens form when ferrous chloride hydrate seed crystals are added or concentrated solutions are injected into solutions of sodium silicate and potassium phosphate. Various precipitation morphologies are observed depending on silicate and phosphate concentrations, including hollow plumes, bulbs, and tubes. The growth of precipitates is controlled by the internal osmotic pressure, fluid buoyancy, and membrane strength. Additionally, rapid bubble-led growth is observed when silicate concentrations are high. ESEM/EDX analysis confirms compositional gradients within the membranes, and voltage measurements across the membranes during growth show a final potential of around 150-200 mV, indicating that electrochemical gradients are maintained across the membranes as growth proceeds. The characterization of chemical gardens formed with iron, silicate, and phosphate, three important components of an early earth prebiotic hydrothermal system, can help us understand the properties of analogous structures that likely formed at submarine alkaline hydrothermal vents in the Hadean-structures offering themselves as the hatchery of life.

  3. The crystalline fraction of interstellar silicates in starburst galaxies

    Kemper, F; Woods, Paul M


    We present a model using the evolution of the stellar population in a starburst galaxy to predict the crystallinity of the silicates in the interstellar medium of this galaxy. We take into account dust production in stellar ejecta, and amorphisation and destruction in the interstellar medium and find that a detectable amount of crystalline silicates may be formed, particularly at high star formation rates, and in case supernovae are efficient dust producers. We discuss the effect of dust destruction and amorphisation by supernovae, and the effect of a low dust-production efficiency by supernovae, and find that when taking this into account, crystallinity in the interstellar medium becomes hard to detect. Levels of 6.5-13% crystallinity in the interstellar medium of starburst galaxies have been observed and thus we conclude that not all these crystalline silicates can be of stellar origin, and an additional source of crystalline silicates associated with the Active Galactic Nucleus must be present.

  4. Spinning dust emission from ultrasmall silicates: emissivity and polarization spectrum

    Hoang, Thiem; Lan, Nguyen Quynh


    Anomalous microwave emission (AME) is an important Galactic foreground of Cosmic Microwave Background (CMB) radiation. It is believed that the AME arises from rotational emission by spinning polycyclic aromatic hydrocarbons (PAHs) in the interstellar medium (ISM). In this paper, we assume that a population of ultrasmall silicate grains may exist in the ISM, and quantify rotational emissivity from these tiny particles and its polarization spectrum. We found that spinning silicate nanoparticles can produce strong rotational emission when those small grains follow a log-normal size distribution. The polarization fraction of spinning dust emission from tiny silicates increases with decreasing the dipole moment per atom ($\\beta$) and can reach $P\\sim 20\\%$ for $\\beta\\sim 0.1$D at grain temperature of 60 K. We identify a parameter space $(\\beta,Y_{Si})$ for silicate nanoparticles in which its rotational emission can adequately reproduce both the observed AME and the polarization of the AME, without violating the ob...

  5. Determination of reactivity rates of silicate particle-size fractions

    Angélica Cristina Fernandes Deus; Leonardo Theodoro Büll; Juliano Corulli Corrêa; Roberto Lyra Villas Boas


    The efficiency of sources used for soil acidity correction depends on reactivity rate (RR) and neutralization power (NP), indicated by effective calcium carbonate (ECC). Few studies establish relative efficiency of reactivity (RER) for silicate particle-size fractions, therefore, the RER applied for lime are used. This study aimed to evaluate the reactivity of silicate materials affected by particle size throughout incubation periods in comparison to lime, and to calculate the RER for silicat...

  6. Synthesis and stability of {alpha}-tricalcium phosphate doped with dicalcium silicate in the system Ca{sub 3}(PO{sub 4}){sub 2}-Ca{sub 2}SiO{sub 4}

    Martinez, I.M., E-mail: [Instituto de Bioingenieria, Universidad Miguel Hernandez, Avda. de la Universidad s/n. 03202-Elche (Alicante) (Spain); Velasquez, P.A., E-mail: [Instituto de Bioingenieria, Universidad Miguel Hernandez, Avda. de la Universidad s/n. 03202-Elche (Alicante) (Spain); De Aza, P.N., E-mail: [Instituto de Bioingenieria, Universidad Miguel Hernandez, Avda. de la Universidad s/n. 03202-Elche (Alicante) (Spain)


    The aim of this study was to synthesize materials of {alpha}-tricalcium phosphate doped with small amounts of dicalcium silicate, by solid state reaction, at high temperature and slow cooling to room temperature. The obtained materials were characterized by X-ray diffraction, Scanning Electron Microscopy and Fourier Transform Infrared Spectroscopy, showing that there is a region between 0.5 and 4.0 wt.% of dicalcium silicate where solid solution {alpha}-tricalcium phosphate ({alpha}-TCPss) is stable to room temperature.

  7. Friction and Wear Behaviors of Nano-Silicates in Water

    Chen Boshui; Lou Fang; Fang Jianhua; Wang Jiu; Li Jia


    Nano-metric magnesium silicate and zinc silicate with particle size of about 50--70nm were prepared in water by the method of chemical deposition. The antiwear and friction reducing abilities of the nano-silicates, as well as their compos-ites with oleie acid tri-ethanolamine (OATEA), were evaluated on a four-ball friction tester. The topographies and tribochemical features of the worn surfaces were analyzed by scanning electron microscope (SEM) and X-ray photoelectron spectroscope (XPS). Results show that nano-silicates alone provide poor antiwear and friction reducing abilities in water, but exhibits excellent synergism with OATEA in reducing friction and wear. The synergism in reducing friction and wear between naao-silicates and OATEA does exist almost regardless of particle sizes and species, and may be attributed, on one hand, to the formation of an adsorption film of OATEA, and, on the other hand, to the formation oftdbochemical species of silicon dioxide and iron oxides on the friction surfaces. Tribo-reactions and tribo-adsorptions of nano-silicates and OATEA would produce hereby an effective composite boondary lubrication film, which could efficiently enhance the anti-wear and friction-reducing abilities of water.

  8. High Pressure/Temperature Metal Silicate Partitioning of Tungsten

    Shofner, G. A.; Danielson, L.; Righter, K.; Campbell, A. J.


    The behavior of chemical elements during metal/silicate segregation and their resulting distribution in Earth's mantle and core provide insight into core formation processes. Experimental determination of partition coefficients allows calculations of element distributions that can be compared to accepted values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Tungsten (W) is a moderately siderophile element and thus preferentially partitions into metal versus silicate under many planetary conditions. The partitioning behavior has been shown to vary with temperature, silicate composition, oxygen fugacity, and pressure. Most of the previous work on W partitioning has been conducted at 1-bar conditions or at relatively low pressures, i.e. <10 GPa, and in two cases at or near 20 GPa. According to those data, the stronger influences on the distribution coefficient of W are temperature, composition, and oxygen fugacity with a relatively slight influence in pressure. Predictions based on extrapolation of existing data and parameterizations suggest an increased pressured dependence on metal/ silicate partitioning of W at higher pressures 5. However, the dependence on pressure is not as well constrained as T, fO2, and silicate composition. This poses a problem because proposed equilibration pressures for core formation range from 27 to 50 GPa, falling well outside the experimental range, therefore requiring exptrapolation of a parametereized model. Higher pressure data are needed to improve our understanding of W partitioning at these more extreme conditions.

  9. X-ray photoelectron studies of the mechanism of iron silicate dissolution during weathering

    Schott, Jacques; Berner, Robert A.


    Iron silicate minerals (bronzite, fayalite), exposed to aqueous dissolution in the laboratory for up to 60 days at room temperature and pH 1, 1.5, and 6, have been studied for evidence of changes in surface composition, using XPS, and these results compared with those obtained from solution chemical analysis. In the absence of dissolved O 2 or at low pH (1-1.5) dissolution proceeds congruently after the initial formation of a thin (occupation by Fe +2 of more weakly bonded M 2 sites. The behavior of the layer is similar to that found earlier on iron-free pyroxene ( SCHOTTet al., 1981); in other words, because of its thinness and instability it is not diffusion-inhibiting or protective toward dissolution. In the presence of dissolved O 2, as would be the case in most weathering solutions, dissolution of bronzite and fayalite results in the formation of two surface layers whose compositions were deduced by measurements of XPS binding energies. The outer layer, consisting of hydrous ferric oxide, is readily removed by ultrasonic cleaning and, most likely, is not protective toward dissolution. The inner layer consists of Fe +3 in a protonated or hydroxylated silicate (Mg-silicate in the case of bronzite) matrix. This layer appears to impede dissolution over the time scale of the experiment as attested to by parabolic dissolution rates. However, the layer does not continue to grow on the time scale of weathering because ultrasonically cleaned soil grains ( BERNER and SCHOTT, 1982) exhibit surface compositions similar to those found in the present month-long laboratory experiments. In other words, a thick, highly altered, diffusion-inhibiting, protective surface layer does not form at the acidic pH of most soils.

  10. Calcium silicate ceramic scaffolds toughened with hydroxyapatite whiskers for bone tissue engineering

    Feng, Pei [State Key Laboratory of High Performance Complex Manufacturing, Central South University, Changsha 410083, PR China, (China); Wei, Pingpin [Cancer Research Institute, Central South University, Changsha 410078 (China); Li, Pengjian; Gao, Chengde [State Key Laboratory of High Performance Complex Manufacturing, Central South University, Changsha 410083, PR China, (China); Shuai, Cijun, E-mail: [State Key Laboratory of High Performance Complex Manufacturing, Central South University, Changsha 410083, PR China, (China); Department of Regenerative Medicine and Cell Biology, Medical University of South Carolina, Charleston, SC 29425 (United States); Peng, Shuping, E-mail: [Cancer Research Institute, Central South University, Changsha 410078 (China)


    Calcium silicate possessed excellent biocompatibility, bioactivity and degradability, while the high brittleness limited its application in load-bearing sites. Hydroxyapatite whiskers ranging from 0 to 30 wt.% were incorporated into the calcium silicate matrix to improve the strength and fracture resistance. Porous scaffolds were fabricated by selective laser sintering. The effects of hydroxyapatite whiskers on the mechanical properties and toughening mechanisms were investigated. The results showed that the scaffolds had a uniform and continuous inner network with the pore size ranging between 0.5 mm and 0.8 mm. The mechanical properties were enhanced with increasing hydroxyapatite whiskers, reached a maximum at 20 wt.% (compressive strength: 27.28 MPa, compressive Young's modulus: 156.2 MPa, flexural strength: 15.64 MPa and fracture toughness: 1.43 MPa·m{sup 1/2}) and then decreased by addition of more hydroxyapatite whiskers. The improvement of mechanical properties was due to whisker pull-out, crack deflection and crack bridging. Moreover, the degradation rate decreased with the increase of hydroxyapatite whisker content. A layer of bone-like apatite was formed on the scaffold surfaces after being soaked in simulated body fluid. Human osteoblast-like MG-63 cells spread well on the scaffolds and proliferated with increasing culture time. These findings suggested that the calcium silicate scaffolds reinforced with hydroxyapatite whiskers showed great potential for bone regeneration and tissue engineering applications. - Highlights: • HA whiskers were incorporated into CS to improve the properties. • The scaffolds were successfully fabricated by SLS. • Toughening mechanisms was whisker pull-out, crack deflection and bridging. • The scaffolds showed excellent apatite forming ability.

  11. Potassium silicate and calcium silicate on the resistance of soybean to Phakopsora pachyrhizi infection

    Maria Fernanda Cruz


    Full Text Available The control of Asian Soybean Rust (ASR, caused by Phakopsora pachyrhizi, has been difficult due to the aggressiveness of the pathogen and the lack of resistant cultivars. The objective of this study was to evaluate the effects of spray of potassium silicate (PS and soil amendment with calcium silicate (CS on soybean resistance to ASR. The PS solution was sprayed to leaves 24 hours prior to fungal inoculation while CS was amended to the soil at thirty-five days before sowing. The infection process of P. pachyrhizi was investigated by scanning electron microscopy. The uredia on leaves of plants sprayed with PS were smaller and more compact than those observed on the leaves of plants grown in soil amended with CS or in soil non-amended with CS (control treatment. On leaves of plants from the control treatment, uredia produced many urediniospores at 9 days after inoculation, and the ASR severity was 15, 8 and 9%, respectively, for plants from control, PS and CS treatments. In conclusion, the spray of PS contributed to reduce the number of uredia per cm² of leaf area and both PS spray and CS resulted in lower ASR symptoms.


    Wurm, Gerhard [Fakultaet fuer Physik, Universitaet Duisburg-Essen, Lotharstr. 1, D-47057 Duisburg (Germany); Trieloff, Mario [Institut fuer Geowissenschaften, Universitaet Heidelberg, Im Neuenheimer Feld 234-236, D-69120 Heidelberg (Germany); Rauer, Heike, E-mail: [Institut fuer Planetenforschung, Extrasolare Planeten und Atmosphaeren, Deutsches Zentrum fuer Luft- und Raumfahrt (DLR), Rutherfordstrasse 2, D-12489 Berlin (Germany)


    Mercury's high uncompressed mass density suggests that the planet is largely composed of iron, either bound within metal (mainly Fe-Ni) or iron sulfide. Recent results from the MESSENGER mission to Mercury imply a low temperature history of the planet which questions the standard formation models of impact mantle stripping or evaporation to explain the high metal content. Like Mercury, the two smallest extrasolar rocky planets with mass and size determination, CoRoT-7b and Kepler-10b, were found to be of high density. As they orbit close to their host stars, this indicates that iron-rich inner planets might not be a nuisance of the solar system but be part of a general scheme of planet formation. From undifferentiated chondrites, it is also known that the metal to silicate ratio is highly variable, which must be ascribed to preplanetary fractionation processes. Due to this fractionation, most chondritic parent bodies-most of them originated in the asteroid belt-are depleted in iron relative to average solar system abundances. The astrophysical processes leading to metal silicate fractionation in the solar nebula are essentially unknown. Here, we consider photophoretic forces. As these forces particularly act on irradiated solids, they might play a significant role in the composition of planetesimals forming at the inner edge of protoplanetary disks. Photophoresis can separate high thermal conductivity materials (iron) from lower thermal conductivity solids (silicate). We suggest that the silicates are preferentially pushed into the optically thick disk. Subsequent planetesimal formation at the edge moving outward leads to metal-rich planetesimals close to the star and metal depleted planetesimals farther out in the nebula.

  13. Experimental investigation of the partitioning of phosphorus between metal and silicate phases - Implications for the earth, moon and eucrite parent body

    Newsom, H. E.; Drake, M. J.


    An experimental study is reported of the partitioning of Phosphorus between solid metal and basaltic silicate liquid as a function of temperature and oxygen fugacity and of the implications for the earth, moon and eucrite parent body (EPB). The relationship established between the partition coefficient and the fugacity is given at 1190 C by log D(P) = -1.12 log fO2 - 15.95 and by log D(P) = -1.53 log fO2 17.73 at 1300 C. The partition coefficient D(P) was determined, and it is found to be consistent with a valence state of 5 for P in the molten silicate. Using the determined coefficient the low P/La ratios of the earth, moon, and eucrites relative to C1 chondrites can be explained. The lowering of the P/La ratio in the eucrites relative to Cl chondrite by a factor of 40 can be explained by partitioning P into 20-25 wt% sulfur-bearing metallic liquid corresponding to 5-25% of the total metal plus silicate system. The low P/La and W/La ratios in the moon may be explained by the partitioning of P and W into metal during formation of a small core by separation of liquid metal from silicate at low degrees of partial melting of the silicates. These observations are consistent with independent formation of the moon and the earth.

  14. Partitioning coefficients between olivine and silicate melts

    Bédard, J. H.


    Variation of Nernst partition coefficients ( D) between olivine and silicate melts cannot be neglected when modeling partial melting and fractional crystallization. Published natural and experimental olivine/liquidD data were examined for covariation with pressure, temperature, olivine forsterite content, and melt SiO 2, H 2O, MgO and MgO/MgO + FeO total. Values of olivine/liquidD generally increase with decreasing temperature and melt MgO content, and with increasing melt SiO 2 content, but generally show poor correlations with other variables. Multi-element olivine/liquidD profiles calculated from regressions of D REE-Sc-Y vs. melt MgO content are compared to results of the Lattice Strain Model to link melt MgO and: D0 (the strain compensated partition coefficient), EM3+ (Young's Modulus), and r0 (the size of the M site). Ln D0 varies linearly with Ln MgO in the melt; EM3+ varies linearly with melt MgO, with a dog-leg at ca. 1.5% MgO; and r0 remains constant at 0.807 Å. These equations are then used to calculate olivine/liquidD for these elements using the Lattice Strain Model. These empirical parameterizations of olivine/liquidD variations yield results comparable to experimental or natural partitioning data, and can easily be integrated into existing trace element modeling algorithms. The olivine/liquidD data suggest that basaltic melts in equilibrium with pure olivine may acquire small negative Ta-Hf-Zr-Ti anomalies, but that negative Nb anomalies are unlikely to develop. Misfits between results of the Lattice Strain Model and most light rare earth and large ion lithophile partitioning data suggest that kinetic effects may limit the lower value of D for extremely incompatible elements in natural situations characterized by high cooling/crystallization rates.

  15. An Atomistic Study of the Incorporation and Diffusion of Noble Gases in Silicate Minerals

    Pinilla, C.; Valencia, K.; Martinez-Mendoza, C.; Allan, N.


    Trace elements are widely used to unravel magmatic processes and constrain the chemical differentiation of the Earth. Central to this enterprise is understanding the controls on trace element fractionation between solid and liquid phases and thus the energetics of incorporating trace elements into crystals. In this contribution we focus on the incorporation of noble gases into crystals, with implications for the degassing processes in the Earth and the atmosphere. We use both ab-initio and classical calculations using interatomic potentials to study the uptake of the noble gases He, Ne and Ar into solid silicates. We calculate atomic defect energies of incorporation both at vacancies and at interstitial positions in solid forsterite. We use these energies to estimate the total uptake of the noble gases bulk into the crystal as a function of temperature. Such concentrations are found to be very low (10-3 and 10-10 ppm) for He up to Ar respectively with the noble gases incorporated predicted to be more favorable at intrinsic vacancies of Si or Mg or at interstitials sites. We also look at the diffusion of these minerals within the lattice and estimate activation energies for such processes. Our results support the hypothesis that noble gases have very low solubilities in bulk solid minerals. Other mechanisms such as adsorption at internal and external interfaces, voids and grain boundaries that can play a mayor role in their storage are also briefly discussed.

  16. Modeling of heat evolution in silicate building materials with electrically conductive admixtures

    Fiala, Lukáš; Maděra, Jiří; Vejmelková, Eva; Černý, Robert


    Silicate building materials are electrically non-conductive, in general. However, a sufficient amount of electrically conductive admixtures can significantly increase their electrical conductivity. Consequently, new practical applications of such materials are available. Materials with enhanced electrical properties can be used as self-sensing sensors monitoring evolution of cracks, electromagnetic shields or cores of deicing systems. This paper deals with the modeling of heat evolution in silicate building materials by the action of passing electric current. Due to the conducting paths formed in the material's matrix by adding a sufficient amount of electrically conductive admixture and applying electric voltage on the installed electrodes, electric current is passing through the material. Thanks to the electric current, Joule heat is successively evolved. As it is crucial to evaluate theoretically the amount of evolved heat in order to assess the effectiveness of such a system, a model describing the Joule heat evolution is proposed and a modeling example based on finite-element method is introduced.

  17. Stable isotope analysis of molecular oxygen from silicates and oxides using CO2 laser extraction

    Perry, Eugene


    A laser-excited system for determination of the oxygen isotope composition of small quantities of silicate and oxide minerals was constructed and tested at JSC. This device is the first reported to use a commercially available helium cryostat to transfer and purify oxygen gas quantitatively within the system. The system uses oxygen gas instead of the conventional CO2 for mass spectrometer analyses. This modification of technique permits determination of all three stable oxygen isotopes, an essential requirement for oxygen isotope analysis of meteoritic material. Tests of the system included analysis of standard silicate materials NBS 28 and UWMG2 garnet, six SNC meteorites, and inclusions and chondrules from the Allende meteorite. Calibration with terrestrial standards was excellent. Meteorite values are close to published values and show no evidence of terrestrial oxygen contamination. The one limitation observed is that, in some runs on fine-grained SNC matrix material, sample results were affected by other samples in the sample holder within the reaction chamber. This reemphasizes the need for special precautions in dealing with fine-grained, reactive samples. Performance of the JSC instrument compares favorably with that of any other instrument currently producing published oxygen isotope data.

  18. Trends in Effective Diffusion Coefficients for Ion-Exchange Strengthening of Soda-Lime-Silicate Glasses

    Stefan Karlsson


    Full Text Available Monovalent cations enable efficient ion-exchange processes due to their high mobility in silicate glasses. Numerous properties can be modified in this way, e.g., mechanical, optical, electrical, or chemical performance. In particular, alkali cation exchange has received significant attention, primarily with respect to introducing compressive stress into the surface region of a glass, which increases mechanical durability. However, most of the present applications rely on specifically tailored matrix compositions in which the cation mobility is enhanced. This largely excludes the major area of soda-lime-silicates (SLS such as are commodity in almost all large-scale applications of glasses. Basic understanding of the relations between structural parameters and the effective diffusion coefficients may help to improve ion-exchanged SLS glass products, on the one hand in terms of obtainable strength and on the other in terms of cost. In the present paper, we discuss the trends in the effective diffusion coefficients when exchanging Na+ for various monovalent cations (K+, Cu+, Ag+, Rb+, and Cs+ by drawing relations to physicochemical properties. Correlations of effective diffusion coefficients were found for the bond dissociation energy and the electronic cation polarizability, indicating that localization and rupture of bonds are of importance for the ion-exchange rate.

  19. Trends in Effective Diffusion Coefficients for Ion-exchange Strengthening of Soda Lime Silicate Glasses

    Karlsson, Stefan; Wondraczek, Lothar; Ali, Sharafat; Jonson, Bo


    Monovalent cations enable efficient ion exchange processes due to their high mobility in silicate glasses. Numerous properties can be modified in this way, e.g., mechanical, optical, electrical or chemical performance. In particular, alkali cation exchange has received significant attention, primarily with respect to introducing compressive stress into the surface region of a glass, which increases mechanical durability. However, most of the present applications rely on specifically tailored matrix compositions in which the cation mobility is enhanced. This largely excludes the major area of soda lime silicates (SLS) such as are commodity in almost all large-scale applications of glasses. Basic understanding of the relations between structural parameters and the effective diffusion coefficients may help to improve ion-exchanged SLS glass products, on the one hand in terms of obtainable strength and on the other in terms of cost. In the present paper, we discuss the trends in the effective diffusion coefficients when exchanging Na+ for various monovalent cations (K+, Cu+, Ag+, Rb+ and Cs+) by drawing relations to physico-chemical properties. Correlations of effective diffusion coefficients were found for the bond dissociation energy and the electronic cation polarizability, indicating that localization and rupture of bonds are of importance for the ion exchange rate.




    Full Text Available The objective of the submitted work was to prepare and to characterize two types of silicate coatings prepared by the sol-gel method using the dip-coating technique on a titanium substrate. Efforts have been made to use mechanical properties of bio-inert titanium and bioactive properties of a silicate layer enriched with an admixture of compounds identified below. The first group consisted of silicate coatings containing silver, brushite and monetite. The other group of silicate coatings contained calcium nitrate and triethyl phosphate. Mechanically and chemically treated titanium substrates were dipped into sols and dried and fired. Silicate coatings from the first group were also chemically treated in 10 mol.l-1 solution of sodium hydroxide. All coatings were measured to determine their adhesive and bioactive properties and furthermore the antibacterial properties were tested in the case of first group. Surfaces of the coated substrates were investigated after the firing and after the individual tests with optical and electron microscopy and X-ray microdiffraction. A tape test demonstrated excellent adhesive property of all coatings to the substrate, classified with degree 5. A static in vitro test demonstrated bioactivity of nearly all the coatings. The basic silicate coating from the first group and one type of coating from the second group were identified as inert. Antibacterial properties of silicate coatings containing silver showed to be different when tested against Escherichia coli bacteria. A complete inhibition of the growth of bacteria under our experimental conditions was observed for the coating containing silver and monetite and a partial inhibition of the growth of bacteria for coatings containing silver and silver in combination with brushite.

  1. Silicic Arc Magmas And Silicic Slab Melts: The Melt-Rock Reaction Link

    Straub, S. M.; Gomez-Tuena, A.; Bolge, L. L.; Espinasa-Perena, R.; Bindeman, I. N.; Stuart, F. M.; Zellmer, G. F.


    While a genetic link between silicic arc magmas and silicic melts from the subducted slab has long been proposed, this hypothesis is commonly refuted because most arc magmas lack a 'garnet-signature' which such slab melts must have. A comprehensive geochemical study of high-Mg# arc magmas from the Quaternary central Mexican Volcanic Belt (MVB), however, shows that this conflict can be reconciled if melt-rock reaction processes in the mantle wedge were essential to arc magma formation. In the central MVB, monogenetic and composite volcanoes erupt high-Mg# basalts to andesites with highly variable trace element patterns. These magmas contain high-Ni olivines (olivine Ni higher than permissible for olivines in partial peridotite melts) with high 3He/4He = 7-8 Ra that provide strong evidence for silicic slab components that infiltrate the subarc mantle to produce olivine-free segregations of 'reaction pyroxenite' in the sources of individual volcanoes. Melting of silica-excess and silica-deficient reaction pyroxenites can then produce high-Mg# basaltic and dacitic primary melts that mix during ascent through mantle and crust to form high-Mg# andesites. Mass balance requires that reaction pyroxenites contain at least >15-18 wt%, and likely more, of slab component. However, because the HREE of the slab component are efficiently retained in the eclogitic slab, elements Ho to Lu in partial melts from reaction pyroxenites remain controlled by the mantle and maintain MORB-normalized Ho/Lun ˜1.15 close to unity. In contrast, the MREE to LREE and fluid mobile LILE of the arc magmas are either controlled, or strongly influenced, by slab-contributions. The origin from hybrid sources also shows in the major elements that are blends of mantle-derived elements (Mg, Ca, Mn, Fe, Ti) and elements augmented by slab contributions (Si, Na, K, P, and possibly Al). Moreover, strong correlations between bulk rock SiO2, 87Sr/86Sr and δ18O (olivines) can be interpreted as mixtures of subarc

  2. Riemann Zeta Matrix Function

    Kargın, Levent; Kurt, Veli


    In this study, obtaining the matrix analog of the Euler's reflection formula for the classical gamma function we expand the domain of the gamma matrix function and give a infinite product expansion of sinπxP.  Furthermore we define Riemann zeta matrix function and evaluate some other matrix integrals. We prove a functional equation for Riemann zeta matrix function.

  3. Infrared photoluminescence from GeSi nanocrystals embedded in a germanium–silicate matrix

    Volodin, V. A., E-mail:; Gambaryan, M. P.; Cherkov, A. G.; Vdovin, V. I. [Russian Academy of Sciences, Rzhanov Institute of Semiconductor Physics, Siberian Branch (Russian Federation); Stoffel, M.; Rinnert, H.; Vergnat, M. [Université de Lorraine, Institut Jean Lamour UMR CNRS 7198 (France)


    We investigate the structural and optical properties of GeO/SiO{sub 2} multilayers obtained by evaporation of GeO{sub 2} and SiO{sub 2} powders under ultrahigh vacuum conditions on Si(001) substrates. Both Raman and infrared absorption spectroscopy measurements indicate the formation of GeSi nanocrystals after postgrowth annealing at 800°C. High-resolution transmission electron microscopy characterizations show that the average size of the nanocrystals is about 5 nm. For samples containing GeSi nanocrystals, photoluminescence is observed at 14 K in the spectral range 1500–1600 nm. The temperature dependence of the photoluminescence is studied.

  4. Infrared photoluminescence from GeSi nanocrystals embedded in a germanium-silicate matrix

    Volodin, V. A.; Gambaryan, M. P.; Cherkov, A. G.; Vdovin, V. I.; Stoffel, M.; Rinnert, H.; Vergnat, M.


    We investigate the structural and optical properties of GeO/SiO2 multilayers obtained by evaporation of GeO2 and SiO2 powders under ultrahigh vacuum conditions on Si(001) substrates. Both Raman and infrared absorption spectroscopy measurements indicate the formation of GeSi nanocrystals after postgrowth annealing at 800°C. High-resolution transmission electron microscopy characterizations show that the average size of the nanocrystals is about 5 nm. For samples containing GeSi nanocrystals, photoluminescence is observed at 14 K in the spectral range 1500-1600 nm. The temperature dependence of the photoluminescence is studied.

  5. Impacts of diffusive transport on carbonate mineral formation from magnesium silicate-CO2-water reactions.

    Giammar, Daniel E; Wang, Fei; Guo, Bin; Surface, J Andrew; Peters, Catherine A; Conradi, Mark S; Hayes, Sophia E


    Reactions of CO2 with magnesium silicate minerals to precipitate magnesium carbonates can result in stable carbon sequestration. This process can be employed in ex situ reactors or during geologic carbon sequestration in magnesium-rich formations. The reaction of aqueous CO2 with the magnesium silicate mineral forsterite was studied in systems with transport controlled by diffusion. The approach integrated bench-scale experiments, an in situ spectroscopic technique, and reactive transport modeling. Experiments were performed using a tube packed with forsterite and open at one end to a CO2-rich solution. The location and amounts of carbonate minerals that formed were determined by postexperiment characterization of the solids. Complementing this ex situ characterization, (13)C NMR spectroscopy tracked the inorganic carbon transport and speciation in situ. The data were compared with the output of reactive transport simulations that accounted for diffusive transport processes, aqueous speciation, and the forsterite dissolution rate. All three approaches found that the onset of magnesium carbonate precipitation was spatially localized about 1 cm from the opening of the forsterite bed. Magnesite was the dominant reaction product. Geochemical gradients that developed in the diffusion-limited zones led to locally supersaturated conditions at specific locations even while the volume-averaged properties of the system remained undersaturated.

  6. Optical properties and Judd–Ofelt analysis of Eu{sup 3+} activated calcium silicate

    Barve, R.A., E-mail:; Suriyamurthy, N.; Panigrahi, B.S.; Venkatraman, B.


    Eu{sup 3+} activated calcium silicate was synthesized in stoichiometric ratio using the co-precipitation technique. The phosphors were characterized using X-ray diffraction and photoluminescence technique. Based on Judd–Ofelt (J–O) analysis, the intensity parameters Ω{sub 2} and Ω{sub 4} were calculated from the emission spectra for various Europium concentrations. The determined values indicate higher hypersensitive behavior of the {sup 5}D{sub 0}→{sup 7}F{sub 2} transition of Eu{sup 3+} ions in the host matrix and a stronger covalency. Different radiative properties have been discussed as the function of Eu{sup 3+} concentration. The lifetime decay pattern recorded for these samples indicated single exponential behavior. The quantum efficiency has been calculated to be 62% from the emission spectrum and the fluorescence lifetime was found to be 2.9 ms.

  7. Mechanical and in vitro biological performance of graphene nanoplatelets reinforced calcium silicate composite.

    Mehrali, Mehdi; Moghaddam, Ehsan; Seyed Shirazi, Seyed Farid; Baradaran, Saeid; Mehrali, Mohammad; Latibari, Sara Tahan; Metselaar, Hendrik Simon Cornelis; Kadri, Nahrizul Adib; Zandi, Keivan; Osman, Noor Azuan Abu


    Calcium silicate (CaSiO3, CS) ceramic composites reinforced with graphene nanoplatelets (GNP) were prepared using hot isostatic pressing (HIP) at 1150°C. Quantitative microstructural analysis suggests that GNP play a role in grain size and is responsible for the improved densification. Raman spectroscopy and scanning electron microscopy showed that GNP survived the harsh processing conditions of the selected HIP processing parameters. The uniform distribution of 1 wt.% GNP in the CS matrix, high densification and fine CS grain size help to improve the fracture toughness by ∼130%, hardness by ∼30% and brittleness index by ∼40% as compared to the CS matrix without GNP. The toughening mechanisms, such as crack bridging, pull-out, branching and deflection induced by GNP are observed and discussed. The GNP/CS composites exhibit good apatite-forming ability in the simulated body fluid (SBF). Our results indicate that the addition of GNP decreased pH value in SBF. Effect of addition of GNP on early adhesion and proliferation of human osteoblast cells (hFOB) was measured in vitro. The GNP/CS composites showed good biocompatibility and promoted cell viability and cell proliferation. The results indicated that the cell viability and proliferation are affected by time and concentration of GNP in the CS matrix.

  8. Mechanical and in vitro biological performance of graphene nanoplatelets reinforced calcium silicate composite.

    Mehdi Mehrali

    Full Text Available Calcium silicate (CaSiO3, CS ceramic composites reinforced with graphene nanoplatelets (GNP were prepared using hot isostatic pressing (HIP at 1150°C. Quantitative microstructural analysis suggests that GNP play a role in grain size and is responsible for the improved densification. Raman spectroscopy and scanning electron microscopy showed that GNP survived the harsh processing conditions of the selected HIP processing parameters. The uniform distribution of 1 wt.% GNP in the CS matrix, high densification and fine CS grain size help to improve the fracture toughness by ∼130%, hardness by ∼30% and brittleness index by ∼40% as compared to the CS matrix without GNP. The toughening mechanisms, such as crack bridging, pull-out, branching and deflection induced by GNP are observed and discussed. The GNP/CS composites exhibit good apatite-forming ability in the simulated body fluid (SBF. Our results indicate that the addition of GNP decreased pH value in SBF. Effect of addition of GNP on early adhesion and proliferation of human osteoblast cells (hFOB was measured in vitro. The GNP/CS composites showed good biocompatibility and promoted cell viability and cell proliferation. The results indicated that the cell viability and proliferation are affected by time and concentration of GNP in the CS matrix.

  9. Heterogeneous nucleation of protein crystals on fluorinated layered silicate.

    Keita Ino

    Full Text Available Here, we describe an improved system for protein crystallization based on heterogeneous nucleation using fluorinated layered silicate. In addition, we also investigated the mechanism of nucleation on the silicate surface. Crystallization of lysozyme using silicates with different chemical compositions indicated that fluorosilicates promoted nucleation whereas the silicates without fluorine did not. The use of synthesized saponites for lysozyme crystallization confirmed that the substitution of hydroxyl groups contained in the lamellae structure for fluorine atoms is responsible for the nucleation-inducing property of the nucleant. Crystallization of twelve proteins with a wide range of pI values revealed that the nucleation promoting effect of the saponites tended to increase with increased substitution rate. Furthermore, the saponite with the highest fluorine content promoted nucleation in all the test proteins regardless of their overall net charge. Adsorption experiments of proteins on the saponites confirmed that the density of adsorbed molecules increased according to the substitution rate, thereby explaining the heterogeneous nucleation on the silicate surface.

  10. Silicate Dust in Evolved Protoplanetary Disks: Growth, Sedimentation, and Accretion

    Sicilia-Aguilar, Aurora; Watson, Dan; Bohac, Chris; Henning, Thomas; Bouwman, Jeroen; 10.1086/512121


    We present the Spitzer IRS spectra for 33 young stars in Tr 37 and NGC 7160. The sample includes the high- and intermediate-mass stars with MIPS 24 microns excess, the only known active accretor in the 12 Myr-old cluster NGC 7160, and 19 low-mass stars with disks in the 4 Myr-old cluster Tr 37. We examine the 10 microns silicate feature, present in the whole sample of low-mass star and in 3 of the high- and intermediate-mass targets, and we find that PAH emission is detectable only in the Herbig Be star. We analyze the composition and size of the warm photospheric silicate grains by fitting the 10 microns silicate feature, and study the possible correlations between the silicate characteristics and the stellar and disk properties (age, SED slope, accretion rate, spectral type). We find indications of dust settling with age and of the effect of turbulent enrichment of the disk atmosphere with large grains. Crystalline grains are only small contributors to the total silicate mass in all disks, and do not seem t...

  11. Theoretical prediction of single-site surface-protonation equilibrium constants for oxides and silicates in water

    Sverjensky, D.A.; Sahai, N. [Johns Hopkins Univ., Baltimore, MD (United States)


    The equilibrium constants for surface protonation of solid oxides and silicates can be estimated from theoretical considerations and known properties of the solids for use in the constant capacitance, diffuse double layer or triple layer models of surface complexation. The theoretical considerations take into account Born solvation theory for the adsorbing proton, electrostatic interactions of the adsorbing proton with a surface oxygen and an underlying metal, and an intrinsic binding of the proton to the surface. As a consequence, the equilibrium constants for the {nu}th ({nu} = 1 or 2) surface protonation reaction on the kth solid can be expressed in terms of the inverse of the dielectric constant of the solid (1/{epsilon}{sub k}) and an average Pauling bond strength per angstrom (s/r{sub M-OH}) for the solid according to log K{sub {nu}} = M{sub {nu}}(1/{epsilon}{sub k}) - B{sub {nu}}(s/r{sub M-OH}) + log K{sub ii,{nu}}{sup {double_prime}}, where the coefficients M{sub {nu}} B{sub {nu}} and K{sub ii{nu}}{sup {double_prime}} are constants characteristic of all oxides and silicates for each surface complexation model. Evaluation of these constants using experimental data for TiO{sub 2}, {gamma}-alumina, Al{sub 2}O{sub 3} FeOOH, Fe(OH){sub 3}, silica, quartz. and kaolinite permits widespread prediction of surface protonation equilibrium constants from the known bulk structure properties 1/{epsilon}{sub k} and s/r{sub M-OH}. Such predictions should replace attempts to estimate surface protonation equilibrium constants for solids from empirical correlations with aqueous equilibrium constants. Surface protonation constants should also not be estimated from correlations with only the Pauling bond strength because these neglect specific treatment of salvation. 92 refs., 14 figs., 4 tabs.

  12. Computational modelling of large deformations in layered-silicate/PET nanocomposites near the glass transition

    Figiel, Łukasz; Dunne, Fionn P. E.; Buckley, C. Paul


    Layered-silicate nanoparticles offer a cost-effective reinforcement for thermoplastics. Computational modelling has been employed to study large deformations in layered-silicate/poly(ethylene terephthalate) (PET) nanocomposites near the glass transition, as would be experienced during industrial forming processes such as thermoforming or injection stretch blow moulding. Non-linear numerical modelling was applied, to predict the macroscopic large deformation behaviour, with morphology evolution and deformation occurring at the microscopic level, using the representative volume element (RVE) approach. A physically based elasto-viscoplastic constitutive model, describing the behaviour of the PET matrix within the RVE, was numerically implemented into a finite element solver (ABAQUS) using an UMAT subroutine. The implementation was designed to be robust, for accommodating large rotations and stretches of the matrix local to, and between, the nanoparticles. The nanocomposite morphology was reconstructed at the RVE level using a Monte-Carlo-based algorithm that placed straight, high-aspect ratio particles according to the specified orientation and volume fraction, with the assumption of periodicity. Computational experiments using this methodology enabled prediction of the strain-stiffening behaviour of the nanocomposite, observed experimentally, as functions of strain, strain rate, temperature and particle volume fraction. These results revealed the probable origins of the enhanced strain stiffening observed: (a) evolution of the morphology (through particle re-orientation) and (b) early onset of stress-induced pre-crystallization (and hence lock-up of viscous flow), triggered by the presence of particles. The computational model enabled prediction of the effects of process parameters (strain rate, temperature) on evolution of the morphology, and hence on the end-use properties.

  13. SON68 glass dissolution driven by magnesium silicate precipitation

    Fleury, Benjamin; Godon, Nicole; Ayral, André; Gin, Stéphane


    layer at the interface with the pristine glass, the gel and the secondary phases. B is not fixed in the gel layer but retention of both B and Li retention is evidenced in one part of the hydrated layer corresponding to a narrow interdiffusion layer [40]. The (H/Li) interdiffusion coefficient decreases by several orders of magnitude when the alteration solution is silica-saturated [41]. This interdiffusion coefficient is a relevant parameter for evaluating the passivation phenomenon. It has also been shown that the nanoporosity of the hydrated glass layer plays an important role [40]. It can be deduced that the precipitation of a silicate secondary phase associated with the consumption of silica strongly affects the hydration rate of the glass and as a consequence its alteration. So the precipitation of secondary phase is a motive force which modifies the physico-chemical properties of the reactive interface situated in the gel or probably in the hydrated glass which has a role of passivation. Currently, the notion of reactive interface and its physico-chemical conditions are under investigations. In our study, solid characterizations are difficult so we use only the general notion of a protective gel. The increased calcium concentrations correspond to congruent dissolution of the gel formed before the addition of magnesium. The Ca/Si molar ratio of the gel was estimated from each experiment based on the data for day 29; in each case the ratio was near 0.1. This hypothesis was not taken into account for the experiment with regular Mg additions because no gel alteration occurred between 45 and 63 days. Glass alteration released boron and silicon in the same proportions as in the glass. No gel formation occurred within the balance period except in the experiment with 100 mg L-1 of Mg at t = 0, for which the cases of 10%, 30% and 50% gel formation (percentage of silicon from glass alteration incorporated in the gel) are indicated as examples. Based on the calcium

  14. CO2 capture properties of lithium silicates with different ratios of Li2O/SiO2: an ab initio thermodynamic and experimental approach.

    Duan, Yuhua; Pfeiffer, Heriberto; Li, Bingyun; Romero-Ibarra, Issis C; Sorescu, Dan C; Luebke, David R; Halley, J Woods


    The lithium silicates have attracted scientific interest due to their potential use as high-temperature sorbents for CO2 capture. The electronic properties and thermodynamic stabilities of lithium silicates with different Li2O/SiO2 ratios (Li2O, Li8SiO6, Li4SiO4, Li6Si2O7, Li2SiO3, Li2Si2O5, Li2Si3O7, and α-SiO2) have been investigated by combining first-principles density functional theory with lattice phonon dynamics. All these lithium silicates examined are insulators with band-gaps larger than 4.5 eV. By decreasing the Li2O/SiO2 ratio, the first valence bandwidth of the corresponding lithium silicate increases. Additionally, by decreasing the Li2O/SiO2 ratio, the vibrational frequencies of the corresponding lithium silicates shift to higher frequencies. Based on the calculated energetic information, their CO2 absorption capabilities were extensively analyzed through thermodynamic investigations on these absorption reactions. We found that by increasing the Li2O/SiO2 ratio when going from Li2Si3O7 to Li8SiO6, the corresponding lithium silicates have higher CO2 capture capacity, higher turnover temperatures and heats of reaction, and require higher energy inputs for regeneration. Based on our experimentally measured isotherms of the CO2 chemisorption by lithium silicates, we found that the CO2 capture reactions are two-stage processes: (1) a superficial reaction to form the external shell composed of Li2CO3 and a metal oxide or lithium silicate secondary phase and (2) lithium diffusion from bulk to the surface with a simultaneous diffusion of CO2 into the shell to continue the CO2 chemisorption process. The second stage is the rate determining step for the capture process. By changing the mixing ratio of Li2O and SiO2, we can obtain different lithium silicate solids which exhibit different thermodynamic behaviors. Based on our results, three mixing scenarios are discussed to provide general guidelines for designing new CO2 sorbents to fit practical needs.

  15. Widespread oxidized and hydrated amorphous silicates in CR chondrites matrices: Implications for alteration conditions and H2 degassing of asteroids

    Le Guillou, Corentin; Changela, Hitesh G.; Brearley, Adrian J.


    The CR chondrites carry one of the most pristine records of the solar nebula materials that accreted to form planetesimals. They have experienced very variable degrees of aqueous alteration, ranging from incipient alteration in their matrices to the complete hydration of all of their components. In order to constrain their chemical alteration pathways and the conditions of alteration, we have investigated the mineralogy and Fe oxidation state of silicates in the matrices of 8 CR chondrites, from type 3 to type 1. Fe-L edge X-ray Absorption Near Edge Structure (XANES) was performed on matrix FIB sections using synchrotron-based scanning transmission X-ray microscopy (STXM). The Fe3+ / ∑ Fe ratio of submicron silicate particles was obtained and coordinated with TEM observations. In all the least altered CR chondrites (QUE 99177, EET 87770, EET 92042, LAP 02342, GRA 95229 and Renazzo), we find that the matrices consist of abundant submicron Fe-rich hydrated amorphous silicate grains, mixed with nanometer-sized phyllosilicates. The Fe3+ / ∑ Fe ratios of both amorphous and nanocrystalline regions are very high with values ranging from 68 to 78%. In the most altered samples (Al Rais and GRO 95577), fine-grained phyllosilicates also have a high Fe3+ / ∑ Fe ratio (around 70%), whereas the coarse, micrometer-sized phyllosilicates are less oxidized (down to 55%) and have a lower iron content. These observations suggest the following sequence: submicron Fe2+-amorphous silicate particles were the building blocks of CR matrices; after accretion they were quickly hydrated and oxidized, leading to a metastable, amorphous gel-like phase. Nucleation and growth of crystalline phyllosilicates was kinetically-limited in most type 3 and 2 CRs, but increased as alteration became more extensive in Al Rais and GRO 95577. The decreasing Fe3+ / ∑ Fe ratio is interpreted as a result of the transfer of Fe3+ from silicates to oxides during growth, while aqueous alteration progressed

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

    Schneider, E.


    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.

  17. Energetic Processing of Interstellar Silicate Grains by Cosmic Rays

    Bringa, E M; Kucheyev, S O; Loeffler, M J; Baragiola, R A; Tielens, A G Q M; Dai, Z R; Graham, G; Bajt, S; Bradley, J; Dukes, C A; Felter, T E; Torres, D F; van Breugel, W


    While a significant fraction of silicate dust in stellar winds has a crystalline structure, in the interstellar medium nearly all of it is amorphous. One possible explanation for this observation is the amorphization of crystalline silicates by relatively 'low' energy, heavy ion cosmic rays. Here we present the results of multiple laboratory experiments showing that single-crystal synthetic forsterite (Mg{sub 2}SiO{sub 4}) amorphizes when irradiated by 10 MeV Xe{sup ++} ions at large enough fluences. Using modeling, we extrapolate these results to show that 0.1-5.0 GeV heavy ion cosmic rays can rapidly ({approx}70 Million yrs) amorphize crystalline silicate grains ejected by stars into the interstellar medium.

  18. Behaviour of Silicate Melts in Respect of Volume

    张金民; 叶大年


    The volumes per oxygen of some silicate melts have been calculated and then compared with those of silicate glasses.It is suggested that the volume of a silicate melt can be divided into two parts.One is contri buted by the silicon-oxygen network and the other by the “oxides”.Variation patterns of VPOs suggest that the volume of the Si-O network generally remains unchanged and the expansion of the melt is caused mainly by the locat expansion of the “oxides”.It is further proposed that the radius of O2- shows little variation,in striking contrast to the radius of cations.The mechanism governing the expansion is discussed in detail.

  19. Functional substitution of coordination polyhedron in crystal structure of silicates


    On the bases of the study of comparative crystal chemistry of silicates it has been concluded that the octahedra and square pyramids of Ti-O and Zr-O play functional role of tetrahedra of Si-O in the construction of crystal structures.Therefore,those silicates may be named titano- and zircono-silicates.Because of the functional similarity of coordination polyhedra,the structures of cristobalite and feldspar have been compared with those of perovskite and garnet,respectively.As a new concept,the functional replacement of tetrahedra by octahedra and/or pyramids is defined by the authors of this paper for favorable comparison of relative crystal structures.

  20. Structural chemistry of anhydrous sodium silicates - a review.

    Kahlenberg, Volker


    Sodium silicates are of considerable importance for many fields of inorganic chemistry and applied mineralogy, being either raw materials for synthesis or already finished products. In addition to their industrial relevance they have also been studied intensively because of their interesting physico-chemical properties including high ion-exchange capacity and selectivity or two-dimensional sodium diffusion and conductivity. Furthermore, the structural chemistry of crystalline sodium silicates offers the crystallographer challenging tasks such as polytypism, polymorphism, temperature and/or pressure-dependent phase transitions, pseudo-symmetry, complex twinning phenomena as well as incommensurately modulated structures. Many of these structural problems have been solved only recently, although in some cases they have been known for several decades. This article will provide an overview on the structurally characterized sodium silicates and their fascinating crystallochemical characteristics.

  1. Effect of Minor Elements on Silicate Cement Clinker

    HUANG Congyun; ZHANG Mingfei; ZHANG Meixiang; LONG Shizong; CHEN Yuankui; MA Baoguo


    The effect of rare-earth and HX addition agent on the burn-ability of silicate cement clinker was investigated by orthogonal experiment. The result shows, compared with blank sample, f- CaO of the samples added with rare-earth and HX agent drops by 84.95% , its 3d and 28d compressive strength enhances by 24.40%and 16.90%, respectively. It was discovered by means of X-ray diffraction and high temperature microscope analysis that sintering temperature of the sample added with rare-earth and HX addition agent is about 1320℃. At the same time, the burning temperature of tricalcium silicate desends and its crystal growth forming-rate increases.Tricalcium silicate content in burning clinker is higher and its crystal is larger.

  2. Evolution of trees and mycorrhizal fungi intensifies silicate mineral weathering

    Quirk, Joe; Beerling, David J.; Banwart, Steve A.; Kakonyi, Gabriella; Romero-Gonzalez, Maria E.; Leake, Jonathan R.


    Forested ecosystems diversified more than 350 Ma to become major engines of continental silicate weathering, regulating the Earth's atmospheric carbon dioxide concentration by driving calcium export into ocean carbonates. Our field experiments with mature trees demonstrate intensification of this weathering engine as tree lineages diversified in concert with their symbiotic mycorrhizal fungi. Preferential hyphal colonization of the calcium silicate-bearing rock, basalt, progressively increased with advancement from arbuscular mycorrhizal (AM) to later, independently evolved ectomycorrhizal (EM) fungi, and from gymnosperm to angiosperm hosts with both fungal groups. This led to ‘trenching’ of silicate mineral surfaces by AM and EM fungi, with EM gymnosperms and angiosperms releasing calcium from basalt at twice the rate of AM gymnosperms. Our findings indicate mycorrhiza-driven weathering may have originated hundreds of millions of years earlier than previously recognized and subsequently intensified with the evolution of trees and mycorrhizas to affect the Earth's long-term CO2 and climate history. PMID:22859556

  3. Electric field-induced softening of alkali silicate glasses

    McLaren, C.; Heffner, W.; Jain, H. [Department of Materials Science and Engineering, Lehigh University, Bethlehem, Pennsylvania 18015 (United States); Tessarollo, R.; Raj, R. [Department of Mechanical Engineering, University of Colorado at Boulder, Boulder, Colorado 80309 (United States)


    Motivated by the advantages of two-electrode flash sintering over normal sintering, we have investigated the effect of an external electric field on the viscosity of glass. The results show remarkable electric field-induced softening (EFIS), as application of DC field significantly lowers the softening temperature of glass. To establish the origin of EFIS, the effect is compared for single vs. mixed-alkali silicate glasses with fixed mole percentage of the alkali ions such that the mobility of alkali ions is greatly reduced while the basic network structure does not change much. The sodium silicate and lithium-sodium mixed alkali silicate glasses were tested mechanically in situ under compression in external electric field ranging from 0 to 250 V/cm in specially designed equipment. A comparison of data for different compositions indicates a complex mechanical response, which is observed as field-induced viscous flow due to a combination of Joule heating, electrolysis and dielectric breakdown.

  4. Electric field-induced softening of alkali silicate glasses

    McLaren, C.; Heffner, W.; Tessarollo, R.; Raj, R.; Jain, H.


    Motivated by the advantages of two-electrode flash sintering over normal sintering, we have investigated the effect of an external electric field on the viscosity of glass. The results show remarkable electric field-induced softening (EFIS), as application of DC field significantly lowers the softening temperature of glass. To establish the origin of EFIS, the effect is compared for single vs. mixed-alkali silicate glasses with fixed mole percentage of the alkali ions such that the mobility of alkali ions is greatly reduced while the basic network structure does not change much. The sodium silicate and lithium-sodium mixed alkali silicate glasses were tested mechanically in situ under compression in external electric field ranging from 0 to 250 V/cm in specially designed equipment. A comparison of data for different compositions indicates a complex mechanical response, which is observed as field-induced viscous flow due to a combination of Joule heating, electrolysis and dielectric breakdown.

  5. Synthesis and characterization of polymer matrix nanocomposites and their components

    Burnside, Shelly Dawn

    Herein we present synthesis schemes and characterization results for polymer matrix nanocomposite reinforced with organically modified layered silicates. These host materials with ultrafine dimensions are promising candidates for polymer and have been previously shown to yield substantial property enhancements at low silicate loadings due to their extreme geometry. Siloxane nanocomposites with a variety of nanostructures were formed. Thermal stability, solvent uptake and moduli of the nanocomposites were explores. Exfoliated nanocomposites displayed enhanced properties when compared to unreinforced siloxanes, and at lower volume fraction filler than in conventional composites. Large amounts of bound polymer, polymer affected by the silicate, were found in exfoliated nanocomposites as a result of the extreme geometry of the layered silicate. This bound polymer was related to the dramatic property enhancements in the nanocomposites. The behavior of these nanocomposites is compared to behavior expected from traditional models developed for conventional composites and model elastomeric networks. A lightly brominated polymer has been intercalated into a single crystal of organically exchanged vermiculite. The intercalation was followed using x-ray diffraction by monitoring the gallery height of the vermiculite host. Rutherford Backscattering Spectroscopy, used to confirm polymer intercalation, showed a constant bromine content in the direction normal to the layers. Atomic Force Microscopy images of a cleaved polymer-intercalated crystal showed raised hemispheres on an otherwise flat background. The hemispheres consist of single chains or aggregates of 3-40 polymer chains resulting from relaxations following cleaving. Three component or Hansen solubility parameters (delta) of organically modified layered silicates, the reinforcing agent in polymer matrix nanocomposites presented herein, have been determined. Two experimental techniques, temporal turbidimetry and

  6. Paleomagnetism and Mineralogy of Unusual Silicate Glasses and Baked Soils on the Surface of the Atacama Desert of Northern Chile: A Major Airburst Impact ~12ka ago?.

    Roperch, P. J.; Blanco, N.; Valenzuela, M.; Gattacceca, J.; Devouard, B.; Lorand, J. P.; Tomlinson, A. J.; Arriagada, C.; Rochette, P.


    Unusual silicate glasses were found in northern Chile in one of the driest place on earth, the Atacama Desert. The scoria-type melted rocks are littered on the ground at several localities distributed along a longitudinal band of about 50km. The silicate glasses have a stable natural remanent magnetization carried by fine-grained magnetite and acquired during cooling. At one locality, fine-grained overbank sediments were heated to form a 10 to 20 cm-thick layer of brick-type samples. Magnetic experiments on oriented samples demonstrate that the baked clays record a thermoremanent magnetization acquired in situ above 600°C down to more than 10cm depth and cooled under a normal polarity geomagnetic field with a paleointensity of 40μT. In some samples of the silicate glass, large grains of iron sulphides (troilite) are found in the glass matrix with numerous droplets of native iron, iron sulphides and iron phosphides indicating high temperature and strong redox conditions during melting. The paleomagnetic record of the baked clays and the unusual mineralogy of the silicate glasses indicate a formation mainly by in situ high temperature radiation. Paleomagnetic experiments and chemical analyses indicate that the silicate glasses are not fulgurite type rocks due to lightning events, nor volcanic glasses or even metallurgical slags related to mining activity. The existence of a well-developped baked clay layer indicates that the silicate glasses are not impact-related ejectas. The field, paleomagnetic and mineralogical observations support evidence for a thermal event likely related to a major airburst. The youngest calibrated 14C age on a charcoal sample closely associated with the glass indicates that the thermal event occurred around 12 to 13 ka BP. The good conservation of the surface effects of this thermal event in the Atacama Desert could provide a good opportunity to further estimate the threats posed by large asteroid airbursts.

  7. Solid propellants.

    Marsh, H. E., Jr.; Hutchison, J. J.


    The basic principles underlying propulsion by rocket motor are examined together with the configuration of a solid propellant motor. Solid propellants and their preparation are discussed, giving attention to homogeneous propellants, composite propellants, energetic considerations in choosing a solid propellant, the processing of composite propellants, and some examples of new developments. The performance of solid propellants is investigated, taking into account characteristics velocity, the specific impulse, and performance calculations. Aspects of propellant development considered include nonperformance requirements for solid propellants, the approach to development, propellant mechanical properties, and future trends.

  8. Nitrogen distribution between aqueous fluids and silicate melts

    Li, Yuan; Huang, Ruifang; Wiedenbeck, Michael; Keppler, Hans


    The partitioning of nitrogen between hydrous fluids and haplogranitic, basaltic, or albitic melts was studied at 1-15 kbar, 800-1200 °C, and oxygen fugacities (fO2) ranging from the Fe-FeO buffer to 3log units above the Ni-NiO buffer. The nitrogen contents in quenched glasses were analyzed either by electron microprobe or by secondary ion mass spectrometry (SIMS), whereas the nitrogen contents in fluids were determined by mass balance. The results show that the nitrogen content in silicate melt increases with increasing nitrogen content in the coexisting fluid at given temperature, pressure, and fO2. Raman spectra of the silicate glasses suggest that nitrogen species change from molecular N2 in oxidized silicate melt to molecular ammonia (NH3) or the ammonium ion (NH4+) in reduced silicate melt, and the normalized Raman band intensities of the nitrogen species linearly correlate with the measured nitrogen content in silicate melt. Elevated nitrogen contents in silicate melts are observed at reduced conditions and are attributed to the dissolution of NH3/NH4+. Measured fluid/melt partition coefficients for nitrogen (DNfluid/ melt) range from 60 for reduced haplogranitic melts to about 10 000 for oxidized basaltic melts, with fO2 and to a lesser extent melt composition being the most important parameters controlling the partitioning of nitrogen. Pressure appears to have only a minor effect on DNfluid/ melt in the range of conditions studied. Our data imply that degassing of nitrogen from both mid-ocean ridge basalts and arc magmas is very efficient, and predicted nitrogen abundances in volcanic gases match well with observations. Our data also confirm that nitrogen degassing at present magma production rates is insufficient to accumulate the atmosphere. Most of the nitrogen in the atmosphere must have degassed very early in Earth's history and degassing was probably enhanced by the oxidation of the mantle.

  9. FeO-rich silicates and Ca,Al-rich inclusions in Qingzhen andYamato 691 (EH3) meteo-rites: Evidence for migration of mass in the solar nebula


    The Qingzhen and Yamato 691 (EH3) enstatite chondrites, which formed under extremely reducing conditions, are studied using the scanning electron microscope and electron probe microanalyzer. Both meteorites contain FeO-rich silicates and minor Ca, Al-rich inclusions. Most FeO-rich silicates are Ca-poor pyroxenes and occur as fragments in matrix. A few grains of FeO-rich silicates were found in chondrules, and FeO-rich olivine is rare. In Qingzhen, FeO-rich silicates commonly contain abundant dust-like Ni-poor metals, which probably formed through reduction of FeO. In contrast, only a few fragments of FeO-rich silicates in Yamato 691 enclose dust-like metals.This difference is consistent with a more reducing condition of Qingzhen than Yamato 691. Ca, Al-rich inclusions have similar modal compositions and mineral chemistry as their counterparts in carbonaceous chondrites. We suggest that (1)the FeO-rich silicates probably formed in oxidized regions of the solar nebula, and then moved into the enstatite chondrite locations; and (2) Ca, Al-rich inclusions in both enstatite chondrites and carbonaceous chondrites may have similar origins and reservoirs.``

  10. Advanced instrumental methods for analyzing organics in solid waste: The use of gas chromatography/matrix isolation infrared spectroscopy (GC/MIIR) and supercritical fluid chromatography (SFC) for waste characterization

    Raphaelian, L.A.; Boparai, A.S.; Schneider, J.F.


    Objectives of this research project were: (1) to enhance the capabilities of analyzing the complex mixtures found in coal wastes by using gas chromatography/matrix isolation infrared spectroscopy (GC/MIIR); (2) to separate, by supercritical fluid chromatography (SFC), the complex mixtures found in coal wastes into a few, less-complex mixtures so that analysis by gas chromatography (GC/MS) and GC/MIIR would be simplified. Preliminary results are presented for the mass spectra and infrared spectra of xylene isomers, gas chromatogram of 12 C/sub 2/-Napthalenes, averaged IR spectrum and a comparison of matrix isolation with light-pipe infrared spectra. A SFC chromatogram of polynuclear aromatic hydrocarbons is also presented. 2 refs., 5 figs.

  11. Structural characterization of magnesium silicate hydrate: towards the design of eco-sustainable cements.

    Tonelli, M; Martini, F; Calucci, L; Fratini, E; Geppi, M; Ridi, F; Borsacchi, S; Baglioni, P


    Magnesium-based cement is one of the most interesting eco-sustainable alternatives to standard cementitious binders. The reasons for the interest towards this material are twofold: (i) its production process, using magnesium silicates, brine or seawater, dramatically reduces CO2 emissions with respect to Portland cement production, and (ii) it is very well suited to applications in radioactive waste encapsulation. In spite of its potential, assessment of the structural properties of its binder phase (magnesium silicate hydrate or M-S-H) is far from complete, especially because of its amorphous character. In this work, a comprehensive structural characterization of M-S-H was obtained using a multi-technique approach, including a detailed solid-state NMR investigation and, in particular, for the first time, quantitative (29)Si solid-state NMR data. M-S-H was prepared through room-temperature hydration of highly reactive MgO and silica fume and was monitored for 28 days. The results clearly evidenced the presence in M-S-H of "chrysotile-like" and "talc-like" sub-nanometric domains, which are approximately in a 1 : 1 molar ratio after long-time hydration. Both these kinds of domains have a high degree of condensation, corresponding to the presence of a small amount of silanols in the tetrahedral sheets. The decisive improvement obtained in the knowledge of M-S-H structure paves the way for tailoring the macroscopic properties of eco-sustainable cements by means of a bottom-up approach.

  12. Discovery of ancient silicate stardust in a meteorite.

    Nguyen, Ann N; Zinner, Ernst


    We have discovered nine presolar silicate grains from the carbonaceous chondrite Acfer 094. Their anomalous oxygen isotopic compositions indicate formation in the atmospheres of evolved stars. Two grains are identified as pyroxene, two as olivine, one as a glass with embedded metal and sulfides (GEMS), and one as an Al-rich silicate. One grain is enriched in 26Mg, which is attributed to the radioactive decay of 26Al and provides information about mixing processes in the parent star. This discovery opens new means for studying stellar processes and conditions in various solar system environments.

  13. Mathematical Viscosity Models for Ternary Metallic and Silicate Melts

    FU Yuan-kun; MENG Xian-min; GUO Han-jie


    The mathematical viscosity models for metallic melts were discussed. The experimental data of Ag-Au-Cu systems were used to verify the models based on Chou's general geometric thermodynamic model and the calculated results are consistent with the reported experimental data. A new model predicting the viscosity of multi-component silicate melts was established. The CaO-MnO-SiO2, CaO-FeO-SiO2 and FeO-MnO-SiO2 silicate slag systems were used to verify the model.

  14. Leaf application of silicic acid to upland rice and corn

    Carlos Alexandre Costa Crusciol


    Full Text Available This study aimed to evaluate the effect of Si (stabilized silicic acid, Silamol® leaf application on mineral nutrition and yield in upland rice and corn crops. The treatments were the control (without Si and Si foliar split spraying using 2 L ha-1 of the Silamol® commercial product, with 0.8% soluble Si as concentrated stabilized silicic acid. Silicon leaf application increased the concentrations of K, Ca and Si in rice and corn leaves, the number of panicles per m2 of rice and the number of grains per ear of corn; accordingly, the Si leaf application provided a higher grain yield in both crops.

  15. Mbosi: An anomalous iron with unique silicate inclusions

    Olsen, Edward J.; Clayton, Robert N.; Mayeda, Toshiko K.; Davis, Andrew M.; Clarke, Roy S., Jr.; Wasson, John T.


    The Mbosi iron meteorite contains millimeter size silicate inclusions. Mbosi is an ungrouped iron meteorite with a Ge/Ga ratio >10, which is an anomalous property shared with the five-member IIF iron group, the Eagle Station pallasites and four other ungrouped irons. Neither the IIF group nor the four other ungrouped irons are known to have silicate inclusions. Chips from three Mbosi inclusions were studied, but most of the work concentrated on a whole 3.1 mm circular inclusion. This inclusion consists of a mantle and a central core of different mineralogies. The mantle is partially devitrified quartz-normative glass, consisting of microscopic crystallites of two pyroxenes and plagioclase, which are crystalline enough to give an x-ray powder diffraction pattern but not coarse enough to permit analyses of individual minerals. The core consists of silica. The bulk composition does not match any known meteorite type, although there is a similarity in mode of occurrence to quartz-normative silicate inclusions in some HE irons. Mbosi silicate appears to be unique. The bulk rare earth element (REE) pattern of the mantle is flat at ≅ 7×C1; the core is depleted in REE but shows a small positive Eu anomaly. The O-isotope composition of bulk silicate lies on a unit slope mixing line (parallel and close to the C3 mixing line) that includes the Eagle Station pallasites and the iron Bocaiuva (related to the IIF irons); all of these share the property of having Ge/Ga ratios >10. It is concluded that Mbosi silicate represents a silica-bearing source rock that was melted and injected into metal. Melting occurred early in the history of the parent body because the metal now shows a normal Widmanstätten structure with only minor distortion that was caused when the parent body broke up and released meteorites into interplanetary space. The cause of Ge/Ga ratios being >10 in these irons is unknown. The fact that silicates in Mbosi, Bocaiuva (related to IIF irons) and the Eagle

  16. Electrical conductivity measurements on silicate melts using the loop technique

    Waff, H. S.


    A new method is described for measurement of the electrical conductivity of silicate melts under controlled oxygen partial pressure at temperatures to 1550 C. The melt samples are suspended as droplets on platinum-rhodium loops, minimizing iron loss from the melt due to alloying with platinum, and providing maximum surface exposure of the melt to the oxygen-buffering gas atmosphere. The latter provides extremely rapid equilibration of the melt with the imposed oxygen partial pressure. The loop technique involves a minimum of setup time and cost, provides reproducible results to within + or - 5% and is well suited to electrical conductivity studies on silicate melts containing redox cations.

  17. Gene Expression Profiling and Molecular Signaling of Dental Pulp Cells in Response to Tricalcium Silicate Cements: A Systematic Review.

    Rathinam, Elanagai; Rajasekharan, Sivaprakash; Chitturi, Ravi Teja; Martens, Luc; De Coster, Peter


    Signaling molecules and responding dental pulp stem cells are the 2 main control keys of dentin regeneration/dentinogenesis. The aim of this study was to present a systematic review investigating the gene expression of various dental pulp cells in response to different variants of tricalcium silicate cements. A systematic search of the literature was performed by 2 independent reviewers followed by article selection and data extraction. Studies analyzing all sorts of dental pulp cells (DPCs) and any variant of tricalcium silicate cement either as the experimental or as the control group were included. A total of 39 articles were included in the review. Among the included studies, ProRoot MTA (Dentsply, Tulsa Dental, OK) was the most commonly used tricalcium silicate cement variant. The extracellular signal regulated kinase/mitogen-activated protein kinase pathway was the most commonly activated pathway to be identified, and similarly, dentin sialophosphoprotein osteocalcin dentin matrix acidic phosphoprotein 1, alkaline phosphatase, bone sialoprotein, osteopontin, type I collagen, and Runx2 were the most commonly expressed genes in that order of frequency. Biodentine (Septodont Ltd, Saint Maur des Faussés, France), Bioaggregate (Innovative Bioceramix, Vancouver, BC, Canada), and mineral trioxide aggregate stimulate the osteogenic/odontogenic capacity of DPCs by proliferation, angiogenesis, and biomineralization through the activation of the extracellular signal regulated kinase ½, nuclear factor E2 related factor 2, p38, c-Jun N-terminal kinase mitogen-activated protein kinase, p42/p44 mitogen-activated protein kinase, nuclear factor kappa B, and fibroblast growth factor receptor pathways. When DPCs are placed into direct contact with tricalcium silicate cements, they show higher levels of gene activation, which in turn could translate into more effective pulpal repair and faster and more predictable formation of reparative dentin. Copyright © 2015 American

  18. Ni2+-doped new silicate glass-ceramics for broadband near infrared luminescence

    Zheng, Jian; Cheng, Yin


    The new composite transparent spinel silicate glass-ceramics containing Ni2+-doped ZnGa2O4 and solid solution MgxZn1-xGa2O4 nanocrystals were fabricated by in situ controlled crystallization method. After heat treatment, the crystal phase content of ZnGa2O4 increase with increasing heat treatment temperature, and the Mg2+ ions could enter the crystal lattice of ZnGa2O4 to replace the Zn2+ ions and form a new solid solution MgxZn1-xGa2O4. The coordination environment of Ni2+ was changed from tetrahedral in glasses to octahedral sites in glass ceramics. The super-broadband infrared luminescence with full width at half maximum (FWHM) of about 400 nm overing 1.1-1.7 μm wavelength region and fluorescent lifetime of about 480 μs were observed from the glass ceramics containing MgxZn1-xGa2O4 nanocrystals. It is probably due to the variety of solid solution structure making Ni2+ ions enter two different octahedral sites. At the same time, the impact of heat treatment temperature and the concentration of NiO on peak position and intensity were also discussed. The results demonstrate that the method presented may be an effective way to fabricate super-broadband optical amplifiers and tunable lasers.

  19. Characterization of Magnesium Doped Lithium Iron Silicate

    Juan A. Jaén


    Full Text Available The synthesis of Mg doped Li2Fe1–xMgxSiO4 (x = 0, 0.10 and 0.15 via solid-state reaction is reported. The product was characterized by Mössbauer spectroscopy (MS, X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FTIR, magnetic measurements and scanning electron microscopy (SEM. The structures of the reaction products were confirmed to be the monoclinic structure P21/n, but impurities were detected in them. In the undoped sample small amounts of lithium iron oxide or lithiated magnetite was obtained, whereas a magnetic phase was found in samples with more than 10 % (mole fraction of Mg doping.

  20. Core Formation Timescale, Silicate-Metal Equilibration, and W Diffusivity

    Yin, Q.; Jacobsen, B.; Tinker, D.; Lesher, C.


    The extent to which material accreted to the proto-Earth and segregated to form the core was chemically and isotopically equilibrated with the silicate mantle is an outstanding problem in planetary science. This is particularly important when attempting to assign a meaningful age for planetary accretion and core formation based on Hf-W isotope systematics. The Earth and other terrestrial planets likely formed by accretion of previously differentiated planetesimals. For the planetesimals themselves the most important energy source for metal-silicate differentiation is the combined radioactive heating due to decay of 26Al (half-life 0.7 Ma) and 60Fe (half-life 1.5 Ma). It is expected that the fractionation of Hf and W during planetesimal core formation will lead to a divergence in the W isotopic compositions of the core and silicate portions of these bodies. This expectation is supported by the enormously radiogenic 182W signatures reported for basaltic eucrites. The observation that the W isotopic compositions of the silicate portions of Earth, Moon and Mars are similar and markedly less radiogenic than eucrites suggests that during planet accretion the pre-differentiated metallic core material containing low 182W must have equilibrated extensively with the more radiogenic (high 182W) silicate material to subdue the ingrowth of 182W in the silicate mantle of the planets. The standard theory of planet formation predicts that after runaway and oligarchic growth, the late stage of planet formation is characterized by impact and merging of Mars-sized objects. This is a tremendously energetic process estimated to raise the temperature of the proto-Earth to about 7000K (a temperature equivalent to a mass spectrometer's plasma source, which indiscriminately ionizes all incoming elements). After the giant impacts, the proto-Earth had a luminosity and surface temperature close to a low mass star for a brief period of time. Stevenson (1990) argued that emulsification caused

  1. Non-conservative controls on distribution of dissolved silicate in Cochin Backwaters

    Balachandran, K.K.; Sankaranarayanan, V.N.; Joseph, T.; Nair, M.

    Cochin backwater system was studied with regard to dissolved silicate (DSi) to understand its seasonal distribution and behaviour during estuarine mixing. Silicate had a linear relationship with salinity during the high river discharge period...

  2. Calcium silicate nanowires - An effective alternative for improving mechanical properties of chitosan-hydroxyethyl methacrylate (HEMA) copolymer nanocomposites.

    Bari, Sarang S; Mishra, Satyendra


    Nanowires of calcium silicate were successfully synthesized by ultrasonic irradiation process and incorporated into chitosan and hydroxyetheyl methacrylate (HEMA) copolymer matrix by solution blending for efficacious preparation of biodegradable nanocomposites. Remarkable improvement in mechanical properties of the nanocomposites was noticed after micro-tensile analysis. Enlarged surface area and higher aspect ratio of CaSiO3 nanowires were the key factors responsible for such improvement. This was supported by EDS and XRD analysis in terms of proper distribution of nanofiller through the copolymer matrix and corresponding rise in percentage crystallanity respectively. Contact angle and biodegradation studies further clarified that nano-CaSiO3 did not affect the hydrophilicity and general degradation route of chitosan copolymer respectively. This renders the nano-CaSiO3 as an ideal substitute for preparing high performance nanocomposites to be applicable for biomedical applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. On the Dissolution Behavior of Sulfur in Ternary Silicate Slags

    Kang, Youn-Bae; Park, Joo Hyun


    Sulfur dissolution behavior, in terms of sulfide capacity ( C S), in ternary silicate slags (molten oxide slags composed of MO - NO - SiO2, where M and N are Ca, Mn, Fe, and Mg), is discussed based on available experimental data. Composition dependence of the sulfur dissolution, at least in the dilute region of sulfur, may be explained by taking into account the cation-anion first-nearest-neighbor (FNN) interaction (stability of sulfide) and the cation-cation second-nearest-neighbor (SNN) interaction over O anion (oxygen proportions in silicate slags). When the Gibbs energy of a reciprocal reaction MO + NS = MS + NO is positive, the sulfide capacity of slags with virtually no SiO2 or low SiO2 concentration decreases as the concentration of MO increases. However, in some slags, as SiO2 concentration increases, replacing NO by MO at a constant SiO2 concentration may increase sulfide capacity when the basicity of NO is less than that of MO. This phenomenon is observed as rotation of iso- C S lines in ternary silicate slags, and it is explained by simultaneous consideration of the stability of sulfide and oxygen proportions in the silicate slags. It is suggested that a solution model for the prediction of sulfide capacity should be based on the actual dissolution mechanism of sulfur rather than on the simple empirical correlation.

  4. Porphyrin-Embedded Silicate Materials for Detection of Hydrocarbon Solvents


    are naturally occurring in petroleum products . The individual compounds are also used in a range of manufacturing and production processes. The BTEX...478-483. 17. Ueno, Y.; Tate, A.; Niwa, O.; Zhou, H.-S.; Yamada, T.; Honma, I. High benzene selectivity of mesoporous silicate for BTX gas sensing

  5. Energetics of silicate melts from thermal diffusion studies

    Walker, D.


    Efforts are reported in the following areas: laboratory equipment (multianvils for high P/T work, pressure media, SERC/DL sychrotron), liquid-state thermal diffusion (silicate liquids, O isotopic fractionation, volatiles, tektites, polymetallic sulfide liquids, carbonate liquids, aqueous sulfate solutions), and liquid-state isothermal diffusion (self-diffusion, basalt-rhyolite interdiffusion, selective contamination, chemical diffusion).

  6. Experiments on metal-silicate plumes and core formation.

    Olson, Peter; Weeraratne, Dayanthie


    Short-lived isotope systematics, mantle siderophile abundances and the power requirements of the geodynamo favour an early and high-temperature core-formation process, in which metals concentrate and partially equilibrate with silicates in a deep magma ocean before descending to the core. We report results of laboratory experiments on liquid metal dynamics in a two-layer stratified viscous fluid, using sucrose solutions to represent the magma ocean and the crystalline, more primitive mantle and liquid gallium to represent the core-forming metals. Single gallium drop experiments and experiments on Rayleigh-Taylor instabilities with gallium layers and gallium mixtures produce metal diapirs that entrain the less viscous upper layer fluid and produce trailing plume conduits in the high-viscosity lower layer. Calculations indicate that viscous dissipation in metal-silicate plumes in the early Earth would result in a large initial core superheat. Our experiments suggest that metal-silicate mantle plumes facilitate high-pressure metal-silicate interaction and may later evolve into buoyant thermal plumes, connecting core formation to ancient hotspot activity on the Earth and possibly on other terrestrial planets.

  7. Decreased water flowing from a forest amended with calcium silicate

    Mark B. Green; Amey S. Bailey; Scott W. Bailey; John J. Battles; John L. Campbell; Charles T. Driscoll; Timothy J. Fahey; Lucie C. Lepine; Gene E. Likens; Scott V. Ollinger; Paul G. Schaberg


    Acid deposition during the 20th century caused widespread depletion of available soil calcium (Ca) throughout much of the industrialized world. To better understand how forest ecosystems respond to changes in a component of acidification stress, an 11.8-ha watershed was amended with wollastonite, a calcium silicate mineral, to restore available soil Ca to preindustrial...

  8. Estimation of high temperature metal-silicate partition coefficients

    Jones, John H.; Capobianco, Christopher J.; Drake, Michael J.


    It has been known for some time that abundances of siderophile elements in the upper mantle of the Earth are far in excess of those expected from equilibrium between metal and silicate at low pressures and temperatures. Murthy (1991) has re-examined this excess of siderophile element problem by estimating liquid metal/liquid silicate partition coefficients reduces from their measured values at a lower temperature, implying that siderophile elements become much less siderophilic at high temperatures. Murthy then draws the important conclusion that metal/silicate equilibrium at high temperatures can account for the abundances of siderophile elements in the Earth's mantle. Of course, his conclusion is critically dependent on the small values of the partition coefficients he calculates. Because the numerical values of most experimentally-determined partition coefficients increase with increasing temperature at both constant oxygen fugacity and at constant redox buffer, we think it is important to try an alternative extrapolation for comparison. We have computed high temperature metal/silicate partition coefficients under a different set of assumptions and show that such long temperature extrapolations yield values which are critically dependent upon the presumed chemical behavior of the siderophile elements in the system.

  9. Suppressive effects of a polymer sodium silicate solution on ...



    Oct 21, 2015 ... roses are available in almost every color, except blue. Flowers can ... Silicon (Si), as a major soil constituent, is an element that ... crops (such as rice) controls diseases and could reduce ... When the pH is 7.0 or less, silicate ions become ... disease) 0% infected of the whole leaves, (1) leaves showing 0 to.

  10. Ubiquitous high-FeO silicates in enstatite chondrites

    Lusby, David; Scott, Edward R. D.; Keil, Klaus


    SEM and EMPA were used to determine the mineral contents of four EH3 chondrites. All four showed the dominant enstatite peak, Fs 0-5, with 4-8 percent of FeO-rich pyroxene with Fs 5-20. Among the 542 objects found to contain high-FeO silicates, 18 were chondrules, 381 were rimmed or unrimmed grains, and 143 were aggregates. The high-FeO silicates in these objects are very largely pyroxene with Fs 5-23. Large grains of both FeO-rich and FeO-poor silicates were found to be present in the FeO-rich chondrules. This fact, together with the absence of clasts of FeO-rich chondritic material in the EH3 chondrites, suggests that FeO-rich grains were introduced before or during chondrule formation. It is concluded that FeO-rich and FeO-poor silicates were both present in the nebular region where E chondrites originated.

  11. Determination of boron in silicates after ion exchange separation

    Kramer, H.


    Existing methods for the determination of boron in silicates are not entirely satisfactory. Separation as the methyl ester is lengthy and frequently erratic. An accurate and rapid method applicable to glass, mineral, ore, and water samples uses ion exchange to remove interfering cations, and boron is determined titrimetrically in the presence of mannitol, using a pH meter to indicate the end point.

  12. Determination of reactivity rates of silicate particle-size fractions

    Angélica Cristina Fernandes Deus


    Full Text Available The efficiency of sources used for soil acidity correction depends on reactivity rate (RR and neutralization power (NP, indicated by effective calcium carbonate (ECC. Few studies establish relative efficiency of reactivity (RER for silicate particle-size fractions, therefore, the RER applied for lime are used. This study aimed to evaluate the reactivity of silicate materials affected by particle size throughout incubation periods in comparison to lime, and to calculate the RER for silicate particle-size fractions. Six correction sources were evaluated: three slags from distinct origins, dolomitic and calcitic lime separated into four particle-size fractions (2, 0.84, 0.30 and <0.30-mm sieves, and wollastonite, as an additional treatment. The treatments were applied to three soils with different texture classes. The dose of neutralizing material (calcium and magnesium oxides was applied at equal quantities, and the only variation was the particle-size material. After a 90-day incubation period, the RER was calculated for each particle-size fraction, as well as the RR and ECC of each source. The neutralization of soil acidity of the same particle-size fraction for different sources showed distinct solubility and a distinct reaction between silicates and lime. The RER for slag were higher than the limits established by Brazilian legislation, indicating that the method used for limes should not be used for the slags studied here.

  13. Phase Diagrams of Silicate Systems: Handbook; Third Issue; Ternary Systems

    In the third issue of the handbook Phase Diagrams of Silicate Systems, information is included on the phase relationships in systems containing...radioelectronics, nuclear engineering, etc. Not only are equilibrium phase diagrams presented in the handbook, but the phases existing in the

  14. Calorimetric signature of structural heterogeneity in a ternary silicate glass

    Zhang, Yanfei; Yang, G.; Yue, Yuanzheng


    We investigate the structural heterogeneity in a silicate glass by hyperquenching–annealing–calorimetry approach. The results show a striking phenomenon: two separated sub-Tg relaxation peaks appear on the calorimetric curve of the hyperquenched CaO–MgO–SiO2 glass, implying the existence of two d...

  15. Nd3+ Doped Silicate Glass Photonic Crystal Fibres

    YANG Lu-Yun; CHEN Dan-Ping; XIA Jin-An; WANG Chen; JIANG Xiong-Wei; ZHU Cong-Shan; QIU Jian-Rong


    @@ We report on the fabrication of two kinds of large core area Nd3+ doped silicate glass photonic crystal fibres, and demonstration of the fibre waveguiding properties. The measured minimum loss of one kind ofibres is 2.5 db/m at 660nm. The fibres sustain only a single mode at least over the wavelength range from 660nm to 980nm.

  16. Solid lubricants

    Sliney, Harold E.


    The state of knowledge of solid lubricants is reviewed. The results of research on solid lubricants from the 1940's to the present are presented from a historical perspective. Emphasis is placed largely, but not exclusively, on work performed at NASA Lewis Research Center with a natural focus on aerospace applications. However, because of the generic nature of the research, the information presented in this review is applicable to most areas where solid lubricant technology is useful.

  17. Effect of layered silicate nanoclay on the properties of silane crosslinked linear low-density polyethylene (LLDPE


    Full Text Available In the present work, the effect of pristine layered silicate montmorillonite (MMT nanoclay on the properties of silane-crosslinked LLDPE prepared by melt compounding is investigated. The effect of the sequence of feeding additives (nanoclay and grafting agent into the mixer on gel content, thermal and mechanical properties were studied. Results demonstrate that the sequence of feeding additives influences the final properties of nanocomposites. For samples prepared by first grafting of silane on LLDPE followed by incorporation of nanoclay into the polymer matrix, the gel content and the rate of crosslinking increased, while the elongation at break decreased. For samples prepared by first mixing nanoclay into the LLDPE matrix followed by the grafting reaction, the rate of crosslinking and the tensile properties did not change significantly. The gel content increased with increasing content of nanoclay for both process routes due to an enhanced permeation of water molecules into the polymer matrix in the presence of polar montmorillonite particles. Wide angle X-ray scattering (WAXS results proved the intercalation/partial exfoliation morphology of nanoclay in the silane-grafted LLDPE matrix. Differential scanning calorimetry (DSC data showed multiple melting behaviour for crosslinked samples which is indicative for different crystalline structures of the sol and gel part of the LLDPE matrix.

  18. Silicate Dispersion and Mechanical Reinforcement in Polysiloxane/Layered Silicate Nanocomposites

    Schmidt, Daniel F.


    We report the first in-depth comparison of the mechanical properties and equilibrium solvent uptake of a range of polysiloxane nanocomposites based on treated and untreated montmorillonite and fumed silica nanofillers. We demonstrate the ability of equilibrium solvent uptake data (and, thus, overall physical and chemical cross-link density) to serve as a proxy for modulus (combining rubber elasticity and Flory-Rehner theory), hardness (via the theory of Boussinesq), and elongation at break, despite the nonideal nature of these networks. In contrast, we find that tensile and tear strength are not well-correlated with solvent uptake. Interfacial strength seems to dominate equilibrium solvent uptake and the mechanical properties it predicts. In the montmorillonite systems in particular, this results in the surprising consequence that equilibrium solvent uptake and mechanical properties are independent of dispersion state. We conclude that edge interactions play a more significant role than degree of exfoliation, a result unique in the field of polymer nanocomposites. This demonstrates that even a combination of polymer/nanofiller compatibility and thermodynamically stable nanofiller dispersion levels may not give rise to reinforcement. These findings provide an important caveat when attempting to connect structure and properties in polymer nanocomposites, and useful guidance in the design of optimized polymer/layered silicate nanocomposites in particular. © 2009 American Chemical Society.

  19. PREFACE: 5th Baltic Conference on Silicate Materials

    Mezinskis, G.; Bragina, L.; Colombo, P.; Frischat, G. H.; Grabis, J.; Greil, P.; Deja, J.; Kaminskas, R.; Kliava, J.; Medvids, A.; Nowak, I.; Siauciunas, R.; Valancius, Z.; Zalite, I.


    Logo This Volume of IOP Conference Series: Materials Science and Engineering presents a selection of the contributions to the 5th Baltic Conference on Silicate Materials (BaltSilica2011) held at Riga Technical University, Riga, Latvia from 23-25 May 2011. The conference was organized by Riga Technical University (Latvia) and Kaunas University of Technology (Lithuania). The series of Baltic conferences on silicate materials was started since 2004: the first conference was held in Riga, Latvia, 2004; the second conference was held in Kaunas, Lithuania 2005; the third was held again in Riga, Latvia, 2007, and the fourth was held in Kaunas, Lithuania 2009. BaltSilica 2011 was attended by around 50 participants from Latvia, Lithuania, Estonia, Germany, Poland, Italy, France, Ukraine and Russia. In comparison with previous silicate materials conferences, the broadening of participating countries is an indication of the interest of scientists, engineers and students to exchange research ideas, latest results, and to find new research topics for cooperation in the fields of silicate, high temperature materials, and inorganic nanomaterials. The scientific programme included 8 invited plenary lectures 23 oral presentations and 25 posters [1]. Scientific themes covered in the conference and in this special issue: Natural and Artificial Stone Materials; Traditional and New Ceramic and Glass-Like Materials; Nanoparticles and Nanomaterials. This volume consists of 23 selected proceeding papers. The Editor of this special issue is grateful to all the contributors to BaltSilica 2011. I am also very grateful to the scientific committee, the local organizing committee, the session chairs, the referees who refereed the submitted articles to this issue, and to students from the Department of Silicate, High Temperature and Inorganic Nanomaterials Technology of the Riga Technical University who ensured the smooth running of the conference. Particular thanks goes to eight plenary

  20. Solid Matter

    Angelo, Joseph A


    Supported by a generous quantity of full-color illustrations and interesting sidebars, Solid Matter introduces the basic characteristics and properties of solid matter. It briefly describes the cosmic connection of the elements, leading readers through several key events in human pre-history that resulted in more advanced uses of matter in the solid state. Chapters include:. -Solid Matter: An Initial Perspective. -Physical Behavior of Matter. -The Gravity of Matter. -Fundamentals of Materials Science. -Rocks and Minerals. -Metals. -Building Materials. -Carbon Earth's Most Versatile Element. -S

  1. On the silicate crystallinities of oxygen-rich evolved stars and their mass-loss rates

    Liu, Jiaming; Jiang, B. W.; Li, Aigen; Gao, Jian


    For decades ever since the early detection in the 1990s of the emission spectral features of crystalline silicates in oxygen-rich evolved stars, there is a long-standing debate on whether the crystallinity of the silicate dust correlates with the stellar mass-loss rate. To investigate the relation between the silicate crystallinities and the mass-loss rates of evolved stars, we carry out a detailed analysis of 28 nearby oxygen-rich stars. We derive the mass-loss rates of these sources by modelling their spectral energy distributions from the optical to the far-infrared. Unlike previous studies in which the silicate crystallinity was often measured in terms of the crystalline-to-amorphous silicate mass ratio, we characterize the silicate crystallinities of these sources with the flux ratios of the emission features of crystalline silicates to that of amorphous silicates. This does not require the knowledge of the silicate dust temperatures, which are the major source of uncertainties in estimating the crystalline-to-amorphous silicate mass ratio. With a Pearson correlation coefficient of ∼-0.24, we find that the silicate crystallinities and the mass-loss rates of these sources are not correlated. This supports the earlier findings that the dust shells of low mass-loss rate stars can contain a significant fraction of crystalline silicates without showing the characteristic features in their emission spectra.

  2. Petrophysical Analysis of Siliceous-Ooze Sediments, More Basin, Norwegian Sea

    Awedalkarim, Ahmed; Sørensen, Morten Kanne; Fabricius, Ida Lykke


    Pelagic siliceous-ooze sediments occur above the hydrocarbon reservoir of the Ormen Lange gas field in More Basin, Norwegian Sea. A possible hydrocarbon prospect of siliceous ooze was proposed, but siliceous ooze is significantly different in texture from most commonly known reservoir rocks...

  3. Atypical behaviour of dissolved silicate in the Cochin backwater and Periyar river

    Sankaranarayanan, V.N.; Joseph, T.; Jayalakshmy, K.V.; Balachandran, K.K.

    Dissolved silicate was determined for 1 y (1982-83) covering a wide range of salinity from the estuarine mouth to the fresh water region. Silicate concentration ranged between 0.03 and 4.75 mgl/1. Silicate-salinity relationship was linear...

  4. Production test IP-728 half-plant sodium silicate test. Final report

    Geier, R.G.


    The sodium silicate addition to the coolant reduced the effluent concentrations of certain radionuclides. Nothing was observed during the course of the test to indicate that sodium silicate could not be used at all plants. However, the reductions obtained in effluent activity are not believed commensurate with the cost of silicate usage.

  5. [Origin of Lewis acidity in solid materials]. DOE Final Report for Grant DE-FG02-90ER14130

    Fripiat, J. J.


    The aim of the research undertaken within the framework of this DOE grant was to further understanding of the origin of the Lewis acidity in solid materials. The study centered around aluminas and alumino-silicates. The main tools for investigation of this phenomenon were high-resolution solid state {sub 27}Al NMR, complemented by EPR and the chemical determination of catalytic activity.

  6. Liquid-liquid extraction followed by solid-phase extraction for the determination of lipophilic pesticides in beeswax by gas chromatography-electron-capture detection and matrix-matched calibration.

    Jiménez, J J; Bernal, J L; del Nozal, Ma J; Alonso, C


    Analytical methods for the simultaneous analysis of lindane, chlorpyriphos, z-chlorfenvinphos, endosulfan A and B, 4,4'-DDE, 4,4'-TDE, acrinathrine, bromopropylate, tetradifon, coumaphos and fluvalinate in pure beeswax samples are studied. For the analysis of bleached beeswaxes, a liquid-liquid extraction with acetonitrile followed by a clean-up on polymeric cartridges is the best option in terms of recovery and precision. However, some interferences that hinder the identification and quantification of important varroacides are found when non-bleached beeswaxes are analyzed. The analysis of all compounds in the latter samples require a clean-up by coupling an ODS cartridge before the polymeric cartridge. Considerations about the influence of the matrix in the quantitative analysis by a classical external standard calibration are also made and the use of a matrix-matched calibration is advised. Recoveries resulted to be about 100% with coefficients of variation between 10% and 20% (n = 5) for concentrations of 0.5 and 5 mg/kg.

  7. Numerical matrix method for quantum periodic potentials

    Le Vot, Felipe; Meléndez, Juan J.; Yuste, Santos B.


    A numerical matrix methodology is applied to quantum problems with periodic potentials. The procedure consists essentially in replacing the true potential by an alternative one, restricted by an infinite square well, and in expressing the wave functions as finite superpositions of eigenfunctions of the infinite well. A matrix eigenvalue equation then yields the energy levels of the periodic potential within an acceptable accuracy. The methodology has been successfully used to deal with problems based on the well-known Kronig-Penney (KP) model. Besides the original model, these problems are a dimerized KP solid, a KP solid containing a surface, and a KP solid under an external field. A short list of additional problems that can be solved with this procedure is presented.

  8. Crystalline silicate dust around evolved stars - II. The crystalline silicate complexes

    Molster, F. J.; Waters, L. B. F. M.; Tielens, A. G. G. M.

    This is the second paper in a series of three in which we present an exhaustive inventory of the solid state emission bands observed in a sample of 17 oxygen-rich dust shells surrounding evolved stars. The data were taken with the Short and Long Wavelength Spectrographs on board of the Infrared

  9. Thermal conductivity of microPCMs-filled epoxy matrix composites

    Su, J.F.; Wang, X.Y; Huang, Z.; Zhao, Y.H.; Yuan, X.Y.


    Microencapsulated phase change materials (microPCMs) have been widely applied in solid matrix as thermal-storage or temperature-controlling functional composites. The thermal conductivity of these microPCMs/matrix composites is an important property need to be considered. In this study, a series of

  10. Stability evaluation of CNBr-Sepharose 4 B for using as solid matrix in immunoradiometric assay antibodies coupling; Avaliacao da estabilidade da CNBr-sepharose 4B para emprego como matriz solida no acoplamento de anticorpos especificos de ensaios imunorradiometricos

    Haber, Esther Piltcher; Silva, Sandra Rosa da; Borghi, Vania Caira [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil); Wajchenberg, Bernardo Leo [Sao Paulo Univ., SP (Brazil). Faculdade de Medicina


    The present work verifies the stability of a CNBr-Sepharose 4 B product (Pharmacia) stored at our laboratory one year after its expire date in view of its application as solid phase antibodies in the development of an immunoradiometric assay for measurement of serum human proinsulin. From rabbit IgG antiserum previously purified and concentrated by ultrafiltration (Publication IPEN 294, 1990) the antibodies were isolated by affinity chromatography. Sheep antiserum anti-rabbit IgG were coupled to cyanogen bromide activated Sepharose 4 B and the rabbit IgG which were bound to the immunosorbent could be obtained by elution with stepwise pH gradient from pH 7.0 to pH 2.5. The complying efficiency of the sheep antiserum to this solid phase material was 97%. The elution profile obtained shows identify of the sample related to the antiserum anti-rabbit IgG by affinity chromatography. These results suggest that this CNBr-Sepharose 4 B lot can be used satisfactorily to attach antibodies for use in the two-site immunoradiometric assay. (author). 7 refs., 1 fig.

  11. Biological and therapeutic effects of ortho-silicic acid and some ortho-silicic acid-releasing compounds: New perspectives for therapy

    Jurkić Lela Munjas


    Full Text Available Abstract Silicon (Si is the most abundant element present in the Earth's crust besides oxygen. However, the exact biological roles of silicon remain unknown. Moreover, the ortho-silicic acid (H4SiO4, as a major form of bioavailable silicon for both humans and animals, has not been given adequate attention so far. Silicon has already been associated with bone mineralization, collagen synthesis, skin, hair and nails health atherosclerosis, Alzheimer disease, immune system enhancement, and with some other disorders or pharmacological effects. Beside the ortho-silicic acid and its stabilized formulations such as choline chloride-stabilized ortho-silicic acid and sodium or potassium silicates (e.g. M2SiO3; M= Na,K, the most important sources that release ortho-silicic acid as a bioavailable form of silicon are: colloidal silicic acid (hydrated silica gel, silica gel (amorphous silicon dioxide, and zeolites. Although all these compounds are characterized by substantial water insolubility, they release small, but significant, equilibrium concentration of ortho-silicic acid (H4SiO4 in contact with water and physiological fluids. Even though certain pharmacological effects of these compounds might be attributed to specific structural characteristics that result in profound adsorption and absorption properties, they all exhibit similar pharmacological profiles readily comparable to ortho-silicic acid effects. The most unusual ortho-silicic acid-releasing agents are certain types of zeolites, a class of aluminosilicates with well described ion(cation-exchange properties. Numerous biological activities of some types of zeolites documented so far might probably be attributable to the ortho-silicic acid-releasing property. In this review, we therefore discuss biological and potential therapeutic effects of ortho-silicic acid and ortho-silicic acid -releasing silicon compounds as its major natural sources.

  12. Mid-IR water and silicate relation in protoplanetary disks

    Antonellini, S.; Bremer, J.; Kamp, I.; Riviere-Marichalar, P.; Lahuis, F.; Thi, W.-F.; Woitke, P.; Meijerink, R.; Aresu, G.; Spaans, M.


    Context. Mid-IR water lines from protoplanetary disks around T Tauri stars have a detection rate of 50%. Models have identified multiple physical properties of disks such as dust-to-gas mass ratio, dust size power law distribution, disk gas mass, disk inner radius, and disk scale height as potential explanations for the current detection rate. Aims: In this study, we aim to break degeneracies through constraints obtained from observations. We search for a connection between mid-IR water line fluxes and the strength of the 10 μm silicate feature. Methods: We analyze observed water line fluxes from three blends at 15.17, 17.22 and 29.85 μm published earlier and compute the 10 μm silicate feature strength from Spitzer spectra to search for possible trends. We use a series of published ProDiMo thermo-chemical models, to explore disk dust and gas properties, and also the effects of different central stars. In addition, we produced two standard models with different dust opacity functions, and one with a parametric prescription for the dust settling. Results: Our series of models that vary properties of the grain size distribution suggest that mid-IR water emission anticorrelates with the strength of the 10 μm silicate feature. The models also show that the increasing stellar bolometric luminosity simultaneously enhance the strength of this dust feature and the water lines fluxes. No correlation is found between the observed mid-IR water lines and the 10 μm silicate strength. Two-thirds of the targets in our sample show crystalline dust features, and the disks are mainly flaring. Our sample shows the same difference in the peak strength between amorphous and crystalline silicates that was noted in earlier studies, but our models do not support this intrinsic difference in silicate peak strength. Individual properties of our models are not able to reproduce the most extreme observations, suggesting that more complex dust properties (e.g., vertically changing) are

  13. Enhancement of ionic conductivity of composite membranes for all-solid-state lithium rechargeable batteries incorporating tetragonal Li7La3Zr2O12 into a polyethylene oxide matrix

    Choi, Jeong-Hee; Lee, Chul-Ho; Yu, Ji-Hyun; Doh, Chil-Hoon; Lee, Sang-Min


    The lithium ion conductivities of as-prepared composite membranes consisting of a polyethylene oxide (PEO) matrix with various contents of tetragonal Li7La3Zr2O12 (LLZO) were evaluated, and the optimum composition (52.5% LLZO) was determined by performing AC impedance measurements. The ionic conductivities of the composite membranes pass through a maximum as the LLZO content varies. Therefore, the hybridization of the organic and inorganic components of these membranes results in synergetic effects on their lithium ionic conductivity. In addition, tests of Li/composite membrane/LiNi0.6Co0.2Mn0.2O2 half-cells found that their charge/discharge properties are better than those of a PEO-only membrane and a membrane containing 52.5% Al2O3 instead of LLZO.

  14. Process for converting sodium nitrate-containing, caustic liquid radioactive wastes to solid insoluble products

    Barney, Gary S.; Brownell, Lloyd E.


    A method for converting sodium nitrate-containing, caustic, radioactive wastes to a solid, relatively insoluble, thermally stable form is provided and comprises the steps of reacting powdered aluminum silicate clay, e.g., kaolin, bentonite, dickite, halloysite, pyrophyllite, etc., with the sodium nitrate-containing radioactive wastes which have a caustic concentration of about 3 to 7 M at a temperature of C to C to thereby entrap the dissolved radioactive salts in the aluminosilicate matrix. In one embodiment the sodium nitrate-containing, caustic, radioactive liquid waste, such as neutralized Purex-type waste, or salts or oxide produced by evaporation or calcination of these liquid wastes (e.g., anhydrous salt cake) is converted at a temperature within the range of C to C to the solid mineral form-cancrinite having an approximate chemical formula 2(NaAlSiO.sub.4) .sup.. xSalt.sup.. y H.sub.2 O with x = 0.52 and y = 0.68 when the entrapped salt is NaNO.sub.3. In another embodiment the sodium nitrate-containing, caustic, radioactive liquid is reacted with the powdered aluminum silicate clay at a temperature within the range of C to C, the resulting reaction product is air dried eitheras loose powder or molded shapes (e.g., bricks) and then fired at a temperature of at least C to form the solid mineral form-nepheline which has the approximate chemical formula of NaAlSiO.sub.4. The leach rate of the entrapped radioactive salts with distilled water is reduced essentially to that of the aluminosilicate lattice which is very low, e.g., in the range of 10.sup.-.sup.2 to 10.sup.-.sup.4 g/cm.sup.2 -- day for cancrinite and 10.sup.-.sup.3 to 10.sup.-.sup.5 g/cm.sup.2 -- day for nepheline.

  15. Characteristics of wasteform composing of phosphate and silicate to immobilize radioactive waste salts.

    Park, Hwan-Seo; Cho, In-Hak; Eun, Hee Chul; Kim, In-Tae; Cho, Yong Zun; Lee, Han-Soo


    In the radioactive waste management, metal chloride wastes from a pyrochemical process is one of problematic wastes not directly applicable to a conventional solidification process. Different from a use of minerals or a specific phosphate glass for immobilizing radioactive waste salts, our research group applied an inorganic composite, SAP (SiO(2)-Al(2)O(3)-P(2)O(5)), to stabilize them by dechlorination. From this method, a unique wasteform composing of phosphate and silicate could be fabricated. This study described the characteristic of the wasteform on the morphology, chemical durability, and some physical properties. The wasteform has a unique "domain-matrix" structure which would be attributed to the incompatibility between silicate and phosphate glass. At higher amounts of chemical binder, "P-rich phase encapsulated by Si-rich phase" was a dominant morphology, but it was changed to be Si-rich phase encapsulated by P-rich phase at a lower amount of binder. The domain and subdomain size in the wasteform was about 0.5-2 μm and hundreds of nm, respectively. The chemical durability of wasteform was confirmed by various leaching test methods (PCT-A, ISO dynamic leaching test, and MCC-1). From the leaching tests, it was found that the P-rich phase had ten times lower leach-resistance than the Si-rich phase. The leach rates of Cs and Sr in the wasteform were about 10(-3)g/m(2)· day, and the leached fractions of them were about 0.04% and 0.06% at 357 days, respectively. Using this method, we could stabilize and solidify the waste salt to form a monolithic wasteform with good leach-resistance. Also, the decrease of waste volume by the dechlorination approach would be beneficial in the final disposal cost, compared with the present immobilization methods for waste salt.

  16. The unique invention of the siliceous sponges: their enzymatically made bio-silica skeleton.

    Müller, Werner E G; Wang, Xiaohong; Chen, Ailin; Hu, Shixue; Gan, Lu; Schröder, Heinz C; Schloßmacher, Ute; Wiens, Matthias


    Sponges are sessile filter feeders that, among the metazoans, evolved first on Earth. In the two classes of the siliceous sponges (the Demospongiae and the Hexactinellida), the complex filigreed body is stabilized by an inorganic skeleton composed of amorphous silica providing them a distinct body shape and plan. It is proposed that the key innovation that allowed the earliest metazoans to form larger specimens was the enzyme silicatein. This enzyme is crucial for the formation of the siliceous skeleton. The first sponge fossils with body preservation were dated back prior to the "Precambrian-Cambrian" boundary [Vendian (610-545 Ma)/Ediacaran (542-580 Ma)]. A further molecule required for the formation of a hard skeleton was collagen, fibrous organic filaments that need oxygen for their formation. Silicatein forming the spicules and collagen shaping their morphology are the two organic components that control the appositional growth of these skeletal elements. This process starts in both demosponges and hexactinellids intracellularly and is completed extracellularly where the spicules may reach sizes of up to 3 m. While the basic strategy of their formation is identical in both sponge classes, it differs on a substructural level. In Hexactinellida, the initial silica layers remain separated, those layers bio-fuse (bio-sinter) together in demosponges. In some sponge taxa, e.g., the freshwater sponges from the Lake Baikal, the individual spicules are embedded in an organic matrix that is composed of the DUF protein. This protein comprises clustered stretches of amino acid sequences composed of pronounced hydrophobic segments, each spanning around 35 aa. We concluded with the remark of Thompson (1942) highlighting that "the sponge-spicule is a typical illustration of the theory of 'bio-crystallisation' to form 'biocrystals' ein Mittelding between an inorganic crystal and an organic secretion." Moreover, the understanding of the enzymatic formation of the spicules

  17. Chemical Zoning of Feldspars in Lunar Granitoids: Implications for the Origins of Lunar Silicic Magmas

    Mills, R. D; Simon, J. I.; Alexander, C.M. O'D.; Wang, J.; Christoffersen, R.; Rahman, Z..


    Fine-scale chemical and textural measurements of alkali and plagioclase feldspars in the Apollo granitoids (ex. Fig. 1) can be used to address their petrologic origin(s). Recent findings suggest that these granitoids may hold clues of global importance, rather than of only local significance for small-scale fractionation. Observations of morphological features that resemble silicic domes on the unsampled portion of the Moon suggest that local, sizable net-works of high-silica melt (>65 wt % SiO2) were present during crust-formation. Remote sensing data from these regions suggest high concentrations of Si and heat-producing elements (K, U, and Th). To help under-stand the role of high-silica melts in the chemical differentiation of the Moon, three questions must be answered: (1) when were these magmas generated?, (2) what was the source material?, and (3) were these magmas produced from internal differentiation. or impact melting and crystallization? Here we focus on #3. It is difficult to produce high-silica melts solely by fractional crystallization. Partial melting of preexisting crust may therefore also have been important and pos-sibly the primary mechanism that produced the silicic magmas on the Moon. Experimental studies demonstrate that partial melting of gabbroic rock under mildly hydrated conditions can produce high-silica compositions and it has been suggested by that partial melting by basaltic underplating is the mechanism by which high-silica melts were produced on the Moon. TEM and SIMS analyses, coordinated with isotopic dating and tracer studies, can help test whether the minerals in the Apollo granitoids formed in a plutonic setting or were the result of impact-induced partial melting. We analyzed granitoid clasts from 3 Apollo samples: polymict breccia 12013,141, crystalline-matrix breccia 14303,353, and breccia 15405,78

  18. The Role of Gas-Silicate Chemisorption Reactions in Modifying Planetary Crusts and Surfaces

    King, P. L.; Henley, R. W.; Wykes, J. L.; Renggli, C.; Troitzsch, U.; Clark, D.; O'Neill, H. S.


    Evidence for gas-solid reactions is found throughout the solar system: for example, sulfidation reactions in some meteorites and secondary phases coating lunar pyroclastic glasses. On Earth, the products of gas-solid reactions are documented in volcanic systems, metalliferous mineral deposits, impact craters, and on dust or meteorites after passage through the atmosphere - such reactions are also likely on the surfaces of Mars and Venus. To understand the chemical dynamics of such gas-solid reactions, we are undertaking systematic experiments and thermochemical modelling. Experiments were conducted in a vertical gas-mixing furnace at 600 - 800 °C and 1 bar, using SO2and a range of Ca-bearing materials: labradorite, feldspar glass and anorthosite (rock). In each case, anhydrite formed rapidly. In shorter experiments with labradorite, isolated anhydrite is observed surrounded by 'moats' of Ca-depleted silicate. In longer experiments, anhydrite is found as clusters of crystals that, in some cases, extend from the substrate forming precarious 'towers' (Figure). Anhydrite fills cracks in porous samples. We propose that the nucleation and rapid growth of anhydrite on the surface of these Ca-rich phases occurs by chemisorption of SO2(g) molecules with slightly negatively charged oxygen onto available near-surface calcium with slight positive charge. Anhydrite growth is sustained by SO2(g) chemisorption and Ca migration through the reacting silicate lattice, accelerated by increased bond lengths at high temperature. Significantly, the chemisorption reaction indicates that SO2 disproportionates to form both oxidized sulfur (as anhydrite) and a reduced sulfur species (e.g., an S* radical ion). On Earth, in the presence of H2O, the predominant reduced sulfur species is H2S, through an overall reaction: 3CaAl2Si2O8 + 4 SO2(g)+ H2O(g) → 3CaSO4 + 3Al2SiO5 + 3SiO2 + H2S(g)The reduced sulfur may react with gas phase Fe, Ni, Zn and Cu cluster compounds to form metal sulfides

  19. Impact of paint matrix composition and thickness of paint layer on the activity of photocatalytic paints

    Homa Piotr


    Full Text Available Silicate, acrylic and latex photocatalytic paints were analyzed in regards to impact of paint matrix composition and paint layer’s thickness on performance in two photocatalytic tests. These included performances in photocatalytic decomposition of benzo[a]pyrene (BaP and assessment of photocatalytic activity through use of smart ink test. Silicate photocatalytic paints displayed lower photocatalytic activity in comparison to acrylic and latex photocatalytic paints in both tests, despite the similar content of nanocrystalline TiO2. Measurements of depth of UV light penetration through the paints layer were performed and it appeared, that more porous structure of coating resulted in deeper penetration of UV light. In the case of acrylic paint, the thickness of the photocatalytic layer was around 9 μm, but for silicate paint DR this thickness was higher, around 21 μm.

  20. Fully Sampled Maps of Ices and Silicates in Front of Cepheus A East with Spitzer

    Sonnentrucker, P; Gerakines, P A; Bergin, E A; Melnick, G J; Forrest, W J; Pipher, J L; Whittet, D C B


    We report the first fully sampled maps of the distribution of interstellar CO2 ices, H2O ices and total hydrogen nuclei, as inferred from the 9.7 micron silicate feature, toward the star-forming region Cepheus A East with the IRS instrument onboard the Spitzer Space Telescope. We find that the column density distributions for these solid state features all peak at, and are distributed around, the location of HW2, the protostar believed to power one of the outflows observed in this star-forming region. A correlation between the column density distributions of CO2 and water ice with that of total hydrogen indicates that the solid state features we mapped mostly arise from the same molecular clumps along the probed sight lines. We therefore derive average CO2 ice and water ice abundances with respect to the total hydrogen column density of X(CO2)_ice~1.9x10^-5 and X(H2O)_ice~7.5x10^-5. Within errors, the abundances for both ices are relatively constant over the mapped region exhibiting both ice absorptions. The ...

  1. Removal of Cadmium Ions from Aqueous Solution by Silicate-incorporated Hydroxyapatite

    SHI Hebin; ZHONG Hong; LIU Yu; DENG Jinyang


    This article reports a preliminary research on silicate-incorporated hydroxyapatite as a new environmental mineral used to remove cadmium ions from aqueous solutions. The silicate-incorporated hydroxyapatite was prepared by coprecipitation and calcining, and silicate was incorporated into the crystal lattice of hydroxyapatite by partial substitution of phosphate. The amount of cadmium ions removed by silicate-incorporated hydroxyapatite was significantly elevated, which was 76% higher than that of pure hydroxyapatite. But the sorption behavior of cadmium ions on silicate-incorporated hydroxyapatite was similar to that of pure hydroxyapatite. Morphological study revealed that silicate incorporation confined the crystal growth and increased the specific surface area of hydroxyapatite,which were in favor of enhancing the cadmium ion sorpfion capacity of the samples. Incorporation of silicate into hydroxyapatite seems to be an effective approach to improve the environmental property of hydroxyapatite on removal of aqueous cadmium ions.


    Ishizuka, Shinnosuke; Kimura, Yuki [Institute of Low Temperature Science, Hokkaido University, Hokkaido Sapporo 060-0819 (Japan); Sakon, Itsuki [Department of Astronomy, School of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan)


    We developed a new experimental system for infrared (IR) measurements on free-flying nucleating nanoparticles in situ and applied it to studies on silicate particles. We monitored the condensation of magnesium-bearing silicate nanoparticles from thermally evaporated magnesium and silicon monoxide vapor under an atmosphere of oxygen and argon. The IR spectrum of newly condensed particles showed a spectral feature for non-crystalline magnesium-bearing silicate that is remarkably consistent with the IR spectrum of astronomically observed non-crystalline silicate around oxygen-rich evolved stars. The silicate crystallized at <500 K and eventually developed a high crystallinity. Because of the size effects of nanoparticles, the silicate would be expected to be like a liquid at least during the initial stages of nucleation and growth. Our experimental results therefore suggest decreasing the possible formation temperature of crystalline silicates in dust formation environments with relatively higher pressure.

  3. The Matrix Cookbook

    Petersen, Kaare Brandt; Pedersen, Michael Syskind

    Matrix identities, relations and approximations. A desktop reference for quick overview of mathematics of matrices.......Matrix identities, relations and approximations. A desktop reference for quick overview of mathematics of matrices....

  4. Solid consistency

    Bordin, Lorenzo; Creminelli, Paolo; Mirbabayi, Mehrdad; Noreña, Jorge


    We argue that isotropic scalar fluctuations in solid inflation are adiabatic in the super-horizon limit. During the solid phase this adiabatic mode has peculiar features: constant energy-density slices and comoving slices do not coincide, and their curvatures, parameterized respectively by ζ and Script R, both evolve in time. The existence of this adiabatic mode implies that Maldacena's squeezed limit consistency relation holds after angular average over the long mode. The correlation functions of a long-wavelength spherical scalar mode with several short scalar or tensor modes is fixed by the scaling behavior of the correlators of short modes, independently of the solid inflation action or dynamics of reheating.

  5. Metal-Silicate Differentiation from a Metal Pond Emulsion during Core Formation

    Fleck, J.; Weeraratne, D. S.


    The terrestrial planets demonstrate a heavy bombardment of impacts in their early formation history. Impacts are violent, energetic collisions that may melt the surface and/or cause segregation of impactor material including silicates and liquid metal iron. Although theoretical studies have been done with conceptual models for metal diapir descent to form terrestrial planetary cores, physical or computer modeling studies are scarce due to the strong variations in physical properties between liquid metals and solid silicates. We use laboratory fluid experiments to study core formation processes using liquid metal gallium and high viscosity glucose syrup which provide the buoyancy ratios expected for planetary interiors and low Reynolds number flow dynamics. Preliminary results indicate that the physical process of sinking metal diapirs form trailing conduits that may drag low density surface magmatic material to the base of the mantle. The low density material collects, grows at the base of the box, and rises back to the surface. We compare two cases of a pond made of 1) liquid metal emulsion and 2) a smooth coalesced metal pond. We find that emulsion experiments entrain greater amounts of low density fluid to the base of the box. Once the metal diapir reaches the base, conduit material exhibits flow reversal to return buoyantly to the surface. In the case of coalesced liquid metal diapirs, low density conduit material returns to the surface through the pre-established conduit. In the emulsion diapir case, we observe the formation of a new thermo-chemical buoyant plume that grows, exits the conduit, and travels along a new pathway to the surface. Metal plume descent and chemical plume rise velocities are consistent with Stokes velocity. Estimates of metal-silicate plume sinking time and thermo-chemical plume rise time for terrestrial planetary interiors are provided. We suggest the observation of a thermo-chemical plume as a source for orogeny at the surface of

  6. Argon Partitioning Between Metal and Silicate Liquids in the Laser-Heated DAC to 25 GPa

    Bouhifd, M. A.; Jephcoat, A. P.


    The accretion of the Earth from primordial material and its subsequent segregation into core and mantle are fundamental problems in terrestrial and solar system science. Many of the questions about the process, although well developed as model scenarios over the last few decades, are still open and much debated, and include, for example, whether the core is, or was, a reservoir for the noble (rare) gases. In the present study we use for the first time the laser-heated diamond-anvil cell (LHDAC) to study the Ar partitioning at high-pressure and temperature between metal and silicate liquids. Little work has been reported on noble gas partitioning at pressure since a single multi-anvil experiment to 10 GPa (Matsuda et al., 1993). We used either compacted glass powders simulating that of a model C1 chondrite and iron metal, or pure metal alloys (pure Fe, FeNiCo alloy, FeSi). Thermal insulation from the diamonds was achieved with solid argon as pressure medium. The samples were heated by a multimode YAG laser for an average of 15 minutes and temperatures were determined spectro-radiometrically with a fit to a grey-body Planck function. Samples recovered after the runs were analysed by electron microprobe with spatial resolution near 1 μ m. The argon melts by conductive heating from the molten sample dissolving into the metal/silicate melt. Preliminary results on Ar solubility at lower pressures show good agreement with data reported by White et al. (1986) for Ar solubility in sanidine (KAlSi3O8). With sanidine melt, Ar solubility increases up to around 5-6 GPa where it reaches about 2.5 wt%, and remains roughly constant to higher pressures, suggesting that a threshold concentration is reached. Similar behavior is observed for a mix of C1-chondrite composition and iron and the results imply that the solubility of Ar is intimately related to liquid structure at high pressure. We also present results on Ar solubility into pure silicate liquids of varying composition in

  7. In situ hydroxyapatite nanofiber growth on calcium borate silicate ceramics in SBF and its structural characteristics

    Pu, Yinfu; Huang, Yanlin; Qi, Shuyun [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Chen, Cuili [Department of Physics and Interdisciplinary Program of Biomedical, Mechanical & Electrical Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of); Seo, Hyo Jin, E-mail: [Department of Physics and Interdisciplinary Program of Biomedical, Mechanical & Electrical Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of)


    A novel calcium silicate borate Ca{sub 11}Si{sub 4}B{sub 2}O{sub 22} ceramic was firstly prepared by the conventional solid-state reaction. In vitro hydroxyapatite mineralization was investigated by soaking the ceramics in simulated body fluid (SBF) solutions at body temperature (37 °C) for various time periods. Scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD) measurements were applied to investigate the samples before and after the immersion of ceramics in SBF solution. The elemental compositions of a hydroxyapatite layer on the ceramics during the mineralization were confirmed by X-ray energy-dispersive spectra (EDS). Meanwhile, the bending strength and elastic modulus of Ca{sub 11}Si{sub 4}B{sub 2}O{sub 22} ceramics were also measured, which indicate that the biomaterials based on Ca{sub 11}Si{sub 4}B{sub 2}O{sub 22} ceramics possess bioactivity and might be a potential candidate as biomaterials for hard tissue repair. The bioactive mineralization ability was evaluated on the base of its crystal structural characteristics, i.e., silanol (Si–OH) and B–OH groups can be easily induced on the surface of Ca{sub 11}Si{sub 4}B{sub 2}O{sub 22} ceramics soaked in SBF solutions. - Highlights: • Calcium silicate borate Ca{sub 11}Si{sub 4}B{sub 2}O{sub 22} ceramics were developed as a new biomaterial. • Ca{sub 11}Si{sub 4}B{sub 2}O{sub 22} shows a superior in vitro bioactivity by inducing bone-like apatite. • Ca{sub 11}Si{sub 4}B{sub 2}O{sub 22} has good mechanical properties as potential candidate biomaterials. • The structure with SiO{sub 4} and BO{sub 3} groups is favorable for hydroxyapatite formation.

  8. Electrochemical Acceleration of Carbonate and Silicate Weathering for CO2 Mitigation

    Rau, G. H.; Carroll, S.


    Carbonate and many silicate minerals dissolve in strong acids, and such acids are commonly generated at the anode of a conventional saline water electrolysis cell. It was therefore reasoned that encasing such an anode with base minerals would lead to enhanced mineral dissolution and hence increased hydroxide (base) generation at the cathode, formed in course of splitting water, generating H2 and OH-. Subsequent exposue of the alkalized solution to CO2 (e.g., as in air) would lead to absorption of the CO2 and formation of stable dissolved or solid (bi)carbonates for carbon sequestration. Previously, it has been demonstrated that mineral carbonate encasement of a seawater electrolysis cell anode indeed generated basic solutions in excess of pH 9 that were subsequently neutralized via contact with air CO2, increasing the carbon content of the initial seawater by 30% (Rau, G.H. 2008. Environ Sci. Techol. 42, 8935-). To test such a weathering/CO2 capture scheme using silicate minerals, either powdered wollastonite or ultramafic rock standard (UM-4) was encased around the anode of an electrolysis cell composed of graphite electrodes and a 0.25M Na2SO4 electrolyte solution. After 0.5 to 1.5 hrs of electricity application (3.5Vdc, 5-10mA), the electrolyte pH rose to as much as 11.1 (initial and blank solution pH's electrolysis times and/or alternative electrolyte solutions might allow formation and precipitation of Ca or Mg carbonates. Such electrochemistry might ultimately provide a safe, efficient way to harness the planet's: i) large, off-peak or off-grid renewable electricity potential, ii) abundant basic minerals, and iii) vast natural brine electrolytes for large-scale air CO2 mitigation and carbon-negative H2 production.


    Suyanta Suyanta


    Full Text Available Researches about the effects of aging time toward crystallinity of products in the synthesis of mesoporous silicates MCM-41 have been done. MCM-41 was synthesized by hydrothermal treatment to the mixture of sodium silicate, sodium hydroxide, cetyltrimetylammoniumbromide (CTMAB and aquadest in the molar ratio of 8Na2SiO3 : CTMAB : NaOH : 400H2O. Hydrothermal treatment was carried out at 110 °C in a teflon-lined stainless steel autoclave heated in the oven, with variation of aging time, i.e.: 4, 8, 12, 16, 24, 36, 48, and 72 h respectively. The solid phase were filtered, then washed with deionised water, and dried in the oven at 100 °C for 2 h. The surfactant CTMAB was removed by calcinations at 550 °C for 10 h with heating rate 2 °C/min. The as-synthesized and calcined powders were characterized by using FTIR spectroscopy and X-ray diffraction method. The relative crystallinity of products was evaluated based on the intensity of d100 peaks. The best product was characterized by using N2 physisorption method in order to determine the specific surface area, mean pore diameter, lattice parameter, and pore walls thickness. It was concluded that the relative crystallinity of the products was sensitively influenced by the aging time. The highest relative crystallinity was achieved when used 36 h of aging time in hydrothermal treatment. In this optimum condition the product has 946.607 m2g-1 of specific surface area, 3.357 nm of mean pore diameter, 4.533 nm of lattice parameter, and 1.176 nm of pore walls thickness.

  10. Immobilization of Zinc Phthalocyanines in Silicate Matrices and Investigation of Their Photobactericidal Effect on E.coli

    Spas Artarsky


    Full Text Available The aim of the present investigation was to immobilize zinc phthalocyanines in a silicate matrix and to test the photobactericidal properties of the matrices so prepared toward Esherichia coli in model aqueous media. For the purpose, tetra tertiary butyl zinc phthalocyanine (TBZnPc and zinc phthalocyanine tetrasulfonic acid (ZnPcTS were used. The abilities of these two photosensitizers to generate singlet oxygen in solution were compared by following the rate of photobleaching of 1,3-diphenylisobenzofuran (DPBF at 430 nm in dimethylformamide (DMF.The results of this study show clearly that, under the conditions used here, the TBZnPc is the more effective generator of singlet oxygen; with it the DPBF was virtually completely photobleached in 4 min, while with the ZnPcTS under the same conditions, it took 12 min to reach this point. Glass conjugates with the two phthalocyanines were obtained by the sol-gel technique and were characterized by a well-defined color due to the phthalocyanine incorporated in the silicate matrix. Glasses with an intense, but inhomogeneous, green color were obtained when the tetrasulfonic derivative of the zinc phthalocyanine was used, while blue glasses of evenly distributed coloration were formed from the tetra tertiary butyl derivative.The ZnPcTS conjugate demonstrates more effective singlet oxygen evolution than is the case with the TBZnPc conjugate. These results are the opposite of those obtained for the free phthalocyanines in solution. The structural formulae of the compounds show that TBZnPc has a more pronounced hydrophobic character than the sulfonic derivative. In our view, the relative reactivities of the conjugates can be explained by the tetrasulfonic derivative being situated mainly in the surface parts of the glass matrix where the hydrophilic character is prevailing, while the tertiary butyl derivative is mainly present in the internal parts of the matrix as a result of which it is less accessible and

  11. Efficient 2 μm emission in Nd3+/Ho3+ co-doped silicate-germanate glass pumped by common 808 nm LD

    Chen, Rong; Tian, Ying; Li, Bingpeng; Huang, Feifei; Wang, Caizhi; Jing, Xufeng; Zhang, Junjie; Xu, Shiqing


    Nd3+/Ho3+ co-doped silicate-germanate glass has been synthesized by high temperature melt-quenching method. Near infrared emission centered at 2 μm has been successfully obtained by incorporating Nd3+ and Ho3+ in present glass. The Judd-Ofelt intensity parameters Ωt (t=2, 4, 6), and radiative properties of Ho3+ were calculated and discussed by using the Judd-Ofelt theory. The energy transfer processes and luminescence properties of Nd3+/Ho3+ co-doped glasses were analyzed pumped by a conventional 808 nm laser diode. Desirable spectroscopic characteristics indicates that Nd3+/Ho3+ co-doped silicate-germanate glass might be a good alternative matrix for 2 μm band mid-infrared laser.

  12. The curing process of layered silicate/epoxy nanocomposites

    Nieminen, Ilkka


    The industrial methods of processing polymeric thermoset matrix nanocomposites require a good knowledge of the matrix curing process. The dispersion of nanoparticles in the matrix effects the curing process due to the interaction between nanoparticles and the matrix at the atomic level, especially when the nanoparticles have been treated with a surfactant agent ( alquilammonium) that is in competition with the reactive groups of the hardener. This thesis investigates the curing process o...

  13. Chemical Fractionation in the Silicate Vapor Atmosphere of the Earth

    Pahlevan, Kaveh; Eiler, John; 10.1016/j.epsl.2010.10.03


    Despite its importance to questions of lunar origin, the chemical composition of the Moon is not precisely known. In recent years, however, the isotopic composition of lunar samples has been determined to high precision and found to be indistinguishable from the terrestrial mantle despite widespread isotopic heterogeneity in the Solar System. In the context of the giant-impact hypothesis, this level of isotopic homogeneity can evolve if the proto-lunar disk and post-impact Earth undergo turbulent mixing into a single uniform reservoir while the system is extensively molten and partially vaporized. In the absence of liquid-vapor separation, such a model leads to the lunar inheritance of the chemical composition of the terrestrial magma ocean. Hence, the turbulent mixing model raises the question of how chemical differences arose between the silicate Earth and Moon. Here we explore the consequences of liquid-vapor separation in one of the settings relevant to the lunar composition: the silicate vapor atmosphere...

  14. Dry reusing and wet reclaiming of used sodium silicate sand


    Based on the characteristics of used sodium silicate sand and the different use requirements for recycled sand, "dry reusing and wet reclaiming of used sodium silicate sand" is considered as the most suitable technique for the used sand. When the recycled sand is used as support sand, the used sand is only reused by dry process including breaking, screening, dust-removal, etc., and it is not necessary that the used sand is reclaimed with strongly rubbing and scraping method, but when the recycled sand is used as facing sand (or single sand), the used sand must be reclaimed by wet method for higher removal rate of the residual binders. The characteristics and the properties of the dry reused sand are compared with the wet reclaimed sand after combining the different use requirements of support sand and facing sand (or single sand), and above the most adaptive scheme has also been validated.

  15. Thermochemistry of Rare Earth Silicates for Environmental Barrier Coatings

    Costa, Gustavo; Jacobson, Nathan


    Rare earth silicates are promising candidates as environmental protective coatings (EBCs) for silica-forming ceramics and composites in combustion environments since they are predicted to have lower reactivity with the water vapor combustion products. The reactivity of rare earth silicates is assessed by the thermodynamic activity of the silica component which is best measured by Knudsen effusion mass spectrometry (KEMS). Here, we discuss a novel method based on a reducing agent to increase the partial pressure of SiO(g) which is then used to calculate thermodynamic activity of silica in Y2O3-SiO2 and Yb2O3-SiO2 systems. After the KEMS measurements, samples were probed by X-ray diffraction and their phase content was calculated from Rietveld refinement.

  16. Calc-silicate mineralization in active geothermal systems

    Bird, D.K.; Schiffman, P.; Elders, W.A.; Williams, A.E.; McDowell, S.D.


    The detailed study of calc-silicate mineral zones and coexisting phase relations in the Cerro Prieto geothermal system were used as examples for thermodynamic evaluation of phase relations among minerals of variable composition and to calculate the chemical characteristics of hydrothermal solutions compatible with the observed calc-silicate assemblages. In general there is a close correlation between calculated and observed fluid compositions. Calculated fugacities of O{sub 2} at about 320{degrees}C in the Cerro Prieto geothermal system are about five orders of magnitude less than that at the nearby Salton Sea geothermal system. This observation is consistent with the occurrence of Fe{sup 3+} rich epidotes in the latter system and the presence of prehnite at Cerro Prieto.

  17. Effective elastic moduli of polymer-layered silicate nanocomposites


    Polymer-layered silicate (PLS) nanocomposites exhibit some mechanical properties that are much better than conventional polymer filled composites. A relatively low content of layered silicate yields a significant enhancement of material performance. After the volume fraction of clay reaches a relatively low "critical value"; however, further increasing does not show a greater stiffening effect. This phenomenon is contrary to previous micromechanical pre-dictions and is not understood well. Based on the analysis on the microstructures of PLS nanocomposites, the present note provides an insight into the physical micromechanisms of the above unexpected phenomenon. The Mori-Tanaka scheme and a numerical method are employed to estimate the effec-tive elastic moduli of such a composite.

  18. Xe and Kr analyses of silicate inclusions from iron meteorites.

    Bogard, D. D.; Huneke, J. C.; Burnett, D. S.; Wasserburg, G. J.


    Measurements have been conducted of the amounts and isotopic composition of Xe and Kr in silicate inclusions of several iron meteorites. It is shown that the Xe and Kr contents are comparable to chondritic values. The isotopic compositions show trapped gas of both chondritic and atmospheric composition. Large spallation effects occur in some of the meteorites; the spallation spectra in some instances differ from those reported for stone meteorites. In several meteorites, very large neutron capture effects on Br and I occur. All samples have pronounced Xe129 excesses which apparently indicate differences in the formation times from chondrites of less than about 100 million years; however, the presence of trapped Xe132 in silicates which were enclosed in molten Fe-Ni and cooled slowly proves that they were not entirely outgassed, so that some of the Xe129 excess may also be trapped.

  19. Modeling the viscosity of silicate melts containing manganese oxide

    Kim Wan-Yi


    Full Text Available Our recently developed model for the viscosity of silicate melts is applied to describe and predict the viscosities of oxide melts containing manganese oxide. The model requires three pairs of adjustable parameters that describe the viscosities in three systems: pure MnO, MnO-SiO2 and MnO-Al2O3-SiO2. The viscosity of other ternary and multicomponent silicate melts containing MnO is then predicted by the model without any additional adjustable model parameters. Experimental viscosity data are reviewed for melts formed by MnO with SiO2, Al2O3, CaO, MgO, PbO, Na2O and K2O. The deviation of the available experimental data from the viscosities predicted by the model is shown to be within experimental error limits.

  20. Matrix with Prescribed Eigenvectors

    Ahmad, Faiz


    It is a routine matter for undergraduates to find eigenvalues and eigenvectors of a given matrix. But the converse problem of finding a matrix with prescribed eigenvalues and eigenvectors is rarely discussed in elementary texts on linear algebra. This problem is related to the "spectral" decomposition of a matrix and has important technical…