Sample records for alkali silica reactions

  1. Effect of Mineral Admixtures on Alkali-Silica Reaction

    Institute of Scientific and Technical Information of China (English)

    ZHANG Chengzhi; WANG Aiqin


    The influence of silica fume,slag and fly ash on alkali-silica reaction under the condition of 70℃ is studied.The results show that silica,slag and fly ash may inhibit alkali-silica reaction only under suitable content.When the content is less than 10%,silica fume does not markedly influence the expansion of alkali-silica reaction.When the content is 15%-20%,silica fume only may delay the expansion of alkali-silica reaction.When the content is 30%-70%,slag may only delay the expansion of alkali-silica reaction,but cannot inhibit the expansion of alkali-silica reaction.When the content is 10%,fly ash does not markedly influence the expansion of alkali-silica reaction.When the content is 20%-30%,fly ash may only delay the expansion of alkali-silica reaction,but cannot inhibit the expansion of alkali-silica reaction.When the content is over 50%,it is possible that fly ash can inhibit effectively alkali-silica reaction.

  2. Effect of Pozzolanic Reaction Products on Alkali-silica Reaction

    Institute of Scientific and Technical Information of China (English)

    WEI Fengyan; LAN Xianghui; LV Yinong; XU Zhongzi


    The effect of fly ash on controlling alkali-silica reaction (ASR) in simulated alkali solution was studied. The expansion of mortar bars and the content of Ca(OH)2 in cement paste cured at 80 ℃ for 91 d were measured. Transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) were employed to study the microstructure of C-S-H. TEM/energy dispersive spectroscopy (EDS) was then used to determine the composition of C-S-H. The pore structure of the paste was analyzed by mercury intrusion porosimetry (MIP). The results show that the contents of fly ash of 30% and 45% can well inhibit ASR. And the content of Ca(OH)2 decreases with the increase of fly ash. That fly ash reacted with Ca(OH)2 to produce C-S-H with a low Ca/Si molar ratio could bind more Na+ and K+ ions, and produce a reduction in the amount of soluble alkali available for ASR. At the same time, the C-S-H produced by pozzolanic reaction converted large pores to smaller ones (gel pores smaller than 10 nm) to densify the pore structure. Perhaps that could inhibit alkali transport to aggregate for ASR.

  3. Effect of Anti-freezing Admixtures on Alkali-silica Reaction in Mortars

    Institute of Scientific and Technical Information of China (English)

    LIU Junzhe; LI Yushun; LV Lihua


    The influence of anti-freezing admixture on the alkali aggregate reaction in mortar was analyzed with accelerated methods. It is confirmed that the addition of sodium salt ingredients of anti-freezing admixture accelerates the alkali silica reaction to some extent, whereas calcium salt ingredient of anti-freezing admixture reduces the expansion of alkali silica reaction caused by high alkali cement. It is found that the addition of the fly ash considerably suppresses the expansion of alkali silica reaction induced by the anti-freezing admixtures.

  4. Alkali-silica reaction resistant concrete using pumice blended cement (United States)

    Ramasamy, Uma

    Durability of structures is a major challenge for the building industry. One of the many types of concrete deterioration that can affect durability is alkali-silica reaction (ASR). ASR has been found in most types of concrete structures, including dams, bridges, pavements, and other structures that are 20 to 50 years old. The degradation mechanism of ASR produces a gel that significantly expands in the presence of water as supplied from the surrounding environment. This expansion gel product can create high stresses and cracking of the concrete, which can lead to other forms of degradation and expensive structural replacement costs. The four essential factors that produce an expansive ASR gel in concrete are the presence of alkalis, siliceous aggregate, moisture, and free calcium hydroxide (CH). If concrete is starved of any one of these essential components, the expansion can be prevented. Reducing CH through the use of a supplementary cementitious material (SCM) such as natural pozzolan pumice is the focus of this research. By using a pozzolan, the amount of CH is reduced with time based on the effectiveness of the pozzolan. Many pozzolans exist, but one such naturally occurring pozzolanic material is pumice. This research focuses on determining the effect of a finely ground pumice as a SCM in terms of its resistance to ASR expansion, as well as improving resistance to other potential concrete durability mechanisms. In spite of having high alkali contents in the pumice, mixtures containing the SCM pumice more effectively mitigated the ASR expansion reaction than other degradation mechanisms. Depending on the reactivity of the aggregates and fineness of the pumice, 10-15% replacement of cement with the pumice was found to reduce the ASR expansion to the acceptable limits. The amount of CH remaining in the concrete was compared to the ASR expansion in order to improve understanding of the role of CH in the ASR reaction. Thermo-gravimetric analysis (TGA) and X

  5. Assessment of concrete bridge decks with alkali silica reactions

    DEFF Research Database (Denmark)

    Eriksen, Kirsten; Jansson, Jacob; Geiker, Mette Rica


    Based on investigations of concrete from an approximately 40 years old bridge a procedure to support the management of maintenance and repair of alkali silica damaged bridges is proposed. Combined petrography and accelerated expansion testing were undertaken on cores from the Bridge at Skovdiget......, Bagsværd, Denmark to provide information on the damage condition as well as the residual reactivity of the concrete. The Danish Road Directory’s guidelines for inspection and assessment of alkali silica damaged bridges will be briefly presented, and proposed modifications will be describe...

  6. In situ alkali-silica reaction observed by x-ray microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kurtis, K.E.; Monteiro, P.J.M. [Univ. of California, Berkeley, CA (United States); Brown, J.T.; Meyer-Ilse, W. [Ernest Orlando Lawrence Berkeley National Lab., CA (United States)


    In concrete, alkali metal ions and hydroxyl ions contributed by the cement and reactive silicates present in aggregate can participate in a destructive alkali-silica reaction (ASR). This reaction of the alkalis with the silicates produces a gel that tends to imbibe water found in the concrete pores, leading to swelling of the gel and eventual cracking of the affected concrete member. Over 104 cases of alkali-aggregate reaction in dams and spillways have been reported around the world. At present, no method exists to arrest the expansive chemical reaction which generates significant distress in the affected structures. Most existing techniques available for the examination of concrete microstructure, including ASR products, demand that samples be dried and exposed to high pressure during the observation period. These sample preparation requirements present a major disadvantage for the study of alkali-silica reaction. Given the nature of the reaction and the affect of water on its products, it is likely that the removal of water will affect the morphology, creating artifacts in the sample. The purpose of this research is to observe and characterize the alkali-silica reaction, including each of the specific reactions identified previously, in situ without introducing sample artifacts. For observation of unconditioned samples, x-ray microscopy offers an opportunity for such an examination of the alkali-silica reaction. Currently, this investigation is focusing on the effect of calcium ions on the alkali-silica reaction.

  7. Alkali-Silica Reaction Inhibited by LiOH and Its Mechanism

    Institute of Scientific and Technical Information of China (English)


    A high alkali reactive aggregate-zeolitization perlite was used to test the long-term effectiveness of LiOH in inhibiting alkali-silica reaction.In this paper,the rigorous conditions were designed that the mortar bars had been cured at 80℃ for 3 years after autoclaved 24 hours at 150℃.Under this condition,LiOH was able to inhibit the alkali-silica reaction long-term effectiveness.Not only the relationship between the molar ratio of n(Li)/(Na) and the alkali contents in systems was established, but also the governing mechanism of such effects was also studied by SEM.

  8. Effect of the Composite of Natural Zeolite and Fly Ash on Alkali-Silica Reaction

    Institute of Scientific and Technical Information of China (English)

    FENG Xiao-xin; FENG Nai-qian; HAN Dong


    The effect of the composite of natural zeolite and fly ash on alkali-silica reaction ( ASR ) was studied with natural alkali-reactive aggregate and quartz glass aggregate respecthvely. The expansive experiment of mortar bar and concrete prism was completed. The results show that ASR can be suppressed effectively by the composite of natural zeolite and fly ash.

  9. Influence of alkalis from different sources than cement in the evolution of alkali-silica reaction

    Directory of Open Access Journals (Sweden)

    Olague, C.


    Full Text Available A bibliographical revision of the existent literature allows showing symptoms of alkali-silica reaction (ASR in highways, and the practical and economic method uranyl acetate to confirm the presence of ASR. The existence of reaction in concrete pavements of Chihuahua City was verified by a visual observation of patterns cracks, examination of gel deposits and the presence of reactive materials. Considering that the cement used to construct this pavements with problems of ASR, was low alkalis cement, the research was devoted to study the influence of alkalis coming from different sources than cement in the evolution of reaction such as: a aggregates: gravel and sand, b mix water, c additives and d minerals additions The initial classification of cements like high and low alkalis concerned to ASR must be revised for accept the fact that there is not a unique maximum limit alkalis of cement under which the expansible reactivity cannot occur.

    Una revisión bibliográfica de la literatura existente permite mostrar las manifestaciones de reacción álcali-sílice (RAS en estructuras de carreteras y el método práctico y económico de acetato de uranilo para confirmar la presencia de RAS. La existencia de la reacción en pavimentos de hormigón de la ciudad de Chihuahua se pudo confirmar tras la observación visual de modelos de grietas, estudios de depósitos de gel y existencia de fuentes de materiales reactivos. Considerando que el cemento utilizado para construir los tramos de pavimento con problemas de RAS, era un cemento bajo en álcalis, se enfocó la investigación al estudio de la influencia de los álcalis provenientes de fuentes distintas al cemento en la evolución de la reacción tales como: a áridos gruesos y finos, b agua de mezclado, c aditivos y d adiciones minerales El concepto inicial de clasificación de cementos altos y bajos en álcalis con respecto a la RAS debe ser revisado para aceptar el hecho de que no hay un solo

  10. Chemical modelling of Alkali Silica reaction: Influence of the reactive aggregate size distribution

    Energy Technology Data Exchange (ETDEWEB)

    Poyet, S. [CEA Saclay, DEN/DANS/DPC/SCCME/LECBA, F-91191 Gif Sur Yvette, (France); Sellier, A. [UPS, LMDC, INSA Toulouse, F-33077 Bordeaux 4, (France); Capra, B. [Oxand SA, F-77210 Avon (France); Foray, G. [Univ Lyon 1, L2MS, PETRA GC, F-69622 Villeurbanne (France); Torrenti, J.M. [IRSN, F-92262 Fontenay Aux Roses (France); Cognon, H. [EdF/DER Les Renardieres, F-77818 Moret Sur Loing (France); Bourdarot, E. [CIH Savoie Technolac, F-73373 Le Bourget du Lac (France)


    This article presents a new model which aims at predicting the expansion induced by Alkali Silica Reaction (ASR) and describing the chemical evolution of affected concretes. It is based on the description of the transport and reaction of alkalis and calcium ions within a Relative Elementary Volume (REV). It takes into account the influence of the reactive aggregate size grading on ASR, i.e. the effect of the simultaneous presence of different sized reactive aggregates within concrete. The constitutive equations are detailed and fitted using experimental results. Results from numerical simulations are presented and compared with experiments. (authors)

  11. Use of Fly Ash in the Mitigation of Alkali-Silica Reaction in Concrete (United States)


    crystallinity of the silica and its solubility. Common reactive minerals susceptible to ASR include strained quartz, cristobalite , opal, obsidian, chert, and...residues, whereas alkali-silica reactive components include opal, cristobalite , tridymite, siliceous and some intermediate volcanic glass, chert

  12. Effect of Grain Size and Reaction Time in Characterisation of Aggregates for Alkali Silica Reaction Using Chemical Method

    Directory of Open Access Journals (Sweden)

    R.P. Pathak


    Full Text Available Concrete can deteriorate as a result of alkali aggregate reaction, an interaction between alkalis present in alkaline pore solution originating from the Portland cement and reactive minerals in certain types of aggregates. Potential reactivity of aggregates with regard to alkalis present in concrete mix can be determined by Mortar Bar method, Chemical Method and Petrographic analysis. Of these the chemical method though is quick and does not require a large quantity of material for testing yet have its own inherent limitations. It does not ensure completion of reaction as the observations are limited to 24hour only and also does not assess the effect of varying the combination of coarse and fine aggregates. A study on chemical method by allowing the reaction for a prolonged time up to 96 hours and also on different grain size ranged matrix was carried at Central Soil and Materials Research Station, New Delhi. Simultaneously the test results of the modified method are compared to the existing Mortar Bar method, Chemical Method and Petrographic analysis The outcome of the studies clearly reflects that the grain size play an important role in the reaction, the reaction time has a demarked impact on reactivity, in the cases having a high value of silica release the choice of reduction in alkalinity as an indicator of degree of reaction is not reliable, instead measuring remaining Na2O concentration in Sodium hydroxide solution after the reaction seems to be much more meaningful in justifying the silica release.

  13. Microstructural Changes Due to Alkali-Silica Reaction during Standard Mortar Test

    Directory of Open Access Journals (Sweden)

    Jun-Ho Shin


    Full Text Available The microstructural development of mortar bars with silica glass aggregate undergoing alkali-silica reaction (ASR under the conditions of American Society for Testing and Materials (ASTM Standard Test C1260 was analyzed using scanning electron microscopy and qualitative X-ray microanalysis. Cracking in the aggregate, the hydrated paste, and the paste-aggregate interface was important in the development of the microstructure. Cracks were characterized according to their location, their relationship to other cracks, and whether they are filled with ASR gel. Expansion of the bars was approximately 1% at 12 days and 2% at 53 days. They fell apart by 63 days. The bars contained two zones, an inner region that was undergoing ASR and an outer and much more highly damaged zone that extended further inward over time. Evidence of ASR was present even during the period when specimens were immersed in water, prior to immersion in NaOH solution.

  14. Alkali silica reaction in concrete induced by mortar adhered to recycled aggregate

    Directory of Open Access Journals (Sweden)

    Etxeberria, M.


    Full Text Available The durability of recycled concrete must be determined before this material can be used in construction. In this paper the alkali-silica reaction in recycled concrete is analyzed. The recycled concrete is made with recycled aggregates, composed by original limestone aggregates and adhered mortar with reactive silica sand, and high alkali content cement. Due to the manufacturing process used for concrete production and the high water absorption capacity of recycled aggregates, cement accumulation happens in the interface (ITZ. The concentration of alkalis on the surface of recycled aggregates- ITZ and the presence of reactive sand in the mortar adhering to the recycled aggregate induce an alkali-silica reaction in 6-month concrete. The existence of this reaction is confirmed by environmental scanning electron microscopy (ESEM and EDX analysis. The mechanical properties of 6-month recycled concrete were similar to those values at 28-days of curing.

    La durabilidad del hormigón fabricado con árido reciclado es necesario determinarla antes de su utilización como material de construcción. En este artículo se analiza la reacción álcali-sílice manifestada en el hormigón fabricado con árido reciclado procedente de hormigón (compuesto de árido original calizo y mortero adherido de arena sílice reactiva, y cemento de alto contenido en álcalis. Debido al proceso de fabricación del hormigón y la alta capacidad de absorción del árido reciclado se produce una acumulación del cemento en la Interfase (ITZ. Debido al contacto directo de los álcalis del cemento con la arena sílice reactiva se produce una reacción álcali sílice a los 6 meses de edad del hormigón. Se realiza un análisis mediante microscopio electrónico de barrido ambiental (ESEM y sistema analítico de EDX. Se determina que las propiedades mecánicas del hormigón reciclado a 6 meses son similares a las obtenidas a los 28 días de curado.

  15. Assessment of Alkali-Silica Reaction Damage in Mortars with Nonlinear Ultrasonic Techniques (United States)

    Chen, J.; Jayapalan, A. R.; Kurtis, K. E.; Kim, J.-Y.; Jacobs, L. J.


    In this work, a nonlinear ultrasonic modulation technique is employed to assess the damage state of portland cement mortar samples induced by alkali-silica reaction (ASR). Due to the nonlinear interaction of propagating waves caused by distributed microcracks that are agitated from its equilibrium state, the ultrasonic responses of samples produce sideband frequencies around the frequency of propagating waves. The amplitude of the sidebands depends on the amplitude of the input signals and is particularly sensitive to the state of damage evolved in the sample. Therefore, the development of internal microcracks with increasing duration of exposure to aggressive conditions can be quantitatively related to the variation of external ultrasonic measurements. The ultrasonic results are compared with results from standard ASR expansion measurements (ASTM C 1260), and a proportionally increasing relation was found in the early stages. In addition, aggregates with different alkali-reactivity (i.e., low reactivity or high reactivity) were examined in a similar manner. The results indicate that the nonlinear parameter obtained from ultrasonic tests directly reflects the difference of aggregate reactivity. This clearly indicates that the developed nonlinear ultrasonic method is potentially a good alternative for a more rapid and still reliable assessment of aggregate alkali-reactivity.

  16. Insights into alkali-silica reaction damage in mortar through acoustic nonlinearity (United States)

    Rashidi, M.; Kim, J.-Y.; Jacobs, L. J.; Kurtis, K. E.


    The progression of damage as a result of alkali-silica reaction in mortar samples is monitored by using the Nonlinear Impact Resonance Acoustic Spectroscopy (NIRAS) method and expansion measurements, which were performed daily. Results of this study show a strong correlation between the cumulative average nonlinearity parameter and expansion for each sample type, and a strong linear relationship between fourteen-day expansion and the cumulative average nonlinearity of among sample types. In addition to the cumulative average nonlinearity parameter, the standard deviation of average nonlinearity parameter shows strong correlation with the fourteen-day expansion of sample types. Results provide insights to the relationship with the acoustic nonlinearity and damage caused by the ASR.

  17. Modeling of alkali-silica reaction in concrete:a review

    Institute of Scientific and Technical Information of China (English)



    This paper presents a comprehensive review of modeling of alkali-silica reaction (ASR) in concrete.Such modeling is essential for investigating the chemical expansion mechanism and the subsequent influence on the mechanical aspects of the material.The concept of ASR and the mechanism of expansion are first outlined,and the stateof-the-art of modeling for ASR,the focus of the paper,is then presented in detail.The modeling includes theoretical approaches,meso-and macroscopic models for ASR analysis.The theoretical approaches dealt with the chemical reaction mechanism and were used for predicting pessimum size of aggregate.Mesoscopic models have attempted to explain the mechanism of mechanical deterioration of ASR-affected concrete at material scale.The macroscopic models,chemomechanical coupling models,have been generally developed by combining the chemical reaction kinetics with linear or nonlinear mechanical constitutive,and were applied to reproduce and predict the long-term behavior of structures suffering from ASR.Finally,a conclusion and discussion of the modeling are given.

  18. Microwave material characterization of alkali-silica reaction (ASR) gel in cementitious materials (United States)

    Hashemi, Ashkan

    Since alkali-silica reaction (ASR) was recognized as a durability challenge in cement-based materials over 70 years ago, numerous methods have been utilized to prevent, detect, and mitigate this issue. However, quantifying the amount of produced ASR byproducts (i.e., ASR gel) in-service is still of great interest in the infrastructure industry. The overarching objective of this dissertation is to bring a new understanding to the fundamentals of ASR formation from a microwave dielectric property characterization point-of-view, and more importantly, to investigate the potential for devising a microwave nondestructive testing approach for ASR gel detection and evaluation. To this end, a comprehensive dielectric mixing model was developed with the potential for predicting the effective dielectric constant of mortar samples with and without the presence of ASR gel. To provide pertinent inputs to the model, critical factors on the influence of ASR gel formation on dielectric and reflection properties of several mortar samples were investigated at R, S, and X-band. Effects of humidity, alkali content, and long-term curing conditions on ASR-prone mortars were also investigated. Additionally, dielectric properties of chemically different synthetic ASR gel were also determined. All of these, collectively, served as critical inputs to the mixing model. The resulting developed dielectric mixing model has the potential to be further utilized to quantify the amount of produced ASR gel in cement-based materials. This methodology, once becomes more mature, will bring new insight to the ASR reaction, allowing for advancements in design, detection and mitigation of ASR, and eventually has the potential to become a method-of-choice for in-situ infrastructure health-monitoring of existing structures.

  19. Monitoring, Modeling, and Diagnosis of Alkali-Silica Reaction in Small Concrete Samples

    Energy Technology Data Exchange (ETDEWEB)

    Agarwal, Vivek [Idaho National Lab. (INL), Idaho Falls, ID (United States); Cai, Guowei [Idaho National Lab. (INL), Idaho Falls, ID (United States); Gribok, Andrei V. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mahadevan, Sankaran [Idaho National Lab. (INL), Idaho Falls, ID (United States)


    Assessment and management of aging concrete structures in nuclear power plants require a more systematic approach than simple reliance on existing code margins of safety. Structural health monitoring of concrete structures aims to understand the current health condition of a structure based on heterogeneous measurements to produce high-confidence actionable information regarding structural integrity that supports operational and maintenance decisions. This report describes alkali-silica reaction (ASR) degradation mechanisms and factors influencing the ASR. A fully coupled thermo-hydro-mechanical-chemical model developed by Saouma and Perotti by taking into consideration the effects of stress on the reaction kinetics and anisotropic volumetric expansion is presented in this report. This model is implemented in the GRIZZLY code based on the Multiphysics Object Oriented Simulation Environment. The implemented model in the GRIZZLY code is randomly used to initiate ASR in a 2D and 3D lattice to study the percolation aspects of concrete. The percolation aspects help determine the transport properties of the material and therefore the durability and service life of concrete. This report summarizes the effort to develop small-size concrete samples with embedded glass to mimic ASR. The concrete samples were treated in water and sodium hydroxide solution at elevated temperature to study how ingress of sodium ions and hydroxide ions at elevated temperature impacts concrete samples embedded with glass. Thermal camera was used to monitor the changes in the concrete sample and results are summarized.

  20. Classification of alkali-silica reaction and corrosion distress using acoustic emission (United States)

    Abdelrahman, Marwa; ElBatanouny, Mohamed; Serrato, Michael; Dixon, Kenneth; Larosche, Carl; Ziehl, Paul


    The Nuclear Regulatory Commission regulates approximately 100 commercial nuclear power reactor facilities that contribute about 20% of the total electric energy produced in the United States. Half of these reactor facilities are over 30 years old and are approaching their original design service life. Due to economic and durability considerations, significant portions of many of the facilities were constructed with reinforced concrete, including the containment facilities, cooling towers, and foundations. While most of these concrete facilities have performed exceptionally well throughout their initial expected service life, some are beginning to exhibit different forms of concrete deterioration. In this study, acoustic emission (AE) is used to monitor two main concrete deterioration mechanisms; alkali-silica reaction (ASR) distress and corrosion of reinforcing steel. An accelerated ASR test was conducted where specimens were continuously monitored with AE. The results show that AE can detect and classify damage due to ASR distress in the specimens. AE was also used to remotely monitor active corrosion regions in a reactor facility. AE monitoring of accelerated corrosion testing was also conducted on a concrete block specimen cut from a similar reactor building. Electrochemical measurements were conducted to correlate AE activity to quantifiable corrosion measurements and to enhance capabilities for service life prediction.

  1. Quantitative diagnosis and prognosis framework for concrete degradation due to alkali-silica reaction (United States)

    Mahadevan, Sankaran; Neal, Kyle; Nath, Paromita; Bao, Yanqing; Cai, Guowei; Orme, Peter; Adams, Douglas; Agarwal, Vivek


    This research is seeking to develop a probabilistic framework for health diagnosis and prognosis of aging concrete structures in nuclear power plants that are subjected to physical, chemical, environment, and mechanical degradation. The proposed framework consists of four elements: monitoring, data analytics, uncertainty quantification, and prognosis. The current work focuses on degradation caused by ASR (alkali-silica reaction). Controlled concrete specimens with reactive aggregate are prepared to develop accelerated ASR degradation. Different monitoring techniques — infrared thermography, digital image correlation (DIC), mechanical deformation measurements, nonlinear impact resonance acoustic spectroscopy (NIRAS), and vibro-acoustic modulation (VAM) — are studied for ASR diagnosis of the specimens. Both DIC and mechanical measurements record the specimen deformation caused by ASR gel expansion. Thermography is used to compare the thermal response of pristine and damaged concrete specimens and generate a 2-D map of the damage (i.e., ASR gel and cracked area), thus facilitating localization and quantification of damage. NIRAS and VAM are two separate vibration-based techniques that detect nonlinear changes in dynamic properties caused by the damage. The diagnosis results from multiple techniques are then fused using a Bayesian network, which also helps to quantify the uncertainty in the diagnosis. Prognosis of ASR degradation is then performed based on the current state of degradation obtained from diagnosis, by using a coupled thermo-hydro-mechanical-chemical (THMC) model for ASR degradation. This comprehensive approach of monitoring, data analytics, and uncertainty-quantified diagnosis and prognosis will facilitate the development of a quantitative, risk informed framework that will support continuous assessment and risk management of structural health and performance.

  2. The Influence of Calcined Clay Pozzolan, Low-Cao Steel Slag and Granite Dust On the Alkali-Silica Reaction in Concrete


    James Sarfo-Ansah; Eugene Atiemo


    The influence of low CaO steel slag, calcined clay and granite dust on the alkali-silica reaction was investigated over a period of 35 days under accelerated curing conditions. The mineral admixtures were used to replace varying portions of high alkali Portland limestone cement up to an admixture content of 25% in order to study their effect on the alkali-silica reaction (ASR). Portland limestone cement used for the study had a total Na2Oeq of 4.32. XRD analysis of hydrated mortar...

  3. Alkali-silica reaction of aggregates for concrete pavements in Chihuahua’s State, Mexico

    Directory of Open Access Journals (Sweden)

    Olague, C.


    Full Text Available The concrete of pavements must resist the climatic conditions, heavy traffic, chemical agents or any other type of aggressive agent. A methodology for characterizing materials that would influence concrete durability was developed considering chemical and physical factors. This methodology allows the consideration of several factors like physiography, geology, and climate, among others that would be of great importance to prevent future durability problems of pavements. This methodology takes into account several tests and this paper presents the results of potential reactivity aggregates of the State of Chihuahua. The tests for evaluating the reactive siliceous aggregate and the potential alkali-silica reactivity were performed according to the: petrographic examination (ASTM C 295 and standard quick chemical test (ASTM C 289. 38% of the tested sites resulted innocuous, 48% potentially reactive and 13% reactive. It is discussed the benefit of applying a conscious methodology in order to obtain the best results with a representative quantity of tests.

    El hormigón de los pavimentos debe ser resistente a las condiciones climáticas, tránsito pesado, agentes químicos o cualquier otro tipo de agente agresivo. Se desarrolló una metodología para caracterización de materiales considerando factores físicos y químicos que influyen en la durabilidad del hormigón. Esta metodología se basa en la consideración de varios factores como: fisiografía, geología y clima, entre otros, que podrían ser de gran importancia para prevenir futuros problemas de durabilidad en pavimentos de hormigón. La metodología en cuestión considera varias pruebas, en este artículo se presentan los resultados de la reactividad potencial de los áridos del Estado de Chihuahua. Las pruebas para evaluar la reactividad de áridos silíceos y la reactividad potencial álcali-sílice fueron ejecutadas de acuerdo a: examen petrográfico (ASTM C 295 y la prueba qu

  4. Development of microwave and impedance spectroscopy methods for in-situ nondestructive evaluation of alkali silica reaction in concrete (United States)

    Heifetz, Alexander; Bakhtiari, Sasan; Lu, Juan; Aranson, Igor S.; Vinokur, Valerii M.; Bentivegna, Anthony F.


    Aging concrete degradation due to alkali silica reaction (ASR) is a challenge to sustainability of critical infrastructure, such as nuclear power plants. Currently, there is no standard, nondestructive method for detecting ASR in concrete. We report on the progress in developing electromagnetic (EM) methods, consisting of microwave and impedance spectroscopy techniques, for nondestructive detection of ASR. The microwave and impedance spectroscopy methods are complementary since they provide information about material electrical properties in GHz and Hz to KHz EM spectral bands, respectively. Preliminary studies were conducted using accelerated testing concrete prism specimens developed according to ASTM C1293 standard. Microwave and impedance spectroscopy measurements were performed on ASR specimens at the first and the second month maturity level, as well as on age-matched controls. Microwave tests consisted of reflection and transmission measurements using dielectric-loaded antennas, with the focus on X-band spectrum. Impedance measurements were performed using flexible electrode patches. Measurement results by both microwave and impedance spectroscopy methods indicate observable differences in electrical properties between reactive and non-reactive specimens. In addition, trends in measurement data obtained with the two complementary EM techniques are consistent and correlate with ASR progression in specimens.

  5. Methods for Controlling Effects of Alkali-Silica Reaction in Concrete. (United States)


    and high-alkali RC-756(2) cements were used. The reactive aggregates were opal, glassy igneous rock, and chert produced by crushing chert gravel. As...tridymite High- and low-temperature Minor cristobalite I i %’I There was probably also some amorphous material. Similar work with a separate hand sample...CONIP STESNOTE. 0. psi WALSE SET-0EN Pd U AUTOCLAVE SRP..%U-O INITAL 5*N/I INAL SET. NO/- :4( AUTOCLAVE SEP.. % INTIAL. SET. NOR/-S FINAL. SGT

  6. The Influence of Calcined Clay Pozzolan, Low-Cao Steel Slag and Granite Dust On the Alkali-Silica Reaction in Concrete

    Directory of Open Access Journals (Sweden)

    James Sarfo-Ansah


    Full Text Available The influence of low CaO steel slag, calcined clay and granite dust on the alkali-silica reaction was investigated over a period of 35 days under accelerated curing conditions. The mineral admixtures were used to replace varying portions of high alkali Portland limestone cement up to an admixture content of 25% in order to study their effect on the alkali-silica reaction (ASR. Portland limestone cement used for the study had a total Na2Oeq of 4.32. XRD analysis of hydrated mortar bar samples confirmed the formation of an expansive sodium silica gel in the reference Portland cement mortar bar as the agent responsible for ASR. Stable calcium silicates were formed in the mortar bars containing calcined clay in increasing quantities whilst the presence of the sodium silicate gel decreased.The occurrence of these stable silicates in hydrated samples containing steel slag and granite dust was however minimal, compared to calcined clay cement mortars. The highest expansion was recorded for granite dust mortar bars, reaching a maximum of 25.98% at 35 days. Mortar-bar expansion decreased as calcined clay content in the cement increased;mortar bars with 25% calcined clay were the least expansive recording expansion less than 0.1% at all test ages. Whilst the expansion was reduced by between 42.5% and 107.8% at 14 days with increasing calcined clay content, expansion rather increased between 36.8% and 169.5% at 14 days with increasing granite dust content.Steel slag mortar bars experienced reduction in 14 days expansion between 14.3% - 46.2%.The study confirms that steel slag and calcined clay pozzolan have greater influence on ASR in mortar bars than granite dust and shows that calcined clay and low CaO steel slag could be considered as remedial admixtures for ASR at replacement levels of 25% and 15% respectively.

  7. High effective silica fume alkali activator

    Indian Academy of Sciences (India)

    Vladimír Živica


    Growing demands on the engineering properties of cement based materials and the urgency to decrease unsuitable ecologic impact of Portland cement manufacturing represent significant motivation for the development of new cement corresponding to these aspects. One category represents prospective alkali activated cements. A significant factor influencing their properties is alkali activator used. In this paper we present a new high effective alkali activator prepared from silica fume and its effectiveness. According to the results obtained this activator seems to be more effective than currently used activators like natrium hydroxide, natrium carbonate, and water glass.

  8. Alkali-silica reactions of mortars produced by using waste glass as fine aggregate and admixtures such as fly ash and Li2CO3. (United States)

    Topçu, Ilker Bekir; Boğa, Ahmet Raif; Bilir, Turhan


    Use of waste glass or glass cullet (GC) as concrete aggregate is becoming more widespread each day because of the increase in resource efficiency. Recycling of wastes is very important for sustainable development. When glass is used as aggregate in concrete or mortar, expansions and internal stresses occur due to an alkali-silica reaction (ASR). Furthermore, rapid loss in durability is generally observed due to extreme crack formation and an increase in permeability. It is necessary to use some kind of chemical or mineral admixture to reduce crack formation. In this study, mortar bars are produced by using three different colors of glass in four different quantities as fine aggregate by weight, and the effects of these glass aggregates on ASR are investigated, corresponding to ASTM C 1260. Additionally, in order to reduce the expansions of mortars, 10% and 20% fly ash (FA) as mineral admixture and 1% and 2% Li(2)CO(3) as chemical admixture are incorporated by weight in the cement and their effects on expansion are examined. It is observed that among white (WG), green (GG) and brown glass (BG) aggregates, WG aggregate causes the greatest expansion. In addition, expansion increases with an increase in amount of glass. According to the test results, it is seen that over 20% FA and 2% Li(2)CO(3) replacements are required to produce mortars which have expansion values below the 0.2% critical value when exposed to ASR. However, usages of these admixtures reduce expansions occurring because of ASR.

  9. GRIZZLY Model of Multi-Reactive Species Diffusion, Moisture/Heat Transfer and Alkali-Silica Reaction for Simulating Concrete Aging and Degradation

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Hai [Idaho National Lab. (INL), Idaho Falls, ID (United States); Spencer, Benjamin W. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Cai, Guowei [Vanderbilt Univ., Nashville, TN (United States)


    Concrete is widely used in the construction of nuclear facilities because of its structural strength and its ability to shield radiation. The use of concrete in nuclear power plants for containment and shielding of radiation and radioactive materials has made its performance crucial for the safe operation of the facility. As such, when life extension is considered for nuclear power plants, it is critical to have accurate and reliable predictive tools to address concerns related to various aging processes of concrete structures and the capacity of structures subjected to age-related degradation. The goal of this report is to document the progress of the development and implementation of a fully coupled thermo-hydro-mechanical-chemical model in GRIZZLY code with the ultimate goal to reliably simulate and predict long-term performance and response of aged NPP concrete structures subjected to a number of aging mechanisms including external chemical attacks and volume-changing chemical reactions within concrete structures induced by alkali-silica reactions and long-term exposure to irradiation. Based on a number of survey reports of concrete aging mechanisms relevant to nuclear power plants and recommendations from researchers in concrete community, we’ve implemented three modules during FY15 in GRIZZLY code, (1) multi-species reactive diffusion model within cement materials; (2) coupled moisture and heat transfer model in concrete; and (3) anisotropic, stress-dependent, alkali-silica reaction induced swelling model. The multi-species reactive diffusion model was implemented with the objective to model aging of concrete structures subjected to aggressive external chemical attacks (e.g., chloride attack, sulfate attack, etc.). It considers multiple processes relevant to external chemical attacks such as diffusion of ions in aqueous phase within pore spaces, equilibrium chemical speciation reactions and kinetic mineral dissolution/precipitation. The moisture

  10. Application of micro X-ray diffraction to investigate the reaction products formed by the alkali silica reaction in concrete structures

    Energy Technology Data Exchange (ETDEWEB)

    Dähn, R.; Arakcheeva, A.; Schaub, Ph.; Pattison, P.; Chapuis, G.; Grolimund, D.; Wieland, E.; Leemann, A. (Ecole); (PSI); (Phase Solutions); (ESRF)


    Alkali–silica reaction (ASR) is one of the most important deterioration mechanisms in concrete leading to substantial damages of structures worldwide. Synchrotron-based micro-X-ray diffraction (micro-XRD) was employed to characterize the mineral phases formed in micro-cracks of concrete aggregates as a consequence of ASR. This particular high spatial resolution technique enables to directly gain structural information on ASR products formed in a 40-year old motorway bridge damaged due to ASR. Micro-X-ray-fluorescence was applied on thin sections to locate the reaction products formed in veins within concrete aggregates. Micro-XRD pattern were collected at selected points of interest along a vein by rotating the sample. Rietveld refinement determined the structure of the ASR product consisting of a new layered framework similar to mountainite and rhodesite. Furthermore, it is conceivable that understanding the structure of the ASR product may help developing new technical treatments inhibiting ASR.

  11. Alkali Aggregate Reaction in Alkali Slag Cement Mortars

    Institute of Scientific and Technical Information of China (English)


    By means of "Mortar Bar Method",the ratio of cement to aggregate was kept as a constant 1∶2.25,the water-cement ratio of the mixture was 0.40,and six prism specimens were prepared for each batch of mixing proportions with dimensions of 10×10×60mm3 at 38±2℃ and RH≥95%, the influences of content and particle size of active aggregate, sort and content of alkali component and type of slag on the expansion ratios of alkali-activated slag cement(ASC) mortars due to alkali aggregate reaction(AAR) were studied. According to atomic absorption spectrometry,the amount of free alkali was measured in ASC mortars at 90d.The results show above factors affect AAR remarkably,but no dangerous AAR will occur in ASC system when the amount of active aggregate is below 15% and the mass fraction of alkali is not more than 5% (Na2O).Alkali participated in reaction as an independent component, and some hydrates containing alkali cations were produced, free alkalis in ASC system can be reduced enormously.Moreover,slag is an effective inhibitor, the possibility of generating dangerous AAR in ASC system is much lower at same conditions than that in ordinary Portland cement system.

  12. Alcali-silica reactions: Mechanisms for crack formations

    DEFF Research Database (Denmark)

    Goltermann, Per


    Alkali-silica reactions (ASR) are found all over the world and cause a large number of damage, which have lead to different sets of requirements in the different countries for the aggregates, the cements and the admixtures. One of the reasons for the damage and the different requirements is that ...

  13. Estudo das reações alcalis-sílica associadas ao uso da lama vermelha em argamassas colantes e de revestimento Study of alkali-silica reactions associated with the use of red mud in plastering mortars

    Directory of Open Access Journals (Sweden)

    D. V. Ribeiro


    Full Text Available A incorporação de resíduos industriais em matrizes cimentícias, com o objetivo de inertização, é uma alternativa de reutilização que tem sido bastante estudada nos últimos anos. No presente trabalho, estudou-se a lama vermelha, resíduo sólido gerado no processo de beneficiamento da bauxita e que, devido a seu elevado pH, é considerado "perigoso". Apesar do uso deste resíduo ter sido reportada em trabalhos anteriores, algumas patologias podem estar associadas à sua utilização, devido à elevada concentração de íons alcalinos (principalmente o sódio, favorecendo as reações álcalis-sílica (RAS e às dificuldades de moldagem (reologia devido à elevada finura deste resíduo. Apesar destes prováveis problemas provenientes do uso indiscriminado da lama vermelha como adição às argamassas e concretos, ainda são poucas as pesquisas que os contemplam, sendo este o foco do presente trabalho. Foram verificadas as propriedades reológicas das argamassas, utilizando um reômetro e a avaliação da RAS, de acordo com as normas ASTM C 1260-07 e NBR 11582. Os resultados obtidos foram bastante satisfatórios quanto ao comportamento das argamassas frente à RAS, apesar da elevada concentração de álcalis na lama vermelha, com grande influência reológica.The incorporation of industrial wastes in cementitious matrices, with the goal of inertization, is an alternative of reuse that has been extensively studied in recent years. In this paper, the red mud, the main waste generated in aluminum and alumina production by the Bayer process from bauxite ore and considered "hazardous" due to the high pH, was studied. Despite the use of this waste have been reported in previous studies, some pathologies may be associated with its use, due to high concentration of alkali ions (mainly sodium, favoring the alkali-silica reactions (ASR and the difficulties of molding (rheology because of high fineness of this waste. Despite these potential

  14. Structural evaluation of a prestressed concrete bridge under an alkali-silica reaction; Evaluacion estructural de un puente de hormigon pretensado afectado por una reaccion alcali-silice

    Energy Technology Data Exchange (ETDEWEB)

    Carpintero Garcia, I.; Bermudez Adriozola, B.


    The Central Laboratory of Structures and Materials (CEDEX) was commissioned by the National Department of Highways to evaluate the safety conditions of one bridge built on 1997, which is part of the net of the Spanish National Highways. Even at the first inspection many cracks were detected in the concrete deck, associated with expansion concrete processes. This examination revealed that concrete deterioration was not associated with any reinforcement corrosion process; in fact, there were no symptoms of this pathology all along the bridge. for that reason the internal chemical reactions were considered as the most probable cause for the expansion of concrete, as no symptoms of deterioration due to external attack were found. In order to check the origin of concrete expansion, some tests were carried out on concrete samples drilled on the decks. Results of these tests show that there had been internal reactions in concrete mass which explains its expansion and the appearance of those cracks observed. Further more, some other activities were also carried out on site to estimate the importance of the structural damages, as topographic levelling and dynamic testing of the decks. Also the mechanical properties of concrete probes were tested at laboratory. This article shows the main results obtained on the study carried on to determine the cause and significance of the structural damages of the bridge. (Author) 3 refs.

  15. The Pozzolanic reaction of silica fume

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede


    Silica fume is a very important supplementary cementitious binder in High-Performance and Ultra High-Performance Concretes. Through its pozzolanic reaction the silica fume densifies the concrete micro-structure, in particular it strengthens the paste-aggregate interfacial transition zone. In the ...... of activation of the pozzolanic reaction of silica fume is estimated. The results show that the pozzolanic reaction of silica fume has notable differences from Portland cement hydration.......Silica fume is a very important supplementary cementitious binder in High-Performance and Ultra High-Performance Concretes. Through its pozzolanic reaction the silica fume densifies the concrete micro-structure, in particular it strengthens the paste-aggregate interfacial transition zone....... In the present paper different aspects of the pozzolanic reaction of silica fume are investigated. These include chemical shrinkage, isothermal heat development and strength development. Key data for these are given and compared with theoretical calculations, and based on presented measurements the energy...

  16. Influence of granitic aggregates from Northeast Brazil on the alkali-aggregate reaction

    Energy Technology Data Exchange (ETDEWEB)

    Gomes Neto, David de Paiva; Santana, Rodrigo Soares de; Barreto, Ledjane Silva, E-mail: [Universidade Federal de Sergipe (UFS), Sao Cristovao, SE (Brazil). Dept. de Ciencias dos Materiais e Engenharia; Conceicao, Herbert; Lisboa, Vinicios Anselmo Carvalho [Universidade Federal de Sergipe (UFS), Sao Cristovao, SE (Brazil). Dept. de Geologia


    The alkali-aggregate reaction (AAR) in concrete structures is a problem that has concerned engineers and researchers for decades. This reaction occurs when silicates in the aggregates react with the alkalis, forming an expanded gel that can cause cracks in the concrete and reduce its lifespan. The aim of this study was to characterize three coarse granitic aggregates employed in concrete production in northeastern Brazil, correlating petrographic analysis with the kinetics of silica dissolution and the evolution of expansions in mortar bars, assisted by SEM/EDS, XRD, and EDX. The presence of grains showing recrystallization into individual microcrystalline quartz subgrains was associated with faster dissolution of silica and greater expansion in mortar bars. Aggregates showing substantial deformation, such as stretched grains of quartz with strong undulatory extinction, experienced slower dissolution, with reaction and expansion occurring over longer periods that could not be detected using accelerated tests with mortar bars. (author)

  17. Study of effect of electric arc furnace slag on expansion of mortars subjected to alkali-aggregate reaction

    Directory of Open Access Journals (Sweden)

    L. SOUZA

    Full Text Available Abstract Alkali-aggregate reaction is a chemical reaction between cement alkalis and some reactive mineral present in some aggregates, leading to concrete expansion and cracking. One kind usually observed and studied in Brazil is the alkali-silica reaction, due to its fast development. There are several methods that are effective to control and mitigate this reaction, and one of them is the partial replacement of cement by mineral additions such as pozzolans like fly-ash, silica fume and slag. In this study, we propose the use of electrical steel slag as a partial replacement of cement, evaluating its effectiveness by NBR 15577:2008, employing different proportions as replacement. It seems that the electrical steel slag, despite its expansive behavior, has been effective in the control of the ASR.

  18. The role of residual cracks on alkali silica reactivity of recycled glass aggregates

    DEFF Research Database (Denmark)

    Maraghechi, Hamed; Shafaatian, Seyed-Mohammad-Hadi; Fischer, Gregor


    Despite its environmental and economical advantages, crushed recycled glass has limited application as concrete aggregates due to its deleterious alkali-silica reaction. To offer feasible mitigation strategies, the mechanism of ASR should be well understood. Recent research showed that unlike some...... natural aggregates, soda-lime glass undergoes ASR within cracks in the interior of glass particles and not at glass–paste interface. These cracks originate during bottle crushing and propagate further by ASR. This paper examines whether glass aggregates could become innocuous if these cracks are healed...... by annealing or when the crack widths are smaller than a critical size. The results confirm that glass annealed at 650°C for 40min or particles containing cracks smaller than approximately 2.5μm can be considered innocuous based on ASTM C1260. Also larger glass particles contain significantly higher...

  19. Silica Microcapsules Prepared by Interfacial Reaction Methods

    Institute of Scientific and Technical Information of China (English)

    M; Fujiwara; K; Shiokawa; Y; Nakahara


    1 Results Silica spherical particles with hollow structure are directly prepared by interfacial reaction methods using W/O/W emulsion (schematic diagram in Fig.1)[1].Fig.1 Silica microcapsule formationThe mixing of W/O emulsion consisting of sodium silicate solution (inner water phase) and n-hexane solution (oil phase) to outer water phase dissolving NH4HCO3 or other salts affords silica microcapsules.The critical feature of this method is the direct formation of hollow structure.Therefore,the core com...

  20. Winning the battles on AAR[Alkali aggregate reaction in dams

    Energy Technology Data Exchange (ETDEWEB)

    Wood, J.


    This article discusses work carried out on four locks on the St. Lawrence Seaway to deal with the alkali aggregate reaction (AAR) in the concrete, on the Mactaquac dam on Canada's St John river which showed evidence of AAR, and also on the Paula Alfonso IV dam in Brazil where cracking was observed in concrete structures near the generators. The pattern of natural cracking is examined, and the source of the problem is identified. The use of admixtures to alleviate the problem is explored, and the utilisation of flyash, waste cement, silica fume, and lithium as concrete constituents is considered. New tests available using powdered rock flour aggregate to decrease alkali concentrations and improve cement workability are described.

  1. Effect of Alkali Ions on the Amorphous to Crystalline Phase Transition of Silica (United States)

    Venezia, A. M.; La Parola, V.; Longo, A.; Martorana, A.


    The effect of the addition of alkali ions to commercial amorphous silica, generally used as support for heterogeneous catalysts, has been investigated from the point of view of morphological and structural changes. Samples of alkali-doped silica were prepared by impregnation and subsequent calcination at various temperatures. The structural effect of Li, Na, K, and Cs was determined by use of techniques such as wide-angle (WAXS) and small-angle X-ray scattering (SAXS). The WAXS diffractograms, analyzed with the Rietveld method using the GSAS program, allowed qualitative and quantitative identification of the fraction of the different silica polymorphs like quartz, tridymite, and cristobalite. SAXS measurements, using the classical method based on Porod's law, yielded the total surface area of the systems. The calculated areas were compared with the surface areas determined by the nitrogen adsorption technique using the analytical method of Brunauer-Emmett-Teller. The results are explained in terms of sizes of the alkali ions and cell volume of the different crystalline phases.

  2. Effect of Glass Powder on Chloride Ion Transport and Alkali-aggregate Reaction Expansion of Lightweight Aggregate Concrete

    Institute of Scientific and Technical Information of China (English)

    WANG Zhi; SHI Caijun; SONG Jianming


    The effects of glass powder on the strength development, chloride permeability and potential alkali-aggregate reaction expansion of lightweight aggregate concrete were investigated.Ground blast furnace slag, coal fly ash and silica fume were used as reference materials. The re-placement of cement with 25% glass powder slightly decreases the strengthes at 7 and 28 d, but shows no effect on 90 d's. Silica fume is very effective in improving both the strength and chloride penetra-tion resistance, while ground glass powder is much more effective than blast furnace slag and fly ash in improving chloride penetration resistance of the concrete. When expanded shale or clay is used as coarse aggregate, the concrete containing glass powder does not exhibit deleterious expansion even if alkali-reactive sand is used as fine aggregate of the concrete.

  3. Nouvelle approche pour le suivi de la réactivité de phases SiO2 soumises à la Réaction Alcali Silice (RAS New approach for monitoring the reactivity of SiO2 phases subject to Alkali Silica Reaction (SAR

    Directory of Open Access Journals (Sweden)

    Harfouche M.


    Full Text Available Nous avons suivi- au moyen de la microscopie électronique à balayage environnementale (MEBE la diffraction X et la spectroscopie d’absorption des rayons X sous rayonnement synchrotron (XANES- la réactivité de certaines phases SiO2 lors du processus de la Réaction Alcali Silice (RAS. Cette réactivité est étroitement liée à la structure locale autour des atomes de silicium ainsi qu’à la présence d’impuretés comme le fer. Dans le cas du silex brut, la raie blanche du seuil K du fer ressemble davantage à celle de Fe3O4 ce qui permet de déduire la présence d’un mélange de Fe2+/Fe3+ dans le silex de départ. Après réaction, l’allure du spectre d’absorption des rayons X au seuil K du fer du silex est conservée avec un léger déplacement de la raie blanche vers les hautes énergies. Cette augmentation montre une prédominance de la valence Fe3+ au détriment de la valence Fe2+. Les résultats montrent que le fer participe à la stabilisation de la structure des phases formées. Cette étude peut être étendue à d’autres éléments traces présents dans la structure du silex de départ. In this study the reactivity of some SiO2 phases under Alkali Silica Reaction (RAS process is followed, using the environmental scanning electron microscopy (ESEM X-ray diffraction and absorption spectroscopy X-ray synchrotron radiation (XANES. This reactivity is closely related to the local structure around the silicon atoms and the presence of impurities such as iron. In the case of flint raw skate white iron K line is more like that of Fe3O4 which allows to deduce the presence of a mixture of Fe2+ / Fe3+ in the flint to start. After reaction, the shape of the spectrum of X-ray absorption K edge of iron in the flint is retained with a slight displacement of the white stripe to high energies. This increase shows a predominance of the valence Fe3+ at the expense of Fe2+ valence. The results show that iron is involved in stabilizing the

  4. Performance at high temperature of alkali-activated slag pastes produced with silica fume and rice husk ash based activators

    Directory of Open Access Journals (Sweden)

    Bernal, S. A.


    Full Text Available This study assessed the mechanical properties, and structural changes induced by high temperature exposure, of alkali-silicate activated slag cements produced with sodium silicates derived from silica fume (SF and rice husk ash (RHA. Similar reaction products were identified, independent of the type of silicate used, but with subtle differences in the composition of the C-S-H gels, leading to different strength losses after elevated temperature exposure. Cements produced with the alternative activators developed higher compressive strengths than those produced with commercial silicate. All samples retained strengths of more than 50 MPa after exposure to 600 °C, however, after exposure to 800 °C only the specimens produced with the RHA-based activator retained measurable strength. This study elucidated that silicate-activated slag binders, either activated with commercial silicate solutions or with sodium silicates based on SF or RHA, are stable up to 600 °C.Este estudio evaluó las propiedades mecánicas, y cambios estructurales inducidos por exposición a temperaturas elevadas, de cementos de escoria activada alcalinamente producidos con silicatos sódicos derivados de humo de sílice (SF y ceniza de cascarilla de arroz (RHA. Se identificaron productos de reacción similares, independiente del tipo de silicato utilizado, pero con diferencias menores en la composición de las geles C-S-H, lo cual indujo diferentes pérdidas de resistencia posterior a exposición a temperaturas elevadas. Los cementantes producidos con los activadores alternativos desarrollaron resistencias a la compresión más altas que aquellos producidos con silicato comercial. Todas las muestras retuvieron resistencias de más de 50 MPa posterior a la exposición a 600 °C, sin embargo, posterior a la exposición a 800 °C únicamente muestras producidas con activadores de RHA retuvieron resistencias medibles. Este estudio elucidó que cementantes de escoria activada con

  5. Reactions between cold methyl halide molecules and alkali-metal atoms. (United States)

    Lutz, Jesse J; Hutson, Jeremy M


    We investigate the potential energy surfaces and activation energies for reactions between methyl halide molecules CH3X (X = F, Cl, Br, I) and alkali-metal atoms A (A = Li, Na, K, Rb) using high-level ab initio calculations. We examine the anisotropy of each intermolecular potential energy surface (PES) and the mechanism and energetics of the only available exothermic reaction pathway, CH3X + A → CH3 + AX. The region of the transition state is explored using two-dimensional PES cuts and estimates of the activation energies are inferred. Nearly all combinations of methyl halide and alkali-metal atom have positive barrier heights, indicating that reactions at low temperatures will be slow.

  6. Reaction mechanisms in irradiated, precipitated, and mesoporous silica. (United States)

    Dondi, D; Buttafava, A; Zeffiro, A; Bracco, S; Sozzani, P; Faucitano, A


    A matrix EPR spectroscopy study of the low temperature γ radiolysis of precipitated (Zeosil) and mesoporous high surface silica has afforded evidence of the formation of trapped H-atoms, H-atom centers, siloxy radicals ≡Si-O(•), anomalous silyl peroxy radicals ≡Si-OO(•) with reduced g tensor anisotropy, siloxy radical-cations (≡Si-O-Si≡)(+•), E' centers, and two species from Ge impurity. Coordination of peroxyl radicals with diamagnetic ≡Si(+) centers is proposed and tested by DFT computations in order to justify the observed g tensor. Coordination of H-atoms to ≡Si(+) centers is also proposed for the structure of the H-atom centers as an alternative model not requiring the intervention of Ge, Sn, or CO impurities. The DFT method has been employed to assess the electronic structure of siloxy radical-cations and its similarity with that of the carbon radical-cation analogues; the results have prompted a revision of the structures proposed in the literature for ST1 and ST2 centers. The comparison between the two types of silica has afforded evidence of different radiolysis mechanisms leading to a greater yield of trapped H-atoms and H-atom centers in zeosil silica, which is reckoned with the 4-fold greater concentration of silanol groups. Parallel radiolysis experiments carried out by using both types of silica with polybutadiene oligomers as adsorbate have afforded evidence of free valence and energy migration phenomena leading to irreversible linking of polybutadiene chains onto silica. Reaction mechanisms are proposed based on the detection of SiO2-bonded free radicals whose structure has been defined by EPR.

  7. Alkali metal mediated C-C bond coupling reaction. (United States)

    Tachikawa, Hiroto


    Metal catalyzed carbon-carbon (C-C) bond formation is one of the important reactions in pharmacy and in organic chemistry. In the present study, the electron and hole capture dynamics of a lithium-benzene sandwich complex, expressed by Li(Bz)2, have been investigated by means of direct ab-initio molecular dynamics method. Following the electron capture of Li(Bz)2, the structure of [Li(Bz)2](-) was drastically changed: Bz-Bz parallel form was rapidly fluctuated as a function of time, and a new C-C single bond was formed in the C1-C1' position of Bz-Bz interaction system. In the hole capture, the intermolecular vibration between Bz-Bz rings was only enhanced. The mechanism of C-C bond formation in the electron capture was discussed on the basis of theoretical results.


    Directory of Open Access Journals (Sweden)

    Korolev Evgeniy Valer’evich


    Full Text Available Portland cement-based concrete is widely used in civil engineering. Therefore, it is very important to determine the preconditions of corrosion of the cement concrete. The service life of concrete structures can be substantially reduced by the alkali-silica reaction. It is well known that this reaction causes formation of the sodium silicate hydrogel. Thus, by identifying this gel, a researcher can make an assumption about the reasons for the corrosion. Obviously, macroscopic quantities of sodium salts can be discerned using analytical chemistry methods. Unfortunately, determinant values of such salts in the concrete structure are usually very small. Thus, there is a need for special research methods.Raman spectroscopy is an advanced method based on the analysis of instantaneous two-photon non-elastic light scattering. This method is applicable even in case of small quantities of chemicals under research. The first successful study of silicates using Raman spectroscopy methods was performed in the 20ies of the 20th century. In this work the authors have proven that sodium hydrogels can be easily identified in the concrete using the Raman spectroscopy. In the course of the analysis of the interphase boundary between the cement stone and the aggregates, the authors observed, at least, one spectral peak which did not belong to cement or to the disperse phases of the concrete. At the same time, this peak can be classified as a peak of the sodium silicate. Thus, sodium silicate gel is generated during the service life of the structure under research, and this research has revealed the presence of the alkali-silica reaction.Щелоче-силикатная реакция может приводить к существенному сокращению срока эксплуатации конструкций из цементных бетонов. Протекание щелоче-силикатной реакции сопровождается об

  9. Effect of reaction time on formation of silica core/shell particles

    Directory of Open Access Journals (Sweden)

    Milan P. Nikolić


    Full Text Available The silica core/shell nanostructures were prepared by a wet-chemical process. Silica core particles were prepared by hydrolysis and condensation of tetraethylorthosilicate. The obtained particles (average size ∼0.4 µm were used as templates for assembling of silica nanoparticles generated from highly basic sodium silicate solution. The silica core particles were functionalized with 3-aminopropyltriethoxysilane (APTES to allow electrostatic assembling of silica nanoparticles on the surface of silica core particles. In order to find the optimal conditions for synthesis of silica core/shell particles with mesoporous shells, the effect of reaction time on formation of silica nanoparticles was investigated. The effect of process parameters on generation and aggregation of silica nanoparticles prepared from highly basic sodium silicate solution was also investigated. It was shown that the size of silica nanoparticles and tendency towards aggregation increase with increasing the reaction time and temperature. These behaviours were reflected on the formation of mesoporous silica shell around silica core particles. Thin and uniform mesoporous silica layers were obtained if reaction times were kept short. When the reaction time was prolonged, the thicker and non-uniform shells were obtained.

  10. Palladium Immobilized on Silica Gel: A Novel and Reusable Catalyst for Heck Reaction

    Institute of Scientific and Technical Information of China (English)

    WANG Zu-Li; WANG Lei; YAN Jin-Can


    The immobilization of palladium on silica gel in Heck reaction has been developed.Iodobenzenes,bromobenzenes and activated chlorobenzenes were coupled with olefins (Heck reaction) smoothly to afford the corresponding cross-coupling products in good to excellent yields under phosphine- and amine-free reaction conditions in the presence of silica gel supported palladium,Silica-Ap-Pd catalyst,potassium carbonate as base and DMF as solvent.Furthermore,the silica-supported palladium catalyst 3 could be recovered and recycled by a simple filtration of the reaction solution and used for 6 consecutive trials without significant loss of its catalytic activity.

  11. A plug flow model for chemical reactions and aerosol nucleation and growth in an alkali-containing flue gas

    DEFF Research Database (Denmark)

    Christensen, K. A.; Livbjerg, Hans


    multicomponent growth models are treated. The local gas phase composition is determined from a gas phase chemical equilibrium calculation combined with finite reaction rate kinetics for slower reactions. The model is useful in the analysis of boiler operation with respect to the formation of particles, HCl, SO2......The paper presents a numerical model for the simulation of gas to particle conversion and the chemical changes during cooling of a flue gas from the combustion of fuels rich in volatile alkali species. For the homogeneous nucleation of alkali species the model uses the classical theory modified...

  12. Rice husk ash as a source of silica in alkali-activated fly ash and granulated blast furnace slag systems

    Directory of Open Access Journals (Sweden)

    Mejía, J. M.


    Full Text Available This study assesses the viability of using an agro-industrial by-product, rice husk ash (RHA from a Colombian rice company’s combustion facility, as a total replacement for the commercial sodium silicate ordinarily used in alkaliactivated binders. Fly ash (FA, granulated blast furnace slag (GBFS and binary 50FA:50GBFS blended pastes were activated with a mix of sodium hydroxide and either sodium silicate or one of two types of RHA. The pastes were characterised for strength, mineralogy and microstructure. The findings showed that the agro-industrial by-product can be used to yield alkali-activated materials with 7-day mechanical strengths on the order of 42 MPa. The study confirmed that both amorphous silica and part of the crystalline silica present in RHA participate in the alkaline activation process, providing the alkalinity is suitably adjusted.Este estudio evalúa la viabilidad de utilizar un subproducto agroindustrial, la ceniza de cascarilla de arroz (RHA proveniente de un equipo combustor de una empresa Arrocera en Colombia, como reemplazo total de la sílice aportada por el silicato de sodio comercial en sistemas cementicios activados alcalinamente. Se prepararon pastas de ceniza volante (FA, de escoria de alto horno (GBFS y un sistema binario 50FA:50GBFS, que fueron activadas por una mezcla de silicato de sodio e hidróxido de sodio, y por dos tipos de RHA. Las mezclas se caracterizaron mecánica, mineralógica y microestructuralmente. Los resultados demuestran que es posible obtener materiales activados alcalinamente con resistencias mecánicas del orden de 42 MPa, a 7 días de curado, utilizando el subproducto agroindustrial. Este estudio corrobora que tanto la sílice amorfa como parte de la sílice cristalina presente en RHA tienen la posibilidad de participar en el proceso de activación alcalina, siempre y cuando las condiciones de alcalinidad estén adecuadamente ajustadas.

  13. Influence of mesostasis in volcanic rocks on the alkali-aggregate reaction

    KAUST Repository

    Tiecher, Francieli


    Mesostasis material present in the interstices of volcanic rocks is the main cause of the alkali-aggregate reaction (AAR) in concretes made with these rock aggregates. Mesostasis often is referred to as volcanic glass, because it has amorphous features when analyzed by optical microscopy. However, this study demonstrates that mesostasis in the interstitials of volcanic rocks most often consists of micro to cryptocrystalline mineral phases of quartz, feldspars, and clays. Mesostasis has been identified as having different characteristics, and, thus, this new characterization calls for a re-evaluation of their influence on the reactivity of the volcanic rocks. The main purpose of this study is to correlate the characteristics of mesostasis with the AAR in mortar bars containing basalts and rhyolites. © 2012 Elsevier Ltd. All rights reserved.

  14. Experimental Investigation of CFRP Confined Columns Damaged by Alkali Aggregate Reaction

    Directory of Open Access Journals (Sweden)

    Siti Radziah Abdullah


    Full Text Available Fiber reinforced polymer is the most effective repair material in use to enhance the strength and ductility of deteriorated reinforced concrete columns. Often, fiber reinforced polymer (FRP provides passive confinement to columns until the dilation and cracking of concrete occurs. In the case of concrete suspected of Alkali Aggregate Reaction (AAR where concrete undergoes expansion, FRP wrap provides active confinement to the expanded concrete. In this study, the performance of carbon fiber reinforced polymer (CFRP wrapped columns damaged by AAR is evaluated based on the number of FRP layers and the time of the polymer application which provides two types of confinement: active or passive. The columns were tested under axial compression to evaluate the residual strength of the columns in comparison with unwrapped columns. The results reveal that the strength of the wrapped columns is enhanced with an increase in the number of CFRP layers. The strength of the columns under passive confinement is higher than the columns under active confinement. Under active confinement, early CFRP wrapping leads to improvement in the strength of the columns.

  15. Methane coupling reaction in an oxy-steam stream through an OH radical pathway by using supported alkali metal catalysts

    KAUST Repository

    Liang, Yin


    A universal reaction mechanism involved in the oxidative coupling of methane (OCM) is demonstrated under oxy-steam conditions using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from a H 2O-O2 reaction followed by C-H activation in CH 4 with an OH radical. Thus, the presence of water enhances both the CH4 conversion rate and the C2 selectivity. This OH radical pathway that is selective for the OCM was observed for the catalyst without Mn, which suggests clearly that Mn is not the essential component in a selective OCM catalyst. The experiments with different catalyst compositions revealed that the OH.-mediated pathway proceeded in the presence of catalysts with different alkali metals (Na, K) and different oxo anions (W, Mo). This difference in catalytic activity for OH radical generation accounts for the different OCM selectivities. As a result, a high C2 yield is achievable by using Na2WO4/SiO2, which catalyzes the OH.-mediated pathway selectively. Make it methane: A universal reaction mechanism involved in the oxidative coupling of methane is demonstrated under oxy-stream conditions by using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from an H2O-O2 reaction, followed by C-H activation in CH4 with an OH radical. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Ordered mesoporous silica prepared by quiescent interfacial growth method - effects of reaction chemistry (United States)

    Alsyouri, Hatem M.; Abu-Daabes, Malyuba A.; Alassali, Ayah; Lin, Jerry YS


    Acidic interfacial growth can provide a number of industrially important mesoporous silica morphologies including fibers, spheres, and other rich shapes. Studying the reaction chemistry under quiescent (no mixing) conditions is important for understanding and for the production of the desired shapes. The focus of this work is to understand the effect of a number of previously untested conditions: acid type (HCl, HNO3, and H2SO4), acid content, silica precursor type (TBOS and TEOS), and surfactant type (CTAB, Tween 20, and Tween 80) on the shape and structure of products formed under quiescent two-phase interfacial configuration. Results show that the quiescent growth is typically slow due to the absence of mixing. The whole process of product formation and pore structuring becomes limited by the slow interfacial diffusion of silica source. TBOS-CTAB-HCl was the typical combination to produce fibers with high order in the interfacial region. The use of other acids (HNO3 and H2SO4), a less hydrophobic silica source (TEOS), and/or a neutral surfactant (Tweens) facilitate diffusion and homogenous supply of silica source into the bulk phase and give spheres and gyroids with low mesoporous order. The results suggest two distinct regions for silica growth (interfacial region and bulk region) in which the rate of solvent evaporation and local concentration affect the speed and dimension of growth. A combined mechanism for the interfacial bulk growth of mesoporous silica under quiescent conditions is proposed.

  17. Linear Array Ultrasonic Test Results from Alkali-Silica Reaction (ASR) Specimens

    Energy Technology Data Exchange (ETDEWEB)

    Clayton, Dwight A [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Khazanovich, Dr. Lev [Univ. of Minnesota, Minneapolis, MN (United States); Salles, Lucio [Univ. of Minnesota, Minneapolis, MN (United States)


    The purpose of the U.S. Department of Energy Office of Nuclear Energy’s Light Water Reactor Sustainability (LWRS) Program is to develop technologies and other solutions that can improve the reliability, sustain the safety, and extend the operating lifetimes of nuclear power plants (NPPs) beyond 60 years. Since many important safety structures in an NPP are constructed of concrete, inspection techniques must be developed and tested to evaluate the internal condition. In-service containment structures generally do not allow for the destructive measures necessary to validate the accuracy of these inspection techniques. This creates a need for comparative testing of the various nondestructive evaluation (NDE) measurement techniques on concrete specimens with known material properties, voids, internal microstructure flaws, and reinforcement locations.This report presents results of the ultrasound evaluation of four concrete slabs with varying levels of ASR damage present. This included an investigation of the experimental results, as well as a supplemental simulation considering the effect of ASR damage by elasto-dynamic wave propagation using a finite integration technique method. It was found that the Hilbert Transform Indicator (HTI), developed for quantification of freeze/thaw damage in concrete structures, could also be successfully utilized for quantification of ASR damage. internal microstructure flaws, and reinforcement locations.

  18. Structrue and Characteristics of Mesoporous Silica Synthesized in Acid Medium and Its Reaction Mechanism

    Institute of Scientific and Technical Information of China (English)

    LEI Jia-heng; ZHAO Jun; CHEN Yong-xi; GUO Li-ping; LIU Dan


    Structrue and pore characteristics of the mesoporous silica synthesized in acid medium were studied by means of XRD, HRTEM, BET, FT-IR, DSC-TGA, and the reaction mechanism was also investigated deeply. The results show that mesopores in the sample possess hexagonal arrays obviously, whereas the structure of silica matrix is amorphous. The results also show that the acting mode of silica and CTMA+ inside the mesopores was chemical bonding force. The structure of mesoporous silica was mainly dependent on the aggregational condition of micelle of CTMA+ as well as their liquid-crystallized status. In addition, condensation and dehydration of silicate radicals were accompanied in the process of calcination, which resulted in the mesoporous structure ordered in local range and the pore sizes largening.

  19. Expansion of powerhouse structures due to alkali-aggregate reaction and the use of low calcium fly ash to ameliorate the reaction in future construction

    Energy Technology Data Exchange (ETDEWEB)

    Langley, W.S. [W.S. Langley Concrete and Material Technology Inc., NS (Canada); Brown, E. [Nova Scotia Power Corp., Halifax, NS (Canada)


    A study was conducted to examine a reaction in concrete between the alkalies found in the pore fluid and certain siliceous aggregates. This reaction, called alkali-aggregate reactivity caused disruptive expansion in a concrete powerhouse structure in Nova Scotia in 1962. The structure was constructed with meta-sediments and biotite schists. This combination caused expansion and resulted in problems with the operation of the plant within 10 years after construction. Subsequent studies showed that the reactive aggregates were widespread and that the problem could be solved using 15 to 30 per cent fly ash replacement of the cement. Now, low calcium fly ash is used on a regular basis to lessen the potential for alkali-aggregate reaction. Nova Scotia fly ash was also being studied for its use as a cement replacement and enhancement of concrete durability. It was concluded that this particular fly ash is an excellent supplementary cement material to offset disruptive expansions. The fly ash has been used since the mid 1980s for solving expansion problems in powerhouses. 6 refs., 3 tabs., 12 figs.

  20. Origin of hydrous alkali feldspar-silica intergrowth in spherulites from intra-plate A2-type rhyolites at the Jabal Shama, Saudi Arabia (United States)

    Surour, Adel A.; El-Nisr, Said A.; Bakhsh, Rami A.


    Miocene rhyolites (19.2 ± 0.9 Ma) at the Jabal Shama in western Saudi Arabia represent an example of rift-related silicic volcanism that took place during the formation of the Red Sea. They mostly consist of tuffaceous varieties with distinct flow banding, and pea-sized spherulites, obsidian and perlitized rhyolite tuffs. Although they have the geochemical signature of A2-type rhyolites, these silicic rocks are not typically alkaline but alkali-calcic to calc-alkaline. They developed in a within-plate regime and possibly derived from a recycled mafic subducted slab in depleted sub-continental mantle beneath the western Arabian plate. The Jabal Shama rhyolites are younger in age than their Miocene counterparts in Yemen and Ethiopia. The Jabal Shama spherulites consist of hydrous alkali feldspar-silica radial intergrowths with an occasional brown glass nucleus. Carbonate- and glass-free spherulites give up to 4.45 wt% L.O.I. The hydrous nature of these silicates and the absence of magnetite in the spherulites is a strong indication of oxidizing conditions. The spherulites contain hydrous feldspars with up to ∼6 wt% H2O, and they develop by diffusion and devitrification of glass in the rhyolite tuff at ∼800 °C. Owing to higher undercooling due to supersaturation, the radial hydrous phases within spherulites might grow faster and led to coagulation. The polygonal contacts between spherulites and the ∼120° dihedral angle suggest solid-state modification and recrystallization as the process of devitrification proceeds as low as ∼300 °C. The sum of FeO + MgO is positively correlated with total alkalies along with magnetite oxidation in the matrix to Fe-oxyhydroxides, and to the incorporation of OH- into silicates within the spehrulites themselves. Structural H2O in glass of the Jabal Shama perlite (obsidian) is considerable (∼9-12 wt%) with 3.72-5.6 wt% L.O.I. of the whole-rock. The presence of deleterious silica impurities would lower the ore grade due to

  1. Silica Induced Early Fibrogenic Reaction in Lung of Mice Ameliorated by Nyctanthes arbortristis Extract

    Institute of Scientific and Technical Information of China (English)


    Objective To investigate the pharmacological effect of Nyctanthes arbortristis (NAT) leaf extract in the prevention of lung injury induced by silica particles. Method Lung injury was induced in Swiss mice through inhalation exposure to silica particles (<5μ) using a Flow Past Nose Only Inhalation Chamber at the rate of -10 mg/m3 respirable mass for 5 h. Lung bronchoalveolar lavage (BAL) fluid collected between 48 and 72 h was subjected to protein profiling by electrophoresis and cytokine evaluation by solid phase sandwich ELISA. Lung histopathology was performed to evaluate lung injury. Results Inhalation of silica increased the level of tumor necrosis factor-α(TNF-α), and of the 66 and 63 kDa peptides in the BAL fluid in comparison to sham-treated control. Pre-treatment of silica exposed mice with NAT leaf extract significantly prevented the accumulation of TNF-α in the BAL fluid, but the 66 and 63 kDa peptides remained unchanged. The extract was also effective in the prevention of silica-induced early fibrogenic reactions like congestion, edema and infiltration of nucleated cells in the interstitial alveolar spaces, and thickening of alveolar septa in mouse lung. Conclusion NAT leaf extract helps in bypassing silica induced initial lung injury in mice.

  2. 40 CFR 721.10154 - Quaternary ammonium compounds, dicoco alkyldimethyl, chlorides, reaction products with silica. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Quaternary ammonium compounds, dicoco alkyldimethyl, chlorides, reaction products with silica. 721.10154 Section 721.10154 Protection of Environment... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10154 Quaternary ammonium...

  3. Modelling The Effects of Aggregate Size on Alkali Aggregate Reaction Expansion

    Directory of Open Access Journals (Sweden)

    N. Z. Sekrane


    Full Text Available This work aims at developing models to predict the potential expansion of concrete containing alkali-reactive aggregates. The paper gives measurements in order to provide experimental data concerning the effect of particle size of an alkali-reactive siliceous limestone on mortar expansion. Results show that no expansion was measured on the mortars using small particles (0.5-1.0 mm while the particles (1.0–2.0 mm gave the largest expansions (0.217%. Two models are proposed, the first one studies the correlations between the measured expansions and the size of aggregates, the second one calculates the thickness of the porous zone necessary to take again all the volume of the gel created.

  4. Reaction of chromalumozirconium refractory with alkali-free borosilicate glass melt

    Energy Technology Data Exchange (ETDEWEB)

    Popov, O.N.; Frolova, V.P.


    The corrosion mechanism of chromalumozirconium refractory synthesized on the base of the Cr/sub 2/O/sub 3/-Al/sub 2/O/sub 3/-ZrO/sub 2/-SiO/sub 2/ system by the alkali-free borosilicate ''E'' glass melt is investigated. It is estalished that in the process of refractory destruction the diffusion zonality is formed in it being a reflection of comparative migration activity of refractory components.

  5. Strength development, hydration reaction and pore structure of autoclaved slag cement with added silica fume

    Energy Technology Data Exchange (ETDEWEB)

    Xi, Y. [China Building Materials Academy, Beijing (China); Siemer, D.D. [LITCO, Idaho Falls, ID (United States); Scheetz, B.E. [Pennsylvania State Univ., University Park, PA (United States). Materials Research Lab.


    Under continuous hydrothermal treatment the strength of portland cement paste decreases with curing time and the pore structure coarsens. It was found in this study that the compressive strength of slag cement paste containing 67.5 wt.% ggbfs also decreases with time after 24 hour hydrothermal processing, but with a small addition of silica fume to the slag cement, the cement strength increases and the pore structure densifies when processed under comparable conditions. Based on observations XRD and SEM, these changes are attributed to: (1) changes in the hydration reactions and products by highly reactive silica fume, such that amorphous products dominate and the strength reducing phase {alpha}-C{sub 2}SH does not form; (2) slower hydration of slag, partially caused by the decreased pH of the pore solution, favors the formation of a dense pore structure; and (3) the space filling properties of the micro particles of silica fume.

  6. Inhibitions by hydrogen-occluding silica microcluster to melanogenesis in human pigment cells and tyrosinase reaction. (United States)

    Kato, Shinya; Saitoh, Yasukazu; Miwa, Nobuhiko


    We investigated the anti-melanogenetic efficacy of hydrogen-occluding silica microcluster (H2-Silica), which is a silsesquioxane-based compound with hydrogen interstitially embedded in a matrix of caged silica, against melanogenesis in HMV-II human melanoma cells and L-DOPA-tyrosinase reaction [EC1.14.18.1]. HMV-II cells were subjected to oxidative stress by ultraviolet ray-A (UVA) exposure of 3-times of 0.65 J/cm2 summed up to 1.95 J/cm2. After UVA irradiation, HMV-II cells were stimulated to produce melanin by 2.72-fold more abundantly than unirradiated control. When HMV-II cells were treated with H2-Silica of 20 ppm or kojic acid of 28.4 ppm before and after UVA-irradiation, the amount of melanin was repressed to 12.2% or 14.5% as compared to that of UVA-irradiated control, respectively. That is, H2-Silica exhibited a comparable efficacy to the whitening agent kojic acid. The H2-Silica could prevent melanogenesis in HMV-II cells by low-level doses at 1-10 ppm, and cell viability and apoptosis event did not change even by high-level doses at 100-1000 ppm. On the contrary, kojic acid was cytotoxic at the concentration of 14-28 ppm or more. By microscopic observation, H2-Silica suppressed such properties indicative of melanin-rich cells as cellular hypertrophy, cell process formation, and melanogenesis around the outside of nuclei. The enzymatic assay using L-DOPA and mushroom tyrosinase demonstrated that H2-Silica restrained UVA-mediated melanin formation owing to down-regulation of tyrosinase activity, which could be attributed to scavenging of free radicals and inhibition of L-DOPA-to-dopachrome oxidation by hydrogen released from H2-Silica. Thus H2-Silica has a potential to prevent melanin production against UVA and serves as a skin-lightening ingredient for supplements or cosmetics.

  7. Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang, E-mail:; Gao, Ziwei, E-mail:


    A successive anchoring of Ti(NMe{sub 2}){sub 4}, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, {sup 13}C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, {sup 13}C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated.

  8. Monodisperse metal nanoparticle catalysts on silica mesoporous supports: synthesis, characterizations, and catalytic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Somorjai, G.A.


    The design of high performance catalyst achieving near 100% product selectivity at maximum activity is one of the most important goals in the modern catalytic science research. To this end, the preparation of model catalysts whose catalytic performances can be predicted in a systematic and rational manner is of significant importance, which thereby allows understanding of the molecular ingredients affecting the catalytic performances. We have designed novel 3-dimensional (3D) high surface area model catalysts by the integration of colloidal metal nanoparticles and mesoporous silica supports. Monodisperse colloidal metal NPs with controllable size and shape were synthesized using dendrimers, polymers, or surfactants as the surface stabilizers. The size of Pt, and Rh nanoparticles can be varied from sub 1 nm to 15 nm, while the shape of Pt can be controlled to cube, cuboctahedron, and octahedron. The 3D model catalysts were generated by the incorporation of metal nanoparticles into the pores of mesoporous silica supports via two methods: capillary inclusion (CI) and nanoparticle encapsulation (NE). The former method relies on the sonication-induced inclusion of metal nanoparticles into the pores of mesoporous silica, whereas the latter is performed by the encapsulation of metal nanoparticles during the hydrothermal synthesis of mesoporous silica. The 3D model catalysts were comprehensively characterized by a variety of physical and chemical methods. These catalysts were found to show structure sensitivity in hydrocarbon conversion reactions. The Pt NPs supported on mesoporous SBA-15 silica (Pt/SBA-15) displayed significant particle size sensitivity in ethane hydrogenolysis over the size range of 1-7 nm. The Pt/SBA-15 catalysts also exhibited particle size dependent product selectivity in cyclohexene hydrogenation, crotonaldehyde hydrogenation, and pyrrole hydrogenation. The Rh loaded SBA-15 silica catalyst showed structure sensitivity in CO oxidation reaction. In

  9. Synthesis of palladium-doped silica nanofibers by sol-gel reaction and electrospinning process

    Energy Technology Data Exchange (ETDEWEB)

    San, Thiam Hui; Daud, Wan Ramli Wan; Kadhum, Abdul Amir Hassan; Mohamad, Abu Bakar; Kamarudin, Siti Kartom; Shyuan, Loh Kee; Majlan, Edy Herianto [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia); Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia and Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia); Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia)


    Nanofiber is drawing great attention nowadays with their high surface area per volume and flexibility in surface functionalities that make them favorable as a proton exchange membrane in fuel cell application. In this study, incorporation of palladium nanoparticles in silica nanofibers was prepared by combination of a tetraorthosilane (TEOS) sol-gel reaction with electrospinning process. This method can prevent the nanoparticles from aggregation by direct mixing of palladium nanoparticles in silica sol. The as-produced electrospun fibers were thermally treated to remove poly(vinyl pyrrolidone) (PVP) and condensation of silanol in silica framework. PVP is chosen as fiber shaping agent because of its insulting and capping properties for various metal nanoparticles. Scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectroscopy (FTIR) were used to characterize the silica fibers and Pd nanoparticles on the fibers. Spun fibers with average diameter ranged from 100nm to 400nm were obtained at optimum operating condition and distribution of Pd nanoparticles on silica fibers was investigated.

  10. Click on silica: systematic immobilization of Co(II) Schiff bases to the mesoporous silica via click reaction and their catalytic activity for aerobic oxidation of alcohols. (United States)

    Rana, Bharat S; Jain, Suman L; Singh, Bhawan; Bhaumik, Asim; Sain, Bir; Sinha, Anil K


    The systematic immobilization of cobalt(II) Schiff base complexes on SBA-15 mesoporous silica via copper catalyzed [3 + 2] azide-alkyne cycloaddition (CuAAC) "click reaction" involving either step-wise synthesis of silica-bound Schiff base ligand followed by its subsequent complexation with cobalt ions, or by the direct immobilization of preformed Co(II) Schiff base complex to the silica support is described. The catalytic activity of the prepared complexes was studied for the oxidation of alcohols to carbonyl compounds using molecular oxygen as oxidant. The immobilized complexes were recycled for several runs without loss in catalytic activity and no leaching was observed during this course.

  11. Reactions of chromium-aluminum-zirconium refractory with a molten alkali-free borosilicate glass

    Energy Technology Data Exchange (ETDEWEB)

    Popov, O.N.; Frolova, V.P.


    The authors consider the scope for using KhTs-45 refractory containing in mass % 45.0 Cr2O3, 5.0 Al2O3, 32.5 ZrO2, 16.0 SiO2, and 1.5 Na2O for melting alkali-free borosilicate glass E, and they also present some experimental results on the corrosion of the refractory in contact with the molten glass and on the contact mineral formation. They conclude that during the attack on the refractory diffusion zoning is formed, which reflects the relative component migration activities.

  12. Diffusion with chemical reaction: An attempt to explain number density anomalies in experiments involving alkali vapor (United States)

    Snow, W. L.


    The mutual diffusion of two reacting gases is examined which takes place in a bath of inert gas atoms. Solutions are obtained between concentric spheres, each sphere acting as a source for one of the reactants. The calculational model is used to illustrate severe number density gradients observed in absorption experiments with alkali vapor. Severe gradients result when sq root k/D R is approximately 5 where k, D, and R are respectively the second order rate constant, the multicomponent diffusion constant, and the geometrical dimension of the experiment.

  13. Probing the interplay between factors determining reaction rates on silica gel using termolecular systems. (United States)

    Kirkpatrick, Iain; Worrall, David R; Williams, Siân L; Buck, Craig J T; Meseguer, Rafael G


    In this study we have compared energy and electron transfer reactions in termolecular systems using a nanosecond diffuse reflectance laser flash photolysis technique. We have previously investigated these processes on silica gel surfaces for bimolecular systems and electron transfer in termolecular systems. The latter systems involved electron transfer between three arene molecules with azulene acting as a molecular shuttle. In this study we present an alternative electron transfer system using trans β-carotene as an electron donor in order to effectively immobilise all species except the shuttle, providing the first unambiguous evidence for radical ion mobility. In the energy transfer system we use naphthalene, a structural isomer of azulene, as the shuttle, facilitating energy transfer from a selectively excited benzophenone sensitiser to 9-cyanoanthracene. Bimolecular rate constants for all of these processes have been measured and new insights into the factors determining the rates of these reactions on silica gel have been obtained.

  14. Reactions of synthesis gas on silica supported transition metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Niemelae, M. [VTT Chemical Technology, Espoo (Finland). Lab. of Industrial Chemistry


    The effect of catalyst precursor and composition on the activation of CO was investigated using CO hydrogenation as a test reaction. The interrelations of preparation, pretreatment, characteristics and activity were clarified. For Co/SiO{sub 2} catalyst, MgO promotion increased the CO adsorption capacity and the hydrogen uptake, although the extent of reduction for cobalt remained the same or decreased. The conversion per active metallic cobalt site consequently increased in conjunction with MgO promotion, while the effect on overall performance per 1 g of catalyst remained moderate. The precursor affected the performance of Co/SiO{sub 2} considerably. CO was more strongly adsorbed on catalysts of carbonyl origin than on those derived from cobalt nitrate, the activity thus being higher. Although the nitrate derived Co/SiO{sub 2} appeared both to retain its activity and to regain its adsorption capacity better than the catalysts of carbonyl origin, the performance of the latter was superior with time on stream. For tetranuclear cluster based Co-Ru and Co-Rh catalysts, rhodium or ruthenium was in contact with the support and cobalt was enriched on top. On Co-Ru/SiO{sub 2} ruthenium enhanced deactivation, and no benefits in activity or oxygenate selectivity were achieved relative to the monometallic catalysts of cluster origin. The Co-Rh/SiO{sub 2} catalysts were also less active than those derived from monometallic clusters, but they exhibited higher selectivities to oxygenated compounds due to the presence of active sites on the perimeter of the cobalt particles located on rhodium. The highest selectivity to oxygenates was achieved by changing the decomposition atmosphere of Rh{sub 4}(CO){sub 12}/SiO{sub 2} from hydrogen to carbon monoxide. The results also showed two types of active sites to be operative in the formation of oxygenates - one for ethanol and another for aldehydes. (orig.) 69 refs.

  15. Alkali-activated cementitious materials: Mechanisms, microstructure and properties (United States)

    Jiang, Weimin

    The goal of this study was to examine the activation reaction, microstructure, properties, identify the mechanisms of activation, and achieve an enhanced understanding of activation processes occurring during the synthesis of alkali activated cementitious materials (AAC). The discussions classify the following categories. (1) alkali activated slag cement; (2) alkali activated portland-slag cement; (3) alkali activated fly ash-slag cement; (4) alkali activated pozzolana-lime cement; (5) alkali activated pozzolana cement. The activators involved are NaOH, KOH; Nasb2SOsb4;\\ Nasb2COsb3;\\ CaSOsb4, and soluble silicate of sodium and potassium. The effect of alkali activation on the microstructure of these materials were analyzed at the micro-nanometer scale by SEM, EDS, ESEM, and TEM. Also sp{29}Si and sp{27}Al MAS-NMR, IR, Raman, TGA, and DTA were performed to characterize the phase in these systems. Slag, fly ash, silica fume, as well as blended cements containing mixtures of these and other components were characterized. A set of ordinary portland cement paste samples served as a control. This study confirmed that AAC materials have great potential because they could generate very early high strength, greater durability and high performance. Among the benefits to be derived from this research is a better understanding of the factors that control concrete properties when using AAC materials, and by controlling the chemistry and processing to produce desired microstructures and properties, as well as their durability.

  16. Effect of charge density in chain extension reactions involving complexes of 4, 4'-diaminodiphenylmethane and various alkali metal salts (United States)

    Deshmukh, Subrajeet; Carrasquillo, Katherine; Tsai, Fang Chang; Wu, Lina; Hsu, Shaw Ling; University of Massachusetts Amherst Team

    Controlling the reaction of methylene diphenyl diisocyanate (MDI)-terminated polyester prepolymer and 4, 4'-diaminodiphenylmethane (MDA) is extremely important in many large scale applications. The ion-diamine complex has the advantage of blocking the instantaneous reaction between the diamine and isocyanate from taking place until it is released at elevated temperatures. We synthesized complexes of MDA with various alkali metal salts. These complexes create a barrier between the diamine and isocyanate thus preventing the premature reaction. We compared the complexes in terms of their dissociation and the subsequent curing with the prepolymer. Charge density had a tremendous effect. DSC showed that Na complexes dissociated at a lower temperature and needed less energy to dissociate than the Li complexes. The effect of change in cation on complex dissociation was more pronounced compared to the change in anion. Also, the ionic liquid introduced greatly altered the dissociation behavior. Temperature and time resolved IR spectroscopy was used to monitor the urea and NH band. By DSC and IR, we showed that NaCl complex is best suited for the curing of prepolymer with regards to curing temperature and energy.

  17. Assesment of Alkali Resistance of Basalt Used as Concrete Aggregates

    Directory of Open Access Journals (Sweden)

    al-Swaidani Aref M.


    Full Text Available The objective of this paper is to report a part of an ongoing research on the influence of using crushed basalt as aggregates on one of durability-related properties of concrete (i.e. alkali-silica reaction which is the most common form of Alkali-Aggregate Reaction. Alkali resistance has been assessed through several methods specified in the American Standards. Results of petrographic examination, chemical test (ASTM C289 and accelerated mortar bar test (ASTM C1260 have particularly been reported. In addition, the weight change and compressive strength of 28 days cured concrete containing basaltic aggregates were also reported after 90 days of exposure to 10% NaOH solution. Dolomite aggregate were used in the latter test for comparison. The experimental results revealed that basaltic rocks quarried from As-Swaida’a region were suitable for production of aggregates for concrete. According to the test results, the studied basalt aggregates can be classified as innocuous with regard to alkali-silica reaction. Further, the 10% sodium hydroxide attack did not affect the compressive strength of concrete.

  18. Fibrous nano-silica (KCC-1)-supported palladium catalyst: Suzuki coupling reactions under sustainable conditions

    KAUST Repository

    Fihri, Aziz


    Noble amines recycled: Fibrous high-surface-area nano-silica functionalized with aminopropyl groups and loaded with well-dispersed Pd nanoparticles is evaluated for the Suzuki coupling of aromatic halides. It is active for the reaction of a range of aryl bromides and iodides as well as chlorides with aryl boronic acids in good to excellent yields. The catalyst can be recovered and reused for a number of cycles with negligible loss in activity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Thermally Stable Nanocatalyst for High Temperature Reactions: Pt-Mesoporous Silica Core-Shell Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Joo, Sang Hoon; Park, J.Y.; Tsung, C.-K.; Yamada, Y.; Yang, P.; Somorjai, G.A.


    Recent advances in colloidal synthesis enabled the precise control of size, shape and composition of catalytic metal nanoparticles, allowing their use as model catalysts for systematic investigations of the atomic-scale properties affecting catalytic activity and selectivity. The organic capping agents stabilizing colloidal nanoparticles, however, often limit their application in high-temperature catalytic reactions. Here we report the design of a high-temperature stable model catalytic system that consists of Pt metal core coated with a mesoporous silica shell (Pt{at}mSiO{sub 2}). While inorganic silica shells encaged the Pt cores up to 750 C in air, the mesopores directly accessible to Pt cores made the Pt{at}mSiO{sub 2} nanoparticles as catalytically active as bare Pt metal for ethylene hydrogenation and CO oxidation. The high thermal stability of Pt{at}mSiO{sub 2} nanoparticles permitted high-temperature CO oxidation studies, including ignition behavior, which was not possible for bare Pt nanoparticles because of their deformation or aggregation. The results suggest that the Pt{at}mSiO{sub 2} nanoparticles are excellent nanocatalytic systems for high-temperature catalytic reactions or surface chemical processes, and the design concept employed in the Pt{at}mSiO{sub 2} core-shell catalyst can be extended to other metal-metal oxide compositions.

  20. Assessing the potential of ToF-SIMS as a complementary approach to investigate cement-based materials — Applications related to alkali–silica reaction

    Energy Technology Data Exchange (ETDEWEB)

    Bernard, Laetitia, E-mail: [Laboratory for Nanoscale Materials Science, Empa, Swiss Federal Laboratories for Material Science and Technology, Ueberlandstr. 129, 8600 Duebendorf (Switzerland); Leemann, Andreas [Laboratory for Concrete/Construction Chemistry, Empa, Swiss Federal Laboratories for Material Science and Technology, Ueberlandstr. 129, 8600 Duebendorf (Switzerland)


    In this study, the potential of time-of-flight secondary ion mass spectrometry (ToF-SIMS) for the application in cement-based materials is assessed in combination and comparison with scanning electron microscopy (SEM) and energy dispersive X-ray (EDX). Mortar, concrete and samples from model systems providing products formed by the alkali–silica reaction (ASR) were studied. ToF-SIMS provides qualitative data on alkalis in cases where EDX reaches its limits in regard to detectable concentration, lateral resolution and atomic number of the elements. Due to its high in-depth resolution of a few atomic monolayers, thin layers of reaction products can be detected on the surfaces and chemically analyzed with ToF-SIMS. Additionally, it delivers information on the molecular conformation within the ASR product, its hydrogen content and its isotope ratios, information not provided by EDX. Provided the samples are carefully prepared, ToF-SIMS opens up new possibilities in the analysis of cement-based materials.

  1. Study on Alkali-activated Silica Fume and Fly Ash Based Geopolymer%碱激发硅灰-粉煤灰基矿物聚合物的研究

    Institute of Scientific and Technical Information of China (English)

    王亚超; 张耀君; 徐德龙


    本文在碱激发粉煤灰矿物聚合物的基础上,研究了在粉煤灰中掺人适量硅灰形成碱激发硅灰-粉煤灰基矿物聚合物的性能.结果表明,当碱激发剂Na2SiO3·9H7O用量20wt%,硅灰掺量10wt%时,碱激发硅灰-粉煤灰基矿物聚合物在室温养护下抗压强度达到58.83 Mpa,较不掺硅灰的矿物聚合物强度提高了72%.X衍射分析表明,形成的矿物聚合物为无定形矿物相,SEM微观形貌分析表明,掺入硅灰后,矿物聚合物的微观结构更加致密,其强度大幅度提高.%The performances of alkali-activated silica fume and fly ash based geopolymer were studied based on alkali-activated fly ash geopolymer. The results showed that the compressive strength of geopolymer was 58.83 MPa in the curing time of ambient temperature and it increased by 72% comparing to the geopolymer without silica fume when the amount of activator, Na2SiO3 · 9H20, was 20wt% and incorporation of silica fume was 10wt%. The XRD results demonstrated that the geopolymer took the shape of amorphous phase. SEM images showed that the microstructure of geopolymer was further densification and the compressive strength was significantly improved after silica fume was added.

  2. Alkali-aggregate reactivity of typical siliceious glass and carbonate rocks in alkali-activated fly ash based geopolymers (United States)

    Lu, Duyou; Liu, Yongdao; Zheng, Yanzeng; Xu, Zhongzi; Shen, Xiaodong


    For exploring the behaviour of alkali-aggregate reactivity (AAR) in alkali-activated geopolymeric materials and assessing the procedures for testing AAR in geopolymers, the expansion behaviour of fly ash based geopolymer mortars with pure silica glass and typical carbonate rocks were studied respectively by curing at various conditions, i.e. 23°C and 38°C with relative humidity over 95%, immersed in 1M NaOH solution at 80°C. Results show that, at various curing conditions, neither harmful ASR nor harmful ACR was observed in geopolymers with the criteria specified for OPC system. However, with the change of curing conditions, the geopolymer binder and reactive aggregates may experience different reaction processes leading to quite different dimensional changes, especially with additional alkalis and elevated temperatures. It suggests that high temperature with additional alkali for accelerating AAR in traditional OPC system may not appropriate for assessing the alkali-aggregate reactivity behaviour in geopolymers designed for normal conditions. On the other hand, it is hopeful to control the dimensional change of geopolymer mortar or concrete by selecting the type of aggregates and the appropriate curing conditions, thus changing the harmful AAR in OPC into beneficial AAR in geopolymers and other alkali-activated cementitious systems.

  3. Influence of curing conditions on durability of alkali-resistant glass fibres in cement matrix

    Indian Academy of Sciences (India)

    Arabi Nourredine


    Glass fibres in concrete material often increase the flexural strength. However, these fibres when in contact with cement are altered by alkali reactions due to the presence of portlandite. This study presents the results of investigation to show the effect of curing conditions on the durability of alkali-resistant glass fibres in cement matrix. Test results show that even alkali resistant fibres treated with zirconium oxide present the same degradation phenomenon. They also show that the nature of the cement has a large influence on the protection of the fibres: the Portland CEM II is less damaging than the CEM I. The substitutions of a part of cement by silica fume gave no substantial improvements to the mechanical strength of the glass fibre reinforced cement (GFRC). However, the observed microstructures in the samples show that the degradation is weakened with the addition of silica fumes. The analytical techniques used in this study are scanning electron microscope (SEM) and X-ray diffraction.

  4. SiC Conversion Coating Prepared from Silica-Graphite Reaction

    Directory of Open Access Journals (Sweden)

    Back-Sub Sung


    Full Text Available The β-SiC conversion coatings were successfully synthesized by the SiO(v-graphite(s reaction between silica powder and graphite specimen. This paper is to describe the effects on the characteristics of the SiC conversion coatings, fabricated according to two different reaction conditions. FE-SEM, FE-TEM microstructural morphologies, XRD patterns, pore size distribution, and oxidation behavior of the SiC-coated graphite were investigated. In the XRD pattern and SAD pattern, the coating layers showed cubic SiC peak as well as hexagonal SiC peak. The SiC coatings showed somewhat different characteristics with the reaction conditions according to the position arrangement of the graphite samples. The SiC coating on graphite, prepared in reaction zone (2, shows higher intensity of beta-SiC main peak (111 in XRD pattern as well as rather lower porosity and smaller main pore size peak under 1 μm.

  5. Reaction parameter study for the chemical synthesis of adsorbent silica gel

    Directory of Open Access Journals (Sweden)

    María Carolina Sáenz


    Full Text Available This article presents an appropriate set of reaction parameters (reaction temperature, sulphuric acid and sodium silicate reagent concentration for obtaining adsorbent silica gel (ASG using Colombian-produced raw materials. The core of ASG synthesis lies in sulphuric acid’s neutralisation reaction with sodium silicate. Their effect on final ASG moisture adsorption capacity was measured after changing such synthesis’ above–mentioned reaction parameters. Within the range of conditions studied, it was found that the highest adsorption capacity occurred by combining both low sodium silicate concentration with high temperatures or high sulphuric acid concentration and temperature. Synthesised ASG was also compared to a commercial product (Gel de sílice granulare con indicatore. Montedison group. Batch number 1684G100. Code number 453301 using adsorption capacity plots, BET areas, X–ray di-ffraction, mass and infrared spectrometry and mechanical strength measurements. Synthesised ASG presented larger specific surface areas but weaker mechanical strength than the commercial one. Likewise, all evaluated samples exhibited a low degree of molecular arrangement and conventional ASG chemical structure.

  6. SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions

    KAUST Repository

    Qureshi, Ziyauddin S.


    Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

  7. Extending the Life of Lithium-Based Rechargeable Batteries by Reaction of Lithium Dendrites with a Novel Silica Nanoparticle Sandwiched Separator. (United States)

    Liu, Kai; Zhuo, Denys; Lee, Hyun-Wook; Liu, Wei; Lin, Dingchang; Lu, Yingying; Cui, Yi


    A reaction-protective separator that slows the growth of lithium dendrites penetrating into the separator is produced by sandwiching silica nanoparticles between two polymer separators. The reaction between lithium dendrites and silica nanoparticles consumes the dendrites and can extend the life of the battery by approximately five times.

  8. Alkali- or acid-induced changes in structure, moisture absorption ability and deacetylating reaction of β-chitin extracted from jumbo squid (Dosidicus gigas) pens. (United States)

    Jung, Jooyeoun; Zhao, Yanyun


    Alkali- or acid-induced structural modifications in β-chitin from squid (Dosidicus gigas, d'Orbigny, 1835) pens and their moisture absorption ability (MAA) and deacetylating reaction were investigated and compared with α-chitin from shrimp shells. β-Chitin was converted into the α-form after 3h in 40% NaOH or 1-3 h in 40% HCl solution, and α-chitin obtained from NaOH treatment had higher MAA than had native α-chitin, due to polymorphic destructions. In contrast, induced α-chitin from acid treatment of β-chitin had few polymorphic modifications, showing no significant change (P>0.05) in MAA. β-Chitin was more susceptible to alkali deacetylation than was α-chitin, and required a lower concentration of NaOH and shorter reaction time. These results demonstrate that alkali- or acid-treated β-chitin retained high susceptibility toward solvents, which in turn resulted in good biological activity of β-chitosan for use as a natural antioxidant and antimicrobial substance or application as edible coatings and films for various food applications.

  9. Synthesis of Au-Ag alloy nanoparticles supported on silica gel via galvanic replacement reaction

    Institute of Scientific and Technical Information of China (English)

    Xiaoyan Liu; Aiqin Wang; Lin Li; Tao Zhang; Chung-Yuan Mou; Jyh-Fu Lee


    Synthesis of supported Au-Ag bimetallic has attracted much attention since we found for the first time that Au and Ag had synergistic effect on CO oxidation and preferential CO oxidation in rich hydrogen. In this work, the formation of Au-Ag alloy nanoparticles supported on silica gel by galvanic replacement reaction has been investigated. We applied various characterizations including X-ray diffraction (XRD), transmission electronic microscopy (TEM), ultraviolet-visible spectroscopy (UV-vis), X-ray absorption spectroscopy (XAS) to characterize the formation process of Au-Ag alloy. Although the average particle sizes of the Au-Ag alloy nanoparticles obtained by the galvanic replacement reaction are relatively large comparing with that of loading Au first, the catalytic activity of the catalyst in preferential CO oxidation is almost the same. This result manifested that the particle size effect of Au-Ag nanoparticles was not as tremendous as that of monometallic gold. The formation of Au-Ag alloy made it less sensitive to the particle size.

  10. A test on reactive force fields for the study of silica dimerization reactions

    Energy Technology Data Exchange (ETDEWEB)

    Moqadam, Mahmoud; Riccardi, Enrico; Trinh, Thuat T.; Åstrand, Per-Olof; Erp, Titus S. van, E-mail: [Department of Chemistry, Norwegian University of Science and Technology (NTNU), Høgskoleringen 5, Realfagbygget D3-117, 7491 Trondheim (Norway)


    We studied silica dimerization reactions in the gas and aqueous phase by density functional theory (DFT) and reactive force fields based on two parameterizations of ReaxFF. For each method (both ReaxFF force fields and DFT), we performed constrained geometry optimizations, which were subsequently evaluated in single point energy calculations using the other two methods. Standard fitting procedures typically compare the force field energies and geometries with those from quantum mechanical data after a geometry optimization. The initial configurations for the force field optimization are usually the minimum energy structures of the ab initio database. Hence, the ab initio method dictates which structures are being examined and force field parameters are being adjusted in order to minimize the differences with the ab initio data. As a result, this approach will not exclude the possibility that the force field predicts stable geometries or low transition states which are realistically very high in energy and, therefore, never considered by the ab initio method. Our analysis reveals the existence of such unphysical geometries even at unreactive conditions where the distance between the reactants is large. To test the effect of these discrepancies, we launched molecular dynamics simulations using DFT and ReaxFF and observed spurious reactions for both ReaxFF force fields. Our results suggest that the standard procedures for parameter fitting need to be improved by a mutual comparative method.

  11. Novel multiparametric approach to elucidate the surface amine-silanization reaction profile on fluorescent silica nanoparticles. (United States)

    Roy, Shibsekhar; Dixit, Chandra K; Woolley, Robert; MacCraith, Brian D; O'Kennedy, Richard; McDonagh, Colette


    This Article addresses the important issue of the characterization of surface functional groups for optical bioassay applications. We use a model system consisting of spherical dye-doped silica nanoparticles (NPs) that have been functionalized with amine groups whereby the encapsulated cyanine-based near-infrared dye fluorescence acts as a probe of the NP surface environment. This facilitates the identification of the optimum deposition parameters for the formation of a stable ordered amine monolayer and also elucidates the functionalization profile of the amine-silanization process. Specifically, we use a novel approach where the techniques of fluorescence correlation spectroscopy (FCS) and fluorescence lifetime measurement (FL) are used in conjunction with the more conventional analytical techniques of zeta potential measurement and Fourier transfer infrared spectroscopy (FTIR). The dynamics of the ordering of the amine layer in different stages of the reaction have been characterized by FTIR, FL, and FCS. The results indicate an optimum reaction time for the formation of a stable amine layer, which is optimized for further biomolecular conjugation, whereas extended reaction times lead to a disordered cross-linked layer. The results have been validated using an immunoglobulin (IgG) plate-based direct binding assay where the maximum number of IgG-conjugated aminated NPs were captured by immobilized anti-IgG antibodies for the NP sample corresponding to the optimized amine-silanization condition. Importantly, these results point to the potential of FCS and FL as useful analytical tools in diverse fields such as characterization of surface functionalization.

  12. A coupled mechanical and chemical damage model for concrete affected by alkali–silica reaction

    Energy Technology Data Exchange (ETDEWEB)

    Pignatelli, Rossella, E-mail: [Department of Civil and Environmental Engineering, Politecnico di Milano, Piazza L. da Vinci 32, 20133 Milano (Italy); Lombardi Ingegneria S.r.l., Via Giotto 36, 20145 Milano (Italy); Comi, Claudia, E-mail: [Department of Civil and Environmental Engineering, Politecnico di Milano, Piazza L. da Vinci 32, 20133 Milano (Italy); Monteiro, Paulo J.M., E-mail: [Department of Civil and Environmental Engineering, University of California, Berkeley, CA 94720 (United States)


    To model the complex degradation phenomena occurring in concrete affected by alkali–silica reaction (ASR), we formulate a poro-mechanical model with two isotropic internal variables: the chemical and the mechanical damage. The chemical damage, related to the evolution of the reaction, is caused by the pressure generated by the expanding ASR gel on the solid concrete skeleton. The mechanical damage describes the strength and stiffness degradation induced by the external loads. As suggested by experimental results, degradation due to ASR is considered to be localized around reactive sites. The effect of the degree of saturation and of the temperature on the reaction development is also modeled. The chemical damage evolution is calibrated using the value of the gel pressure estimated by applying the electrical diffuse double-layer theory to experimental values of the surface charge density in ASR gel specimens reported in the literature. The chemo-damage model is first validated by simulating expansion tests on reactive specimens and beams; the coupled chemo-mechanical damage model is then employed to simulate compression and flexure tests results also taken from the literature. -- Highlights: •Concrete degradation due to ASR in variable environmental conditions is modeled. •Two isotropic internal variables – chemical and mechanical damage – are introduced. •The value of the swelling pressure is estimated by the diffuse double layer theory. •A simplified scheme is proposed to relate macro- and microscopic properties. •The chemo-mechanical damage model is validated by simulating tests in literature.

  13. Mecanismes d'action des fines et des granulats de verre sur la reaction alcali-silice et la reaction pouzzolanique (United States)

    Idir, Rachida

    Recycling composite glass with different colours in order to be manufactured into new glass products is at present not economically viable. Therefore, the search for new issues other than stockpile areas or dumping sites could be a serious opportunity. To a certain extent, one of the possible solutions is to use the recycled glass in manufacturing cements and in the preparation of concrete mixtures. However, it is essential to manage the two main behaviours that the glass can have when used in cement-based materials: (1) the use of glass as coarse aggregates reveals harmful behaviour related to alkali-silica reaction; (2) on the other hand, it can result in useful behaviour related to pozzolanic reaction if used as fine particles. Furthermore, the significant alkali content should not be overlooked as their mass corresponds to about 13% of the total mass of the glass and as they may activate the alkali-silica reaction. An experimental programme was conducted to provide answers to the various questions raised about the use of glass in cement-based materials. The first part of this work was primarily devoted to the evaluation of the reactive potential of glass in mortars (alkali and pozzolanic reactions). At this stage, nine classes of glass particles ranging from 3mum to 2.5 mm were considered. Then, fine glass particles were used in order to counteract the negative effect of some classes of coarse aggregates having revealed alkali-reactive behaviour. The second part of this work was performed to study the mechanisms that could explain the behaviours of fine and coarse particles in aqueous and concentrated environments. Different answers have been proposed to explain the observed behaviour in terms of grain sizes of glass. Keywords: Glass, Powder, Pozzolan, aggregates, alkali-reaction, alkali-aggregate reaction, alkali-silica reaction, Pouzzolanicity, alkalis, Mortars

  14. A Piezoelectric Immunosensor Based on Agglutination Reaction with Amplification of Silica Nanoparticles

    Institute of Scientific and Technical Information of China (English)

    JIN,Xiao-Yong; JIN,Xue-Fang; DING,Yan-Jun; JIANG,Jian-Hui; SHEN,Guo-Li; Ru-Qin


    A simple piezoelectric immunoagglutination assay technique with antibody-modified nanoparticles has been developed for direct quantitative detection of protein. The proposed technique is based on the specific agglutination of goat anti-hlgG-coated silica (or gold) nanoparticles in the presence of human immunoglobulin G (hlgG), which causes a frequency change and is monitored by a piezoelectric device. The antibody modified on the probe surface would combine with antibody-coated nanoparticles in the presence of antigen (hlgG) when the surface agglutination reaction took place, which couples both the mass effect and viscoelastic effect acting on the probe. The results indi-cate that the background interference can be substantially minimized and the probe signal can be observably multi-plied. In addition, the surface of the modified probe and that after combining the complex of immunoagglutination were imaged by scanning electronic microscopy (SEM). Moreover, an optimization of assay medium composition with the addition of poly(ethylene glycol) (PEG) serving as immunoagglutination enhancer and sodium chloride to control the ion-strength was investigated. The frequency responses of the immunoagglutination assay were found to correlate well with the hlgG concentration with a detection limit of 84 ng.mL-1.

  15. Synthesis of organic-inorganic hybrid sols with nano silica particles and organoalkoxysilanes for transparent and high-thermal-resistance coating films using sol-gel reaction. (United States)

    Na, Moonkyong; Park, Hoyyul; Ahn, Myeongsang; Lee, Hyeonhwa; Chung, Ildoo


    Organic-inorganic hybrid sols were synthesized from nano silica particles dispersed in water and from organoalkoxysilanes, using the sol-gel reaction. This work focuses on the effects of the three multifunctional organoalkoxysilanes dimethyldimethoxysilane (DMDMS), methyltrimethoxysilane (MTMS), and tetramethoxysilane (TMOS) to form a transparent and high-thermal-resistance coating film. The stability of the hybrid sol was evaluated as a function of the reaction time for 10 d through the variation of the viscosity. The viscosity of the silica/DMDMS and silica/MTMS sol was slightly increased for 10 d. The multifunctional organoalkoxysilanes formed dense silica networks through hydrolysis and condensation reaction, which enhanced the thermal resistance of the coating films. No thermal degradation of the silica/DMDMS sample occurred up to 600 degrees C, and none of the silica/MTMS and silica/TMOS samples occurred either up to 700 degrees C. The organic-inorganic hybrid sols were coated on the glass substrate using a spin-coating procedure. The organic-inorganic hybrid sols formed flat coating films without cracks. The transmittance of the hybrid sol coating films using MTMS and DMDMS was shown to be over 90%. The transmittance of the silica/TMOS sol coating film reacted for 10 d abruptly decreased due to faster gelation. The silica/DMDMS and silica/MTMS hybrid sols formed smooth coating films while the surface roughness of the silica/TMOS coating film markedly increased when the hybrid sol reacted for 10 d. The increase of the surface roughness of the silica/TMOS coating film can be attributed to the degradation of the stability of the hybrid sol and to the loss of transmittance of the coating film. It was confirmed in this study that the use of organic-inorganic hybrid sol can yield transparent and high-thermal-resistance coating films.

  16. Reaction Kinetics of LiOH· H2O and CO2 Improved with Composite Silica Gel of Lanthanum Chloride

    Institute of Scientific and Technical Information of China (English)

    Zhao Zhuo; Fu Pingfeng; Wang Jingxin


    Reaction kinetics of LiOH·H2O and C·2 within a closed system were studied under the adsorption of water vapor by composite silica gel of lanthanum chloride. At the reaction temperature of 273~323K and initial CO2 pressures of 40~100kPa, reaction kinetics obeyed the Erofeev model. The reaction rate decreased slightly while the initial CO2 pressure reduced. When the reaction occurred at 273~299K, the reaction rate was so low that it was almost independent of the reaction temperature. However, as the temperature rose up to 300~323K, LiOH·H2O dehydrated its crystal water, and both the dehydrated and reaction-generated water were evaporated from solid reactant. For the dehydration rate increased, the reaction rate also increased as the reaction temperature rose. While the temperature was higher than 323K, the reaction apparent activation energy of LiOH·H2O and CO2, was higher than 52.5kJ·mol-1 and close to 61.4kJ·mol-1 of the LiOH·H2O dehydrated enthalpy variable at 298K, in which anhydrous LiOH was the major reactant and showed the reaction characteristics of LiOH crystals.

  17. An Experimental Study on Mitigating Alkali Silica Reaction by Using Fly Ash (FA in Combination with Silica Fume and Expanded Perlite Powder (EPP

    Directory of Open Access Journals (Sweden)

    Isneini Mohd


    Full Text Available ASR suppression by FA, SF, EPP, FA in combination with SF and EPP were evaluated by both mortar bar and concrete prism test. Mortar bars were made based on JIS A 1146, meanwhile concrete prism bars were casted in accordance with Rilem AAR-3. Both specimens were stored in 40°C 100% R.H. controlled room. Mortar and concrete mixtures used reactive aggregate in pessimum proportion. The results indicated that FA in combination with SF and EPP showed smaller expansion compared to FA. The best of concrete mixtures in reducing expansion is combination of FA with SF (FA15SF10.

  18. Reaction Kinetics of LiOH Improved with Composite Silica Gel of Lanthanum Chloride for Absorbing CO2

    Institute of Scientific and Technical Information of China (English)

    Zhao Zhuo; Fu Pingfeng; Wang Jingxin


    A static method was employed to study the reaction kinetics of anhydrous lithium hydroxide (LiOH) and CO2. The reaction generated water was absorbed with the composite silica gel of lanthanum chloride to make the experiment repeatable. At the reaction temperature of 15~60℃ and initial CO2 pressures of 25~100kPa, the reaction rate of anhydrous LiOH and CO2 decreased slightly with the reduction of initial CO2 pressure and the rise of reaction temperature, indicating that the reaction activation energy of LiOH and CO2 was negative and close to zero. During the middle period (1~5 min) of the isothermal reaction, the ratio of reaction efficiency was approximately the power of 0.4 to that of initial CO2 pressures. As anhydrous LiOH reacted to CO2, the solid product Li2CO3 covered on the surface of LiOH was not compact, so it did not hinder the subsequent reaction of absorbing the CO2 gas. The reaction kinetics of anhydrous LiOH and CO2 obeyed the Erofeev's model.

  19. Structural and catalytic properties of a novel vanadium containing solid core mesoporous silica shell catalysts for gas phase oxidation reaction

    Indian Academy of Sciences (India)

    N Venkatathri; Vijayamohanan K Pillai; A Rajini; M Nooka Raju; I A K Reddy


    A novel vanadium containing solid core mesoporous silica shell catalyst was synthesized with different Si/V ratios by sol-gel method under neutral conditions. The synthesized materials were characterized by various techniques and gas phase diphenyl methane oxidation reaction. The mesoporosity combined with microporosity are formed by incorporation of octadecyltrichloro silane and triethylamine in the catalyst and it was found out from E-DAX and BET—surface area analysis. The material was found to be nanocrystalline. Vanadium is present as V4+ species in as-synthesized samples and convert to V5+ on calcination. Most of the vanadium is present in tetrahedral or square pyramidal environment. Incorporation of vanadium in silica framework was confirmed by 29Si MAS NMR analysis. Among the various vanadium containing solid core mesoporous silica shell catalysts, the Si/V =100 ratio exhibited maximum efficiency towards diphenyl methane to benzophenone gas phase reaction. The optimum condition required for maximum conversion and selectivity was found out from the catalytic studies.

  20. Unified ZnO Q-dot growth mechanism from simultaneous UV-Vis and EXAFS monitoring of sol-gel reactions induced by different alkali base (United States)

    Caetano, Bruno L.; Silva, Marlon N.; Santilli, Celso V.; Briois, Valérie; Pulcinelli, Sandra H.


    This article aims to give experimental evidences of the universality of main steps involved in ZnO nanoparticles formation and growth from sol-gel process. In this way, we revisit the effect of the alkali base (LiOH, NaOH, KOH) used to induce the hydrolysis-condensation reaction in order to unfold the ZnO Q-dot formation mechanisms by using simultaneous time resolved monitoring of zinc species and Q-dot size by combining EXAFS and UV-Vis spectroscopy. Irrespective of the alkali base used, nucleation and growth of ZnO Q-dots occur by consumption of zinc oxy-acetate precursor. Higher amounts of ZnO nanocrystal are produced as the strength of the base increases. After achieving the steady state equilibrium regime the Q-dot growth occurs initially by oriented attachment coalescence mechanism followed by the Ostwald ripening coarsening. The dependence of the formation and growth mechanisms on the base strength allows the fine tuning of the Q-dot size and photoluminescence properties.

  1. A thermodynamic and kinetic model for paste–aggregate interactions and the alkali–silica reaction

    Energy Technology Data Exchange (ETDEWEB)

    Guthrie, George D., E-mail:; Carey, J. William


    A new conceptual model is developed for ASR formation based on geochemical principles tied to aqueous speciation, silica solubility, kinetically controlled mineral dissolution, and diffusion. ASR development is driven largely by pH and silica gradients that establish geochemical microenvironments between paste and aggregate, with gradients the strongest within the aggregate adjacent to the paste boundary (i.e., where ASR initially forms). Super-saturation of magadiite and okenite (crystalline ASR surrogates) occurs in the zone defined by gradients in pH, dissolved silica, Na{sup +}, and Ca{sup 2} {sup +}. This model provides a thermodynamic rather than kinetic explanation of why quartz generally behaves differently from amorphous silica: quartz solubility does not produce sufficiently high concentrations of H{sub 4}SiO{sub 4} to super-saturate magadiite, whereas amorphous silica does. The model also explains why pozzolans do not generate ASR: their fine-grained character precludes formation of chemical gradients. Finally, these gradients have interesting implications beyond the development of ASR, creating unique biogeochemical environments.

  2. Acid-base bifunctional catalysis of silica-alumina-supported organic amines for carbon-carbon bond-forming reactions. (United States)

    Motokura, Ken; Tomita, Mitsuru; Tada, Mizuki; Iwasawa, Yasuhiro


    Acid-base bifunctional heterogeneous catalysts were prepared by the reaction of an acidic silica-alumina (SA) surface with silane-coupling reagents possessing amino functional groups. The obtained SA-supported amines (SA-NR2) were characterized by solid-state 13C and 29Si NMR spectroscopy, FT-IR spectroscopy, and elemental analysis. The solid-state NMR spectra revealed that the amines were immobilized by acid-base interactions at the SA surface. The interactions between the surface acidic sites and the immobilized basic amines were weaker than the interactions between the SA and free amines. The catalytic performances of the SA-NR2 catalysts for various carbon-carbon bond-forming reactions, such as cyano-ethoxycarbonylation, the Michael reaction, and the nitro-aldol reaction, were investigated and compared with those of homogeneous and other heterogeneous catalysts. The SA-NR2 catalysts showed much higher catalytic activities for the carbon-carbon bond-forming reactions than heterogeneous amine catalysts using other supports, such as SiO2 and Al2O3. On the other hand, homogeneous amines hardly promoted these reactions under similar reaction conditions, and the catalytic behavior of SA-NR2 was also different from that of MgO, which was employed as a typical heterogeneous base. An acid-base dual-activation mechanism for the carbon-carbon bond-forming reactions is proposed.

  3. Alkali metal ion catalysis and inhibition in nucleophilic displacement reactions at phosphorus centers: ethyl and methyl paraoxon and ethyl and methyl parathion. (United States)

    Um, Ik-Hwan; Shin, Young-Hee; Lee, Seung-Eun; Yang, Kiyull; Buncel, Erwin


    We report on the ethanolysis of the P=O and P=S compounds ethyl and methyl paraoxon (1a and 1b) and ethyl and methyl parathion (2a and 2b). Plots of spectrophotometrically measured rate constants, kobsd versus [MOEt], the alkali ethoxide concentration, show distinct upward and downward curvatures, pointing to the importance of ion-pairing phenomena and a differential reactivity of free ions and ion pairs. Three types of reactivity and selectivity patterns have been discerned: (1) For the P=O compounds 1a and 1b, LiOEt > NaOEt > KOEt > EtO-; (2) for the P=S compound 2a, KOEt > EtO- > NaOEt > LiOEt; (3) for P=S, 2b, 18C6-crown-complexed KOEt > KOEt = EtO(-) > NaOEt > LiOEt. These selectivity patterns are characteristic of both catalysis and inhibition by alkali-metal cations depending on the nature of the electrophilic center, P=O vs P=S, and the metal cation. Ground-state (GS) vs transition-state (TS) stabilization energies shed light on the catalytic and inhibitory tendencies. The unprecedented catalytic behavior of crowned-K(+) for the reaction of 2b is noteworthy. Modeling reveals an extreme steric interaction for the reaction of 2a with crowned-K(+), which is responsible for the absence of catalysis in this system. Overall, P=O exhibits greater reactivity than P=S, increasing from 50- to 60-fold with free EtO(-) and up to 2000-fold with LiOEt, reflecting an intrinsic P=O vs P=S reactivity difference (thio effect). The origin of reactivity and selectivity differences in these systems is discussed on the basis of competing electrostatic effects and solvational requirements as function of anionic electric field strength and cation size (Eisenman's theory).

  4. A Novel Approach to Prepare Well-Defined Silica-Supported Polyoxometalate Species by Reaction with a Chlorinated Support

    Directory of Open Access Journals (Sweden)

    Eva Grinenval


    Full Text Available Polyoxometalates were grafted covalently on SBA-15 by a two-step procedure. The dehydroxylated mesoporous silica was first modified by reaction with methyltrichlorosilane in presence of triethylamine. The resulting solid was fully characterized and contained a mixture of mono- and digrafted species . These surface Si–Cl bonds can react with lacunary polyoxometalates as in solution, yielding to a ≡Si–O–POM linkage. However, solid state MAS NMR shows that only the digrafted species react with the polyoxometalate. This new grafting method opens the way to the synthesis of a new class of catalysts which could operate in solution without leaching.

  5. PVP-Stabilized Palladium Nanoparticles in Silica as Effective Catalysts for Hydrogenation Reactions

    Directory of Open Access Journals (Sweden)

    Caroline Pires Ruas


    Full Text Available Palladium nanoparticles stabilized by poly (N-vinyl-2-pyrrolidone (PVP can be synthesized by corresponding Pd(acac2 (acac = acetylacetonate as precursor in methanol at 80°C for 2 h followed by reduction with NaBH4 and immobilized onto SiO2 prepared by sol-gel process under acidic conditions (HF or HCl. The PVP/Pd molar ratio is set to 6. The effect of the sol-gel catalyst on the silica morphology and texture and on Pd(0 content was investigated. The catalysts prepared (ca. 2% Pd(0/SiO2/HF and ca. 0,3% Pd(0/SiO2/HCl were characterized by TEM, FAAS, and SEM-EDS. Palladium nanoparticles supported in silica with a size 6.6 ± 1.4 nm were obtained. The catalytic activity was tested in hydrogenation of alkenes.

  6. Nano Silica with High Surface Area from Rice Husk as a Support for 12-Tungstophosphoric Acid: An Efficient Nano Catalyst in Some Organic Reactions%Nano Silica with High Surface Area from Rice Husk as a Support for 12-Tungstophosphoric Acid:An Efficient Nano Catalyst in Some Organic Reactions

    Institute of Scientific and Technical Information of China (English)



    Nano silica was prepared from rice husk with high surface area.X-ray diffraction (XRD) pattern showed that the amorphous form of silica was produced.Chemical composition of the nano silica was estimated by X-ray fluorescence spectroscopy and CHN analysis.The nano silica was used as a support for H3PW12O40.The nano silica and nano silica supported H3PW12O40were characterized by inductively coupled plasma,XRD,transmission electron microscopy (TEM),N2 adsorption-desorption,and Fourier transform infrared spectroscopy.TEM images of nano silica as well as the supported catalyst displayed average size of 6 and 7 nm,respectively.The catalyst showed excellent activity in some important organic reactions including Biginelli,Hantzsch,Mannich,and Claisen-Schmidt reactions with good reusability.Catalytic activity of this nano catalyst is an improvement over the commercially available silica that is used to support H3PW12O40.

  7. Study on alkali reaction of nickel slag and nickel slag-sand mixtures in Ningde region%宁德地区镍渣及其复掺砂的碱活性研究

    Institute of Scientific and Technical Information of China (English)



    The article discussed the alkali reaction of nickel slag and aggregate mixed with natural sand through petrographic method and al -kali-aggregate reaction .The results showed that the nickel slag could not be used as aggregate in concrete because of its potential alkali -aggregate damage .The research also showed that the potential alkali -aggregate damage could be reduced by mixing natural sand , and there was no alkali-aggregate harm to the aggregate when the natural sand content was not less than 50%.%本文通过岩相法和快速碱-骨料反应法研究了镍渣及其复掺砂的碱活性。研究表明镍渣具有潜在碱-骨料反应危害,不宜单独用作混凝土骨料。通过复掺标准砂可以降低碱-骨料反应危害,实验表明当标准砂掺量不低于50%时,复掺砂不存在碱-骨料反应危害。

  8. Catalytically active Au-O(OH)x-species stabilized by alkali ions on zeolites and mesoporous oxides. (United States)

    Yang, Ming; Li, Sha; Wang, Yuan; Herron, Jeffrey A; Xu, Ye; Allard, Lawrence F; Lee, Sungsik; Huang, Jun; Mavrikakis, Manos; Flytzani-Stephanopoulos, Maria


    We report that the addition of alkali ions (sodium or potassium) to gold on KLTL-zeolite and mesoporous MCM-41 silica stabilizes mononuclear gold in Au-O(OH)x-(Na or K) ensembles. This single-site gold species is active for the low-temperature (alkali ions and establishing an active site on various supports. The intrinsic activity of the single-site gold species is the same on irreducible supports as on reducible ceria, iron oxide, and titania supports, apparently all sharing a common, similarly structured gold active site. This finding paves the way for using earth-abundant supports to disperse and stabilize precious metal atoms with alkali additives for the WGS and potentially other fuel-processing reactions.

  9. Aptamer-based organic-silica hybrid affinity monolith prepared via "thiol-ene" click reaction for extraction of thrombin. (United States)

    Wang, Zheng; Zhao, Jin-cheng; Lian, Hong-zhen; Chen, Hong-yuan


    A novel strategy for preparing aptamer-based organic-silica hybrid monolithic column was developed via "thiol-ene" click chemistry. Due to the large specific surface area of the hybrid matrix and the simplicity, rapidness and high efficiency of "thiol-ene" click reaction, the average coverage density of aptamer on the organic-silica hybrid monolith reached 420 pmol μL(-1). Human α-thrombin can be captured on the prepared affinity monolithic column with high specificity and eluted by NaClO4 solution. N-p-tosyl-Gly-Pro-Arg p-nitroanilide acetate was used as the sensitive chromogenic substrate of thrombin. The thrombin enriched by this affinity column was detected with a detection of limit of 0.01 μM by spectrophotometry. Furthermore, the extraction recovery of thrombin at 0.15 μM in human serum was 91.8% with a relative standard deviation of 4.0%. These results indicated that "thiol-ene" click chemistry provided a promising technique to immobilize aptamer on organic-inorganic hybrid monolith and the easily-assembled affinity monolithic material could be used to realize highly selective recognition of trace proteins.

  10. Effects of a Protic Ionic Liquid on the Reaction Pathway during Non-Aqueous Sol–Gel Synthesis of Silica: A Raman Spectroscopic Investigation

    Directory of Open Access Journals (Sweden)

    Anna Martinelli


    Full Text Available The reaction pathway during the formation of silica via a two-component “non-aqueou” sol-gel synthesis is studied by in situ time-resolved Raman spectroscopy. This synthetic route is followed with and without the addition of the protic ionic liquid 1-ethylimidazolium bis(trifluoromethanesulfonylimide (C2HImTFSI in order to investigate its effect on the reaction pathway. We demonstrate that Raman spectroscopy is suitable to discriminate between different silica intermediates, which are produced and consumed at different rates with respect to the point of gelation. We find that half-way to gelation monomers and shorter chains are the most abundant silica species, while the formation of silica rings strongly correlates to the sol-to-gel transition. Thus, curling up of linear chains is here proposed as a plausible mechanism for the formation of small rings. These in turn act as nucleation sites for the condensation of larger rings and thus the formation of the open and polymeric silica network. We find that the protic ionic liquid does not change the reaction pathway per se, but accelerates the cyclization process, intermediated by the faster inclusion of monomeric species.

  11. Mesoporous silica nanoparticles applied as a support for Pd and Au nanocatalysts in cycloisomerization reactions

    Directory of Open Access Journals (Sweden)

    Oscar Verho


    Full Text Available Ultra-small mesoporous silica nanoparticles (MSNs have been synthesized at room temperature with particle sizes ranging from 28 to 45 nm. These MSNs have been employed as heterogeneous supports for palladium and gold nanocatalysts. The colloidal nature of the MSNs is highly useful for catalytic applications as it allows for better mass transfer properties and a more uniform distribution of the nanocatalysts in solution. The two nanocatalysts were evaluated in the cycloisomerization of alkynoic acids and demonstrated to produce the corresponding alkylidene lactones in good to excellent yields under mild conditions. In addition to their high activity, the catalysts exhibit low degree of metal leaching and straight-forward recycling, which highlight the practical utility of MSNs as supports for nanocatalysts.

  12. RILEM recommendations for the prevention of damage by alkali-aggregate reactions in new concrete structures state-of-the-art report of the RILEM technical committee 219-ACS

    CERN Document Server

    Sims, Ian


    This book contains the full set of RILEM Recommendations which have been produced to enable engineers, specifiers and testing houses to design and produce concrete which will not suffer damage arising from alkali reactions in the concrete. There are five recommended test methods for aggregates (designated AAR-1 to AAR-5), and an overall recommendation which describes how these should be used to enable a comprehensive aggregate assessment (AAR-0). Additionally, there are two Recommended International Specifications for concrete (AAR-7.1 & 7.2) and a Preliminary International Specification for dams and other hydro structures (AAR-7.3), which describe how the aggregate assessment can be combined with other measures in the design of the concrete to produce a concrete with a minimised risk of developing damage from alkali-aggregate reactions.

  13. Comparison of mass loss rate in reaction of silica with carbon from different investigation results

    Directory of Open Access Journals (Sweden)

    J. Węgrzyn


    Full Text Available In the process of carbothermic reaction of SiO2 + mC, key reactions appear on the surfaces of both SiO2 and C grains. However, the values of these surfaces are not known. Assuming the simplest case, quartzite and carbon grains are spheres, total surfaces of reaction were calculated for grains of carbon and quartzite respectively. This enabled to determine the rate of weight loss referred to the unit area of C and SiO2.

  14. Preparation of different amides via Ritter reaction from alcohols and nitriles in the presence of silica-bonded N- propyl sulphamic acid (SBNPSA) under solvent-free conditions

    Indian Academy of Sciences (India)

    Maryam-Sadat Shakeri; Hassan Tajik; Khodabakhsh Niknam


    A number of methods have been proposed for the modification of the Ritter reaction. However, many of these methods involve the use of strongly acidic conditions, stoichiometric amounts of reagents, harsh reaction conditions and extended reaction times. Therefore, the development of mild, efficient, convenient and benign reagents for the Ritter reaction is desirable. In this research, we have developed a clean and environmentally friendly protocol for the synthesis of amides by using different benzylic or tertiary alcohols and different nitriles in the presence of silica-bonded N- propyl sulphamic acid (SBNPSA) as catalyst under solvent-free conditions in high yields.

  15. Expansive reactions in concrete observed by soft x-ray transmission microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kurtis, K.E.; Monteiro, P.J.M. [Univ. of California, Berkeley, CA (United States). Dept. of Civil and Environmental Engineering; Brown, J.T.; Meyer-Ilse, W. [Lawrence Berkeley National Lab., CA (United States). Center for X-ray Optics


    Alkali-silica reaction, sulfate attack, and reinforcing steel corrosion can compromise the long-term durability of concrete structures. The anticipated economic impact of an extensive infrastructure repair scheme has produced a renewed interest in the development of advanced characterization methods to assess the degree of deterioration in the concrete experiencing these deleterious reactions. The products of the alkali silica reaction, sulfate attack, and corrosion as well as the cement hydration products are extremely sensitive to humidity. Consequently, characterization techniques that require high vacuum or drying, as many existing techniques do, are not particularly appropriate for the study of these reactions in concrete as artifacts are introduced. A high resolution instrument which allows the examination of these reactions and their products without drying and at normal pressures will promote understanding of the reactions and provide further insight into means of mitigating the damage they cause. Only soft x-ray transmission microscopy provides the required high spatial resolution to observe the reaction process in situ. The alkali-silica reaction can be observed over time, in a wet condition, and at normal pressures, features unavailable with most other high resolution techniques. Soft x-rays also reveal information on the internal structure of the sample. This paper reviews published and ongoing applications of soft x-ray transmission microscopy for the study of expansive reactions that occur in concrete.

  16. Economic mixing of silica-rubber compounds : interaction between the chemistry of the silica-silane reaction and the physics of mixing

    NARCIS (Netherlands)

    Dierkes, Wilma Karola


    Within this thesis, a fundamental investigation of the mixing process of silica compounds is done, and the factors influencing the mixing and silanization efficiency are analyzed. However, the final aim of the work is a very practical one: The proposition of adjustments of the production process and

  17. TiO{sub 2} Coated Core-Shell Nanoparticles Fabricated through Sol-Gel Reaction of Titanium Precursor on Surface of Silica Core Templates

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Suk Bon [Korea Hydro and Nuclear Power Co. Ltd., Daejeon (Korea, Republic of)


    TiO{sub 2} hollow capsules have been mainly investigated through various methods using soft and hard templates such as polymer latex and silica nanoparticles (NPs). However, fabrication of these materials inevitably involves the removal process of polymer latex and silica template used through calcination at high temperature and etching with toxic etchants, respectively. As a result, these processes result in the generation of chemical waste as well as serious environmental concerns. To overcome above mentioned problems, although studies on in situ recrystallization transformation of silica into more useful functional nanostructured silica materials such as microporous zeolites or mesoporous silicas instead of removal of the silica templates were reported in recent, the additional process, including hydrothermal reaction and calcination at high temperature in the removal of the organic templates used is required to fabricate these materials. Resulting TiO{sub 2} coated core-shell NPs showed a smooth surface and uniform TiO{sub 2} shell layer. TiO{sub 2} shell layer after the calcination processes at high temperature under air flowing exhibited the crystal structure corresponding to the anatase phase. The formation of the TiO{sub 2} shell layer on the surface of the silica core templates was investigated through the various analyses. TiO{sub 2} shell layer after the calcination treatment at high temperature exhibited the anatase phase with a crystal size of ca. 5.37 nm. Resulting TiO{sub 2} coated core-shell NPs can be utilized as a photocatalyst.

  18. Silica-acac-supported palladium nanoparticles as an efficient and reusable heterogeneous catalyst in the Suzuki-Miyaura cross-coupling reaction in water

    Indian Academy of Sciences (India)

    Abdol Reza Hajipour; Zohre Shirdashtzade; Ghobad Azizi


    Supported Pd nanoparticles on acetyl acetone modified silica gel was prepared and its catalytic application in the Suzuki-Miyaura reaction of various aryl halides with phenylboronic acid was investigated. The reaction was carried out in water as solvent under green conditions in the presence of NaHCO3 as the base. The catalyst was characterized by a combination of powder XRD, XPS, TEM and SEM. The catalyst is not sensitive to air and moisture, so reactions were carried out without using inert atmosphere. The catalyst can be reused up to six times without significant loss of catalyst activity. The cumulative turnover number (TON) over six runs is 13525.

  19. Photoionization in alkali lasers. (United States)

    Knize, R J; Zhdanov, B V; Shaffer, M K


    We have calculated photoionization rates in alkali lasers. The photoionization of alkali atoms in the gain medium of alkali lasers can significantly degrade the laser performance by reducing the neutral alkali density and with it the gain. For a ten atmosphere Rb laser and a Cs exciplex laser, the photoionization induced alkali atom loss rates are greater than 10(5) sec(-1). These high loss rates will quickly deplete the neutral alkali density, reducing gain, and may require fast, possibly, supersonic flow rates to sufficiently replenish the neutral medium for CW operation.

  20. The central tower of the cathedral of Schleswig - New investigations to understand the alcali-silica reaction of historical mortars (United States)

    Wedekind, Wanja; Protz, Andreas


    The damaging alcali-silica reaction leads to crack-formation and structural destruction at noumerous, constructed with cement mortar, buildings worldwide. The ASR-reaction causes the expansion of altered aggregates by the formation of a swelling gel. This gel consists of calcium silicate hydrate (C-S-H) that increases in volume with water, which exerts an expansive pressure inside the material. The cathedral of Schleswig is one of the oldest in northern Germany. The first church was built in 985-965. The Romanesque building part was erected around 1180 and the Gothic nave at the end of the 13th century. The central tower was constructed between 1888 and 1894 with brick and cement mortar. With 112 meters, the tower is the second-largest church spire of the country of Schleswig-Holstein in northern Germany. Due to the formation of cracks and damages from 1953 to 1956 first restoration works took place. Further developments of cracks are making restoration necessary again today. For developing a suitable conservation strategy, different investigations were done. The investigation included the determination of the pore space properties, the hygric and thermal dilatation and mercury porosimetry measurements. Furthermore, the application of cathodoluminescence microscopy may give information about the alteration process and microstructures present and reveal the differences between unaltered and altered mortars. An obvious relation between the porosity and the swelling intensity could be detected. Furthermore it becomes apparent, that a clear zonation of the mortar took place. The mortar near the surface is denser with a lower porosity and has a significantly lower swelling or dilatation.

  1. Chapter K: Progress in the Evaluation of Alkali-Aggregate Reaction in Concrete Construction in the Pacific Northwest, United States and Canada (United States)

    Shrimer, Fred H.


    The supply of aggregates suitable for use in construction and maintenance of infrastructure in western North America is a continuing concern to the engineering and resources-management community. Steady population growth throughout the region has fueled demand for high-quality aggregates, in the face of rapid depletion of existing aggregate resources and slow and difficult permitting of new sources of traditional aggregate types. In addition to these challenges, the requirement for aggregates to meet various engineering standards continues to increase. In addition to their physical-mechanical properties, other performance characteristics of construction aggregates specifically depend on their mineralogy and texture. These properties can result in deleterious chemical reactions when aggregate is used in concrete mixes. When this chemical reaction-termed 'alkali-aggregate reaction' (AAR)-occurs, it can pose a major problem for concrete structures, reducing their service life and requiring expensive repair or even replacement of the concrete. AAR is thus to be avoided in order to promote the longevity of concrete structures and to ensure that public moneys invested in infrastructure are well spent. Because the AAR phenomenon is directly related to the mineral composition, texture, and petrogenesis of the rock particles that make up aggregates, an understanding of the relation between the geology and the performance of aggregates in concrete is important. In the Pacific Northwest, some aggregates have a moderate to high AAR potential, but many others have no or only a low AAR potential. Overall, AAR is not as widespread or serious a problem in the Pacific Northwest as in other regions of North America. The identification of reactive aggregates in the Pacific Northwest and the accurate prediction of their behavior in concrete continue to present challenges for the assessment and management of geologic resources to the owners and operators of pits and quarries and to the

  2. Milk-alkali syndrome (United States)

    ... this page: // Milk-alkali syndrome To use the sharing features on this page, please enable JavaScript. Milk-alkali syndrome is a condition in which there ...

  3. Sulfate Resistance of Alkali Activated Pozzolans


    Bondar, Dali


    The consequence of sulfate attack on geopolymer concrete, made from an alkali activated natural pozzolan (AANP) has been studied in this paper. Changes in the compressive strength, expansion and capillary water absorption of specimens have been investigated combined with phases determination by means of X-ray diffraction. At the end of present investigation which was to evaluate the performance of natural alumina silica based geopolymer concrete in sodium and magnesium sulfate solution, the l...

  4. Reaction pathway led by silicate structure transformation on decomposition of CaSiO3 in alkali fusion process using NaOH%NaOH碱熔分解CaSiO 3过程中导致硅酸盐结构转变的反应路径

    Institute of Scientific and Technical Information of China (English)

    赵昌明; 王国承; 李胜利; 艾新港; 王子睿; 翟玉春


    以NaSiO 3·9H 2 O和CaCl 2为原料,通过化学沉积法合成链状硅酸盐(CaSiO 3)。采用拉曼光谱、X射线衍射和红外光谱研究其在NaOH碱熔过程中的分解机制。结果表明,CaSiO 3在碱熔过程中链状结构的硅氧四面体结构逐渐断裂、转变生成岛状结构的硅氧四面体。CaSiO3分解过程中同时生成3种中间体:Ca2SiO4, Na2CaSiO4和Na2SiO3,最终产物是Ca(OH)2和 Na4SiO4。因此,CaSiO3在NaOH碱熔融反应过程中存在两条反应途径,分别以离子交换和硅酸盐骨架结构改变为主要形式,碱熔过程中硅酸盐结构的变化贯穿于整个反应过程。%The mechanism of decomposition of calcium inosilicate (CaSiO3) synthesized through chemical deposition method using analytical reagent NaSiO3∙9H2O and CaCl2 during the alkali fusion process using NaOH was investigated by Raman spectroscopy in situ, X-ray diffraction and Fourier transform infrared spectrometer (FTIR). The results show that the tetrahedral silica chains within CaSiO3 are gradually disrupted and transformed into nesosilicate with the isolated SiO4 tetrahedra at the beginning of the alkali fusion process. The three intermediates including Ca2SiO4, Na2CaSiO4 and Na2SiO3 appear simultaneously in the decomposition of CaSiO3, while the final products are Ca(OH)2 and Na4SiO4. It can be concluded that there exist two reaction pathways in the alkali fusion process of CaSiO3: one is ion exchange, the other is in the main form of the framework structure change of silicate. The reaction pathway is led by silicate structure transformation in the alkali fusion process.

  5. Discoid Bicelles as Efficient Templates for Pillared Lamellar Periodic Mesoporous Silicas at pH 7 and Ultrafast Reaction Times

    Directory of Open Access Journals (Sweden)

    Mohanty Paritosh


    Full Text Available Abstract We report the first synthesis of periodic mesoporous silicas templated by bicelles. The obtained materials form novel pillared lamellar structures with a high degree of periodic order, narrow pore size distributions, and exceptionally high surface areas.

  6. Improved Reactivity of Fly Ash-Slag Geopolymer by the Addition of Silica Fume

    Directory of Open Access Journals (Sweden)

    N. K. Lee


    Full Text Available This study investigates the improved reactivity of a geopolymer based on a combination of fly ash and blast furnace slag (BFS by the addition of silica fume. The geopolymer was synthesized by activating a mixture of fly ash, BFS, and three different types of silica fume with alkali activator. X-ray diffraction (XRD and inductively coupled plasma-optical emission spectroscopy (ICP-OES were utilized to characterize the reaction. The silicate structure was also analyzed by nuclear magnetic resonance (NMR spectroscopy. From these results, it was found that the replacement of fly ash with the silica fume led to a significant decrease in the Q4(1Al and an increase in the Q4(2Al, Q4(3Al, and Q4(4Al. The Si/Al ratio of the aluminosilicate gel was relatively constant, ranging from 2.0 to 2.6, while the Si/Al ratio of the C-S-H gel increased with the addition of silica fume. Therefore, some of the Al dissolved from the slag contributed to the formation of aluminosilicate gel, and the remnant slag particles mostly participated in the formation of the C-(A-S-H gel with a decrease in the Q2(1Al. The increase in the reactivity of slag caused by the addition of silica fume was attributed to the reaction of the Al in the slag with the silica fume.

  7. PVDF-HFP/silica-SH nanocomposite synthesis for PEMFC membranes through simultaneous one-step sol–gel reaction and reactive extrusion

    Energy Technology Data Exchange (ETDEWEB)

    Seck, S. [Université de Lyon, Université Lyon 1, UMR CNRS 5223 Ingénierie des Matériaux Polymères, IMP@Lyon1, Bât PolyTech, 15 Boulevard Latarjet, 69622 Villeurbanne Cedex (France); Université de Lyon, INSA, UMR CNRS 5223 Ingénierie des Matériaux Polymères IMP@INSA, Batîment Jules Verne, 17 avenue Jean Capelle, 69621 Villeurbanne Cedex (France); Magana, S. [Université de Lyon, Université Lyon 1, UMR CNRS 5223 Ingénierie des Matériaux Polymères, IMP@Lyon1, Bât PolyTech, 15 Boulevard Latarjet, 69622 Villeurbanne Cedex (France); Prébé, A.; Niepceron, F. [Université de Lyon, Université Lyon 1, UMR CNRS 5223 Ingénierie des Matériaux Polymères, IMP@Lyon1, Bât PolyTech, 15 Boulevard Latarjet, 69622 Villeurbanne Cedex (France); Université de Lyon, INSA, UMR CNRS 5223 Ingénierie des Matériaux Polymères IMP@INSA, Batîment Jules Verne, 17 avenue Jean Capelle, 69621 Villeurbanne Cedex (France); and others


    In this study, synthesis of thiol-functionalized silica/PVDF-HFP [poly(vinylidene fluoride-hexafluoropropylene)] nanocomposite materials was carried out by reactive extrusion through in situ sol–gel reactions of an alkoxysilane inorganic precursor solution composed of polydimethoxysiloxane (PDMOS) and mercaptopropyltriethoxysilane (MPTES). Successful introduction of the functional MPTES and structural PDMOS alkoxysilanes, and subsequent condensation reactions in the PVDF-HFP, were obtained through pre-hydrolysis reactions of the precursors. {sup 29}Si-Nuclear magnetic resonance was used to assess the hydrolysis level of the inorganic precursor solution and condensation state in the resulting PVDF-HFP/functionalized silica nanocomposites, while the morphology was observed using scanning electron microscopy (SEM). The hydrolysis-condensation reactions resulting in the inorganic phase were optimized by setting an appropriate R{sub 0} molar ratio (H{sub 2}O/alkoxy function), R{sub 1} molar ratio (MPTES/PDMOS) and pH of the solution. Increasing the R{sub 0} ratio barely affected the hydrolysis kinetics. However, a higher R{sub 1} ratio led to a decrease in the inorganic precursors condensation state and consequently to an increase in the reaction time in the extruder to reach the subsequent condensation state. Hence the morphology of the obtained nanocomposites was finer for the highest R{sub 1} ratio and in agreement with the evolution of the solubility parameters. Promising ionic exchange capacity (IEC) and conductivity values were obtained for these innovative nanocomposite materials thanks to a controlled oxidation reaction of the thiol groups into sulfonic acid functions. This original approach demonstrated the possibility of incorporating in situ functionalized silica into a molten fluorinated polymer matrix in a unique reactive extrusion procedure. - Highlights: • Thiol-functionalized silica/PVDF-HFP nanocomposite synthesis by sol–gel and extrusion.

  8. The Effectiveness of High Quality Supplementary Cementitious Materials for Mitigating ASR Expansion in Concrete with High Alkali Content

    Directory of Open Access Journals (Sweden)

    I. Prasetia


    Full Text Available Alkali silica reaction (ASR is influenced by external factors such as the surrounding environment of high alkalinity. Countries with cold climate have a high probability to be exposed to high concentrations of NaCl solution by the deicing salt. This condition will lead to serious ASR problems in concrete, if the aggregates contain reactive silica. The main research work in this paper is to investigate the effect of 15% replacement ratio of high quality fine fly ash (FA15% and 42% replacement ratio of blast furnace slag (BFS42% on the ASR mitigation in concrete with different alkali amount inside the pore solution. The experiments were conducted according to the accelerated mortar bars experiment following the JIS A1146 mortar bar test method. In addition, post-analysis such as observation of ASR gel formation by the Uranyl Acetate Fluorescence Method and observation of thin sections using a Polarizing Microscope were also conducted. The mortar bar tests show a very good mitigation effect of supplementary cementitious materials (SCMs. The results show that only small ASR expansions, which can be categorized as “innocuous”, occurred for specimens with 1.2% Na2Oeq using FA15% and BFS42%. However, larger alkali amount inside the system will require more SCMs amount.

  9. Enzymatic hydrolysate-induced displacement reaction with multifunctional silica beads doped with horseradish peroxidase-thionine conjugate for ultrasensitive electrochemical immunoassay. (United States)

    Lin, Youxiu; Zhou, Qian; Lin, Yuping; Tang, Dianping; Niessner, Reinhard; Knopp, Dietmar


    A novel (invertase) enzymatic hydrolysate-triggered displacement reaction strategy with multifunctional silica beads, doped with horseradish peroxidase-thionine (HRP-Thi) conjugate, was developed for competitive-type electrochemical immunoassay of small molecular aflatoxin B1 (AFB1). The competitive-type displacement reaction was carried out on the basis of the affinity difference between enzymatic hydrolysate (glucose) and its analogue (dextran) for concanavalin A (Con A) binding sites. Initially, thionine-HRP conjugates were doped into nanometer-sized silica beads using the reverse micelle method. Then monoclonal anti-AFB1 antibody and Con A were covalently conjugated to the silica beads. The immunosensor was prepared by means of immobilizing the multifunctional silica beads on a dextran-modified sensing interface via the dextran-Con A binding reaction. Gold nanoparticles functionalized with AFB1-bovine serum albumin conjugate (AFB1-BSA) and invertase were utilized as the trace tag. Upon target AFB1 introduction, a competitive-type immunoreaction was implemented between the analyte and the labeled AFB1-BSA on the nanogold particles for the immobilized anti-AFB1 antibody on the electrode. The invertase followed by gold nanoparticles hydrolyzed sucrose into glucose and fructose. The produced glucose displaced the multifunctional silica beads from the electrode based on the classical dextran-Con A-glucose system, thus decreasing the catalytic efficiency of the immobilized HRP on the electrode relative to that of the H2O2-thionine system. Under optimal conditions, the detectable electrochemical signal increased with the increasing target AFB1 in a dynamic working range from 3.0 pg mL(-1) to 20 ng mL(-1) with a detection limit of 2.7 pg mL(-1). The strong bioconjugation with two nanostructures also resulted in a good repeatability and interassay precision down to 9.3%. Finally, the methodology was further validated for analysis of naturally contaminated or spiked AFB1

  10. Chromo- and fluorophoric water-soluble polymers and silica particles by nucleophilic substitution reaction of poly(vinyl amine)


    Katja Hofmann; Ingolf Kahle; Frank Simon; Stefan Spange


    Novel chromophoric and fluorescent carbonitrile-functionalized poly(vinyl amine) (PVAm) and PVAm/silica particles were synthesized by means of nucleophilic aromatic substitution of 8-oxo-8H-acenaphtho[1,2-b]pyrrol-9-carbonitrile (1) with PVAm in water. The water solubility of 1 has been mediated by 2,6-O-β-dimethylcyclodextrin or by pre-adsorption onto silica particles. Furthermore, 1 was converted with isopropylamine into the model compound 1-M. All new compounds were characterized by N...

  11. Synthetic aspects and characterization of polypropylene–silica nanocomposites prepared via solid-state modification and sol–gel reactions

    NARCIS (Netherlands)

    Jain, Sachin; Goossens, Han; Picchioni, Francesco; Magusin, Pieter; Mezari, Brahim; Duin, Martin van


    A new route is developed by combining solid-state modification (SSM) by grafting vinyl triethoxysilane (VTES) with a sol–gel method to prepare PP/silica nanocomposites with varying degree of adhesion between filler and matrix. VTES was grafted via SSM in porous PP particles. Bulk polymerization unde

  12. Synthetic aspects and characterization of polypropylene-silica nanocomposites prepared via solid-state modification and sol-gel reactions

    NARCIS (Netherlands)

    Jain, S; Goossens, H; Picchioni, F; Magusin, P; Mezari, B


    A new route is developed by combining solid-state modification (SSM) by grafting vinyl triethoxysilane (VTES) with a sol-gel method to prepare PP/silica nanocomposites with varying degree of adhesion between filler and matrix. VTES was grafted via SSM in porous PP particles. Bulk polymerization unde

  13. Chromo- and fluorophoric water-soluble polymers and silica particles by nucleophilic substitution reaction of poly(vinyl amine

    Directory of Open Access Journals (Sweden)

    Katja Hofmann


    Full Text Available Novel chromophoric and fluorescent carbonitrile-functionalized poly(vinyl amine (PVAm and PVAm/silica particles were synthesized by means of nucleophilic aromatic substitution of 8-oxo-8H-acenaphtho[1,2-b]pyrrol-9-carbonitrile (1 with PVAm in water. The water solubility of 1 has been mediated by 2,6-O-β-dimethylcyclodextrin or by pre-adsorption onto silica particles. Furthermore, 1 was converted with isopropylamine into the model compound 1-M. All new compounds were characterized by NMR, FTIR, UV–vis and fluorescence spectroscopy. The solvent-dependent UV–vis absorption and fluorescence emission band positions of the model compound and the carbonitrile-functionalized PVAm were studied and interpreted using the empirical Kamlet–Taft solvent parameters π* (dipolarity/polarizability, α (hydrogen-bond donating capacity and β (hydrogen-accepting ability in terms of the linear solvation energy relationship (LSER. The solvent-independent regression coefficients a, b and s were determined using multiple linear correlation analysis. It is shown, that the chains of the polymer have a significant influence on the solvatochromic behavior of 1-P. The structure of the carbonitrile 1-Si bound to polymer-modified silica particles was studied by means of X-ray photoelectron spectroscopy (XPS and Brunauer–Emmett–Teller (BET measurements. Fluorescent silica particles were obtained as shown by fluorescence spectroscopy with a diffuse reflectance technique.

  14. Bifunctional heterogeneous catalysis of silica-alumina-supported tertiary amines with controlled acid-base interactions for efficient 1,4-addition reactions. (United States)

    Motokura, Ken; Tanaka, Satoka; Tada, Mizuki; Iwasawa, Yasuhiro


    We report the first tunable bifunctional surface of silica-alumina-supported tertiary amines (SA-NEt(2)) active for catalytic 1,4-addition reactions of nitroalkanes and thiols to electron-deficient alkenes. The 1,4-addition reaction of nitroalkanes to electron-deficient alkenes is one of the most useful carbon-carbon bond-forming reactions and applicable toward a wide range of organic syntheses. The reaction between nitroethane and methyl vinyl ketone scarcely proceeded with either SA or homogeneous amines, and a mixture of SA and amines showed very low catalytic activity. In addition, undesirable side reactions occurred in the case of a strong base like sodium ethoxide employed as a catalytic reagent. Only the present SA-supported amine (SA-NEt(2)) catalyst enabled selective formation of a double-alkylated product without promotions of side reactions such as an intramolecular cyclization reaction. The heterogeneous SA-NEt(2) catalyst was easily recovered from the reaction mixture by simple filtration and reusable with retention of its catalytic activity and selectivity. Furthermore, the SA-NEt(2) catalyst system was applicable to the addition reaction of other nitroalkanes and thiols to various electron-deficient alkenes. The solid-state magic-angle spinning (MAS) NMR spectroscopic analyses, including variable-contact-time (13)C cross-polarization (CP)/MAS NMR spectroscopy, revealed that acid-base interactions between surface acid sites and immobilized amines can be controlled by pretreatment of SA at different temperatures. The catalytic activities for these addition reactions were strongly affected by the surface acid-base interactions.

  15. One-Pot and Efficient Synthesis of Triazolo[1,2-a]indazole-triones via Reaction of Arylaldehydes with Urazole and Dimedone Catalyzed by Silica Nanoparticles Prepared from Rice Husk


    Asadollah Hassankhani; Sayed Zia Mohammadi; Hooshang Hamidian; Samieh Fozooni


    A novel synthesis of triazolo[1,2-a]indazole-1,3,8-trione derivatives by reaction of urazole, dimedone and aromatic aldehydes under conventional heating and microwave irradiation and solvent-free conditions using silica nanoparticles prepared from rice husk ash as catalyst is described. The new method features high yields, multicomponent reactions and environmental friendliness.

  16. One-Pot and Efficient Synthesis of Triazolo[1,2-a]indazole-triones via Reaction of Arylaldehydes with Urazole and Dimedone Catalyzed by Silica Nanoparticles Prepared from Rice Husk

    Directory of Open Access Journals (Sweden)

    Asadollah Hassankhani


    Full Text Available A novel synthesis of triazolo[1,2-a]indazole-1,3,8-trione derivatives by reaction of urazole, dimedone and aromatic aldehydes under conventional heating and microwave irradiation and solvent-free conditions using silica nanoparticles prepared from rice husk ash as catalyst is described. The new method features high yields, multicomponent reactions and environmental friendliness.

  17. One-pot and efficient synthesis of triazolo[1,2-a]indazole-triones via reaction of arylaldehydes with urazole and dimedone catalyzed by silica nanoparticles prepared from rice husk. (United States)

    Hamidian, Hooshang; Fozooni, Samieh; Hassankhani, Asadollah; Mohammadi, Sayed Zia


    A novel synthesis of triazolo[1,2-a]indazole-1,3,8-trione derivatives by reaction of urazole, dimedone and aromatic aldehydes under conventional heating and microwave irradiation and solvent-free conditions using silica nanoparticles prepared from rice husk ash as catalyst is described. The new method features high yields, multicomponent reactions and environmental friendliness.

  18. Alkali cation specific adsorption onto fcc(111) transition metal electrodes. (United States)

    Mills, J N; McCrum, I T; Janik, M J


    The presence of alkali cations in electrolyte solutions is known to impact the rate of electrocatalytic reactions, though the mechanism of such impact is not conclusively determined. We use density functional theory (DFT) to examine the specific adsorption of alkali cations to fcc(111) electrode surfaces, as specific adsorption may block catalyst sites or otherwise impact surface catalytic chemistry. Solvation of the cation-metal surface structure was investigated using explicit water models. Computed equilibrium potentials for alkali cation adsorption suggest that alkali and alkaline earth cations will specifically adsorb onto Pt(111) and Pd(111) surfaces in the potential range of hydrogen oxidation and hydrogen evolution catalysis in alkaline solutions.

  19. FTIR Analysis of Alkali Activated Slag and Fly Ash Using Deconvolution Techniques (United States)

    Madavarapu, Sateesh Babu

    The studies on aluminosilicate materials to replace traditional construction materials such as ordinary Portland cement (OPC) to reduce the effects caused has been an important research area for the past decades. Many properties like strength have already been studied and the primary focus is to learn about the reaction mechanism and the effect of the parameters on the formed products. The aim of this research was to explore the structural changes and reaction product analysis of geopolymers (Slag & Fly Ash) using Fourier transform infrared spectroscopy (FTIR) and deconvolution techniques. Spectroscopic techniques give valuable information at a molecular level but not all methods are economic and simple. To understand the mechanisms of alkali activated aluminosilicate materials, attenuated total reflectance (ATR) FTIR has been used where the effect of the parameters on the reaction products have been analyzed. To analyze complex systems like geopolymers using FTIR, deconvolution techniques help to obtain the properties of a particular peak attributed to a certain molecular vibration. Time and temperature dependent analysis were done on slag pastes to understand the polymerization of reactive silica in the system with time and temperature variance. For time dependent analysis slag has been activated with sodium and potassium silicates using two different `n'values and three different silica modulus [Ms- (SiO2 /M2 O)] values. The temperature dependent analysis was done by curing the samples at 60°C and 80°C. Similarly fly ash has been studied by activating with alkali hydroxides and alkali silicates. Under the same curing conditions the fly ash samples were evaluated to analyze the effects of added silicates for alkali activation. The peak shifts in the FTIR explains the changes in the structural nature of the matrix and can be identified using the deconvolution technique. A strong correlation is found between the concentrations of silicate monomer in the

  20. Synthesis of nanosilica from silica fume using an acid-base precipitation technique and PVA as a nonionic surfactant

    Directory of Open Access Journals (Sweden)

    Vajihe Jafari


    Full Text Available The purpose of the present study was to synthesize and characterize nanosilica from alkali-extraction of silica fume under controlled conditions using poly (vinyl alcohol (PVA as a dispersing agent. The dissolution efficiency of silica fume was affected by various factors such as concentration of the reagent, reaction time and temperature. A maximum dissolution efficiency of 91% was achieved at the sodium hydroxide solution concentration of 2.5 M, after areaction time of 30 minutes and at areaction temperature of 80°C. The microstructure and morphology of the obtained nanosilica powder at the optimum conditions were characterized using scanning electron microscopy (SEM. SEM images confirmed the formation of smaller and less agglomerated nanosilica particles due to the existence of the surfactant. Further, the synthesized nanosilica was characterized by Fourier transform infrared (FTIR spectroscopy, X-ray diffractometry (XRF and X-ray diffraction (XRD. The results show that the synthesized nanosilica consisted of pure silica particles.

  1. Microstructure Assessment of Metakaolin Based-Geopolymers Produced with Alternative Silica Sources Exposed to High Temperatures

    Directory of Open Access Journals (Sweden)

    Villaquirán-Caicedo Mónica Alejandra


    Full Text Available Ceramic materials more environment friendly and with similar or even better performance than traditional ones can be produced by alkali activation of natural minerals, wastes or industrial by-products. The present study assesses the effect of exposure at 600° and 1200°C of a MK-based geopolymers. Rice husk ash (RHA and silica fume were modified chemically in order to obtain an alternative alkali activator. Exposure to elevated temperatures leads to dehydration of the reaction products and structural reorganization associated with the crystallization of the gel to leucite (KAlSi2O6 and kalsilite (KAlSiO4. The structural changes associated with the thermal treatment also promote a densification and reduction of porosity. The unreacted MK particles embedded into the geopolymeric gel lead to the formation of mullite (2Al2O3 × SiO2 after the thermal treatment at 1200°C.

  2. A kinetic study on the adsorption and reaction of hydrogen over silica-supported ruthenium and silver-ruthenium catalysts during the hydrogenation of carbon monoxide

    Energy Technology Data Exchange (ETDEWEB)

    VanderWiel, D.P.


    Although the catalytic hydrogenation of carbon monoxide has been a subject of considerable investigation for many years, its increasing economical attractiveness as an industrial source of hydrocarbons has recently led to a search for more active and selective catalysts. A fundamental problem in the development of such catalysts is an incomplete knowledge of the operative surface processes, due in large part to the inability to accurately measure surface concentrations of reactant species during reaction. Specifically, the concentration of surface hydrogen proves difficult to estimate using normally revealing techniques such as transient isotopic exchange due to kinetic isotope effects. Knowledge of such concentrations is essential to the determination of the mechanisms of adsorption and reaction, since many kinetic parameters are concentration dependent. It is the aim of this research to investigate the mechanism and kinetics of the adsorption and reaction of hydrogen on silica-supported ruthenium and silver-ruthenium catalysts during the hydrogenation of carbon monoxide. By preadsorbing carbon monoxide onto the surface of ruthenium and silver-ruthenium catalysts, the kinetics of hydrogen adsorption and reaction can be monitored upon exposure of this surface to ambient hydrogen gas. This is accomplished by conducting identical experiments on two separate systems. First, the formation of methane is monitored using mass spectroscopy, and specific reaction rates and apparent activation energies are measured. Next, in situ {sup 1}H-NMR is used to monitor the amount of hydrogen present on the catalyst surface during adsorption and reaction. The results for these two sets of experiments are then combined to show a correlation between the rate of reaction and the surface hydrogen concentration. Finally, transition state theory is applied to this system and is used to explain the observed change in the apparent activation energy. The structure sensitivity of hydrogen

  3. Synthesis of Magnetic Rattle-Type Silica with Controllable Magnetite and Tunable Size by Pre-Shell-Post-Core Method. (United States)

    Chen, Xue; Tan, Longfei; Meng, Xianwei


    In this study, we have developed the pre-shell-post-core route to synthesize the magnetic rattle-type silica. This method has not only simplified the precursor's process and reduced the reacting time, but also ameliorated the loss of magnetite and made the magnetite content and the inner core size controllable and tunable. The magnetite contents and inner core size can be easily controlled by changing the type and concentration of alkali, reaction system and addition of water. The results show that alkali aqueous solution promotes the escape of the precursor iron ions from the inner space of rattle-type silica and results in the loss of magnetite. In this case, NaOH ethanol solution is better for the formation of magnetite than ammonia because it not only offers an appropriate alkalinity to facilitate the synthesis of. magnetic particles, but also avoids the escape of the iron ions from the mesopores of rattle-type silica. The synthesis process is very simple and efficient, and it takes no more than 2 hours to complete the total preparation and handling of the magnetic rattle-type silica. The end-product Fe3O4@SiO2 nanocomposites also have good magnetic properties which will perform potential application in biomedical science.

  4. Inhibition of the polymerase chain reaction by sputum samples from tuberculosis patients after processing using a silica-guanidiniumthiocyanate DNA isolation procedure

    Directory of Open Access Journals (Sweden)

    Philip Suffys


    Full Text Available With the objective to evaluate PCR-mediated detection of Mycobacterium tuberculosis DNA as a diagnostic procedure for diagnosis of tuberculosis in individuals attending ambulatory services in Primary Health Units of the City Tuberculosis Program in Rio de Janeiro, Brazil, their sputum samples were collected and treated with a DNA extraction procedure using silica-guanidiniumthiocyanate. This procedure has been described to be highly efficient for extraction of different kind of nucleic acids from bacteria and clinical samples. Upon comparing PCR results with the number of acid-fast bacilli, no direct relation was observed between the number of bacilli present in the sample and PCR positivity. Part of the processed samples was therefore spiked with pure DNA of M. tuberculosis and inhibition of the PCR reaction was verified in 22 out of 36 (61% of the samples, demonstrating that the extraction procedure as originally described should not be used for PCR analysis of sputum samples.

  5. Evidências da formação de monocamada de óxido de alumínio sobre sílica, através de reações de enxerto Evidence of aluminum oxide monolayer formation on a silica gel surface using grafting reactions

    Directory of Open Access Journals (Sweden)

    Julia M. D. Cónsul


    Full Text Available Aluminum oxide was dispersed on a commercial silica gel surface, using successive grafting reactions. The reaction products were characterized by N2 adsorption-desorption isotherms, scanning electron microscopy and infrared spectroscopy. The progressive incorporation of aluminum, up to 5.5% (w/w, does not produce agglomeration of alumina, since changes in the original pore size distribution of the silica matrix were not observed. The aluminum oxide covers homogeneously the silica surface.

  6. Alkali promotion of N-2 dissociation over Ru(0001)

    DEFF Research Database (Denmark)

    Mortensen, Jens Jørgen; Hammer, Bjørk; Nørskov, Jens Kehlet


    Using self-consistent density functional calculations, we show that adsorbed Na and Cs lower the barrier for dissociation of N2 on Ru(0001). Since N2 dissociation is a crucial step in the ammonia synthesis reaction, we explain in this way the experimental observation that alkali metals promote...... the ammonia synthesis reaction over Ru catalysts. We also show that the origin of this effect is predominantly a direct electrostatic attraction between the adsorbed alkali atoms and the dissociating molecule....

  7. Reaction and surface characterization study of higher alcohol synthesis catalysts. 9: Pd- and alkali-promoted Zn/Cr-based spinels containing excess ZnO

    Energy Technology Data Exchange (ETDEWEB)

    Minahan, D.M. [Union Carbide Corp., South Charleston, WV (United States); Epling, W.S.; Hoflund, G.B. [Univ. of Florida, Gainesville, FL (United States). Dept. of Chemical Engineering


    A Zn/Cr spinel support material was prepared which contains excess ZnO and then was promoted with 5.9 wt% Pd and varying amounts ranging from 0 to 7 wt % of either K or Cs. Each of these catalysts were tested at four different reactor operating conditions (T of 400 or 440 C and P of 1000 or 1500 psig) for higher alcohol synthesis (HAS) using a syngas feedstream (1:1 CO:H{sub 2}) after reductive pretreatment. High isobutanol production rates in conjunction with low methanol-to-isobutanol mole ratios ({le}1.0) and low hydrocarbon byproduct rates are desired. For the K-promoted catalysts the highest isobutanol production rates are obtained at the higher pressure and temperature settings of 1500 psig and 440 C, and methanol-to-isobutanol mole ratios below the ideal value of 1.0, which is required for downstream methyl tertiary-butyl ether (MTBE) synthesis, are obtained. The Cs-promoted catalysts generally yield higher isobutanol production rates than the K-promoted catalysts. The highest isobutanol production rate of 170 g/kg-h is obtained using the 3 wt% Cs-promoted catalyst at 1000 psig and 440 C. The lower pressure is economically advantageous with regard to process costs. Most importantly, this isobutanol production rate is quite high compared to others presented in the literature and demonstrates that Pd does enhance the synthesis of isobutanol. The catalytic activity remained stable over a 5-day test period for each catalyst. X-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS) were used to characterize these catalysts. The results obtained from these techniques indicate that pretreating the catalysts in 1 {times} 10{sup {minus}7} Torr of H{sub 2} at 300 C for 4 h causes an enrichment of the near-surface alkali-promotor concentration.

  8. Ruthenium carbenes supported on mesoporous silicas as highly active and selective hybrid catalysts for olefin metathesis reactions under continuous flow. (United States)

    Bru, Miriam; Dehn, Richard; Teles, J Henrique; Deuerlein, Stephan; Danz, Manuel; Müller, Imke B; Limbach, Michael


    In the search for a highly active and selective heterogenized metathesis catalyst, we systematically varied the pore geometry and size of various silica-based mesoporous (i.e., MCM-41, MCM-48, and SBA-15) and microporous (ZSM-5 and MWW) versus macroporous materials (D11-10 and Aerosil 200), besides other process parameters (temperature, dilution, and mean residence time). The activity and, especially, selectivity of such "linker-free" supports for ruthenium metathesis catalysts were evaluated in the cyclodimerization of cis-cyclooctene to form 1,9-cyclohexadecadiene, a valuable intermediate in the flavor and fragrance industry. The optimized material showed not only exceptionally high selectivity to the valuable product, but also turned out to be a truly heterogeneous catalyst with superior activity relative to the unsupported homogeneous complex.

  9. Isolation and Characterization of Well-Defined Silica-Supported Azametallacyclopentane: A Key Intermediate in Catalytic Hydroaminoalkylation Reactions

    KAUST Repository

    Hamzaoui, Bilel


    Intermolecular catalytic hydroaminoalkylation of unactivated alkene occurs with silica-supported azazirconacyclopropane [[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)(η2-NMeCH2)(NMe2)]. Mechanistic studies were conducted using surface organometallic chemistry (SOMC) concepts to identify the key surface intermediates. The azametallacyclopentene intermediate {[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)[η2-NMeCH2CH(Me)CH2](NMe2)} was isolated after treating with 1-propylene and characterized by FT-IR spectroscopy, elemental analysis, 1H 13C HETCOR, DARR SS-NMR and DQ TQ SS-NMR. The regeneration of the catalyst was conducted by dimethylamine protonolysis to yield the pure amine.

  10. Optimization of o-phtaldialdehyde/2-mercaptoethanol postcolumn reaction for the hydrophilic interaction liquid chromatography determination of memantine utilizing a silica hydride stationary phase. (United States)

    Douša, Michal; Pivoňková, Veronika; Sýkora, David


    A rapid procedure for the determination of memantine based on hydrophilic interaction chromatography with fluorescence detection was developed. Fluorescence detection after postcolumn derivatization with o-phtaldialdehyde/2-mercaptoethanol was performed at excitation and emission wavelengths of 345 and 450 nm, respectively. The postcolumn reaction conditions such as reaction temperature, derivatization reagent flow rate, and reagents concentration were studied due to steric hindrance of amino group of memantine. The derivatization reaction was applied for the hydrophilic interaction liquid chromatography method which was based on Cogent Silica-C stationary phase with a mobile phase consisting of a mixture of 10 mmol/L citric acid and 10 mmol/L o-phosphoric acid (pH 6.0) with acetonitrile using an isocratic composition of 2:8 v/v. The benefit of the reported approach consists in a simple sample pretreatment and a quick and sensitive hydrophilic interaction chromatography method. The developed method was validated in terms of linearity, accuracy, precision, and selectivity according to the International Conference on Harmonisation guidelines. The developed method was successfully applied for the analysis of commercial memantine tablets.

  11. A rapid method for the detection of foodborne pathogens by extraction of a trace amount of DNA from raw milk based on label-free amino-modified silica-coated magnetic nanoparticles and polymerase chain reaction (United States)

    A method based on amino-modified silica-coated magnetic nanoparticles (ASMNPs) and polymerase chain reaction (PCR) was developed to rapidly and sensitively detect foodborne pathogens in raw milk. After optimizing parameters such as pH, temperature, and time, a trace amount of genomic DNA of pathogen...

  12. (abstract) Fundamental Mechanisms of Electrode Kinetics and Alkali Metal Atom Transport at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary (United States)

    Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Underwood, M. L.; O'Connor, D.; Kisor, A.; Kikkert, S. K.


    The mechanisms of electrode kinetics and mass transport of alkali metal oxidation and alkali metal cation reduction at the solid electrolyte/porous electrode boundary as well as alkali metal transport through porous metal electrodes has important applications in optimizing device performance in alkali metal thermal to electric converter (AMTEC) cells which are high temperature, high current density electrochemical cells. Basic studies of these processes also affords the opportunity to investigate a very basic electrochemical reaction over a wide range of conditions; and a variety of mass transport modes at high temperatures via electrochemical techniques. The temperature range of these investigations covers 700K to 1240K; the alkali metal vapor pressures range from about 10(sup -2) to 10(sup 2) Pa; and electrodes studied have included Mo, W, Mo/Na(sub 2)MoO(sub 4), W/Na(sub 2)WO(sub 4), WPt(sub x), and WRh(sub x) (1.0 alkali metal vapor and alkali metal vapor/solid electrolyte/vapor cells have been used to characterize the reaction and transport processes. We have previously reported evidence of ionic, free molecular flow, and surface transport of sodium in several types of AMTEC electrodes.

  13. Performance of concrete incorporating colloidal nano-silica (United States)

    Zeidan, Mohamed Sabry

    Nanotechnology, as one of the most modern fields of science, has great market potential and economic impact. The need for research in the field of nanotechnology is continuously on the rise. During the last few decades, nanotechnology was developing rapidly into many fields of applied sciences, engineering and industrial applications, especially through studies of physics, chemistry, medicine and fundamental material science. These new developments may be attributed to the fact that material properties and performance can be significantly improved and controlled through nano-scale processes and nano-structures. This research program aims at 1) further understanding the behavior of cementitious materials when amended on the nano-scale level and 2) exploring the effect of this enhancement on the microstructure of cement matrix. This study may be considered as an important step towards better understanding the use of nano-silica in concrete. The main goal of the study is to investigate the effect of using colloidal nano-silica on properties of concrete, including mechanical properties, durability, transport properties, and microstructure. The experimental program that was conducted included a laboratory investigation of concrete mixtures in which nano-silica was added to cement or to a combination of cement and Class F fly ash. Various ratios of nano-silica were used in concrete mixtures to examine the extent and types of improvements that could be imparted to concrete. The conducted experimental program assessed these improvements in terms of reactivity, mechanical properties, and durability of the mixtures under investigation. Advanced testing techniques---including mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM)---were used to investigate the effect of nano-silica on the microstructure of the tested mixtures. In addition, the effect of nano-silica on the alkali-silica reaction (ASR) was examined using various techniques, including testing

  14. Validity of bioconjugated silica nanoparticles in comparison with direct smear, culture, and polymerase chain reaction for detection of Mycobacterium tuberculosis in sputum specimens

    Directory of Open Access Journals (Sweden)

    Ekrami A


    Full Text Available Alireza Ekrami1, Ali Reza Samarbaf-Zadeh2, Azar Khosravi1, Behrooz Zargar3, Mohamad Alavi1, Mansor Amin2, Alireza Kiasat3 1Infectious and Tropical Diseases Research Center, Ahvaz Jundishapur University of Medical Sciences, 2Department of Microbiology, School of Medicine, Ahvaz Jundishapur University of Medical Sciences, 3Department of Chemistry, School of Science, Shahid Chamran University, Ahvaz, Iran Background: Tuberculosis is a public health problem worldwide, and new easy to perform diagnostic methods with high accuracy are necessary for optimal control of the disease. Recently, fluorescent silica nanoparticles (FSNP has attracted immense interest for the detection of pathogenic microorganisms. The aim of this study was to detect Mycobacterium tuberculosis in clinical samples using bioconjugated FSNP compared with microscopic examination, polymerase chain reaction (PCR, nested PCR, and culture as the gold standard. Methods: In total, 152 sputum specimens were obtained from patients who were suspected to have pulmonary tuberculosis. All samples were examined by the four techniques described. Results: The assay showed 97.1% sensitivity (95% confidence interval [CI] 91–99.2 and 91.35% specificity (CI 78.3–97.1. Furthermore, assays using variable bacterial concentrations indicated that 100 colony forming units/mL of M. tuberculosis could be detected. There were no differences between the results obtained from two types of mouse monoclonal antibody against Hsp-65 and 16 KDa antigens. Conclusion: We performed this assay in a large number of clinical samples to confirm the diagnostic specificity and sensitivity of the test and can recommend its application for diagnosis of M. tuberculosis. We believe that this method is more convenient for routine diagnosis of M. tuberculosis in sputum and will be more easily applicable in the field, and with sufficient sensitivity. Keywords: Mycobacterium tuberculosis, fluorescent silica nanoparticles

  15. Pair natural orbital and canonical coupled cluster reaction enthalpies involving light to heavy alkali and alkaline earth metals: the importance of sub-valence correlation

    KAUST Repository

    Minenkov, Yury


    In this work, we tested canonical and domain based pair natural orbital coupled cluster methods (CCSD(T) and DLPNO-CCSD(T), respectively) for a set of 32 ligand exchange and association/dissociation reaction enthalpies involving ionic complexes of Li, Be, Na, Mg, Ca, Sr, Ba and Pb(ii). Two strategies were investigated: in the former, only valence electrons were included in the correlation treatment, giving rise to the computationally very efficient FC (frozen core) approach; in the latter, all non-ECP electrons were included in the correlation treatment, giving rise to the AE (all electron) approach. Apart from reactions involving Li and Be, the FC approach resulted in non-homogeneous performance. The FC approach leads to very small errors (<2 kcal mol-1) for some reactions of Na, Mg, Ca, Sr, Ba and Pb, while for a few reactions of Ca and Ba deviations up to 40 kcal mol-1 have been obtained. Large errors are both due to artificial mixing of the core (sub-valence) orbitals of metals and the valence orbitals of oxygen and halogens in the molecular orbitals treated as core, and due to neglecting core-core and core-valence correlation effects. These large errors are reduced to a few kcal mol-1 if the AE approach is used or the sub-valence orbitals of metals are included in the correlation treatment. On the technical side, the CCSD(T) and DLPNO-CCSD(T) results differ by a fraction of kcal mol-1, indicating the latter method as the perfect choice when the CPU efficiency is essential. For completely black-box applications, as requested in catalysis or thermochemical calculations, we recommend the DLPNO-CCSD(T) method with all electrons that are not covered by effective core potentials included in the correlation treatment and correlation-consistent polarized core valence basis sets of cc-pwCVQZ(-PP) quality.

  16. Reaction of monocytes to polystyrene and silica nanoparticles in short-term and long-term exposures† (United States)

    Mrakovcic, Maria; Meindl, Claudia; Roblegg, Eva; Fröhlich, Eleonore


    Nanoparticles (NPs) are increasingly used in industrial, health and consumer products. In addition to the intended effects, NPs may also cause cell damage. Typical cytotoxicity assays assess short-term effects in adherent cells but do not evaluate longer exposure times and do not focus on cells in suspension. Since NPs are not removed easily from the organism, non-biodegradable NPs may persist in the systemic circulation and affect monocyte function at low concentrations. To mimic this situation, THP-1 monocytes were exposed to low concentrations of plain polystyrene particles (PPP) in different sizes for short (24 h) and prolonged (16 d) time periods. CELLine CL350, a small two-chamber bioreactor, and sub-culturing in flasks were compared regarding prolonged cytotoxicity testing. Uptake rates of the particles, cytotoxicity screening assays, and interleukin secretion were used for the identification of adverse effects. After 24 h, 50 μg ml−1 20 nm PPP did not affect cellular viability and interleukin secretion, while at higher concentrations the cytotoxicity of PPP (20 nm-500 nm) was correlated to surface area. After 16 d of exposure at 50 μg ml−1 20 nm PPP, the decrease in cell number and the increase in interleukins were significant. 200 nm PPP, by contrast, caused only minimal effects. Due to lower reproducibility, CELLine proved to be less suitable for the assessment as compared to sub-culturing in flasks. After prolonged exposure, silica Aerosil OX50 particles also were more cytotoxic towards THP-1 monocytes. The data suggest that prolonged exposure to NPs leads to cytotoxicity at low doses and that induction of cell death may be involved in the observed pro-inflammatory action of NPs. PMID:26005565


    DEFF Research Database (Denmark)


    The present invention concerns the selective removal of nitrogen oxides (NOx) from gasses. In particular, the invention concerns a process, a catalyst and the use of a catalyst for the selective removal of nitrogen oxides in the presence of ammonia from gases containing a significant amount...... of alkali metal and/or alkali-earth compounds which process comprises using a catalyst combined of (i) a formed porous superacidic support, said superacidic support having an Hammett acidity stronger than Ho=-12, and (ii) a metal oxide catalytic component deposited on said superacidic support selected from...

  18. Application of supported alkali catalysts in Prins reaction%负载碱催化剂在Prins反应中的应用

    Institute of Scientific and Technical Information of China (English)

    王海永; 吕慧; 林晨; 朱振炜; 许康栋; 曹贵平


    Solid base catalysts MnO/Al2O3 (M=Na, K, Cs, Mg, Ca, Sr,n=1 or 2) prepared by impregnation method and C-Cs2O/Al2O3 by co-precipitation method were applied in Prins reaction. Their base amount and pKa in water were determined. The structure and physico-chemical properties of the carrier and prepared catalysts were characterized by CO2-TPD, X-ray diffraction, and nitrogen adsorption. The performance of catalysts was evaluated by condensation reaction of isobutene with paraformaldehyde to produce 3-methyl-3-buten-1-ol. The results showed that the performance of catalysts related directly with their basic property and structure. The C-Cs2O/Al2O3 catalyst had stronger basicity and showed superior catalytic performance, and the conversion of formaldehyde and selectivity to MBO reached up to 100.0% and 86.0% respectively. The mechanism of Prins reaction over solid base catalyst was also discussed. The base sites could active theα-H of isobutene, and so could promote the Prins reaction.%分别采用浸渍法和共沉淀法制备了负载金属氧化物的固体碱催化剂MnO/Al2O3(M=Na,K,Cs,Mg,Ca, Sr;n=1,2)和C-Cs2O/Al2O3,测定了催化剂的碱量和pKa值,分别采用CO2-TPD、X射线衍射、N2物理吸附表征了催化剂的物理化学性质。以异丁烯与多聚甲醛经Prins反应制备3-甲基-3-丁烯-1-醇(MBO)为体系考察催化剂活性。结果表明,催化剂的碱性和结构直接影响其催化活性,采用共沉淀法制备的Cs2O/Al2O3催化剂具有更强的碱性,表现出了优越的反应活性,甲醛的转化率和产物MBO的选择性分别为100.0%和86.0%。探讨了固体碱催化反应的机理,发现碱性位可以活化异丁烯的α-H,促进Prins反应。

  19. Process optimization of reaction of acid leaching residue of asbestos tailing and sodium hydroxide aqueous solution

    Institute of Scientific and Technical Information of China (English)


    Silica is the major component of the acid leaching residue of asbestos tailing. The waterglass solution can be prepared by the reaction of the residue with sodium hydroxide aqueous solution. Compared to the high temperature reaction method, this process is environmental friendly and low cost. In this paper, the reaction process of the residue and the sodium hydroxide aqueous solution is optimized. The optimum reaction process parameters are as follows: the usage of sodium hydroxide is 26.4 g/100 g acid leaching residue, the reaction temperature is 90℃, the reaction time is 1 h, and the ratio of the liquid/solid is 2.0. The significance sequence of the process parameters to the alkali leaching reaction effect is the usage of sodium hydroxide > the ratio of the liquid/solid > the reaction time > the reaction temperature. The significance sequence to the leaching ratio of SiO2 is the ratio of the liquid/solid > the usage of sodium hydroxide > the reaction time > the reaction temperature. The significance sequence to the modulus of the sodium silicate is the ratio of the liquid/solid > the usage of sodium hydroxide > the reaction time > the reaction temperature. Under the optimum conditions, the leaching ratio of the SiO2 is 77.5%, and the modulus of the sodium silicate is 3.15. The XRD analysis result indicates that the major components of the alkali leaching residue are serpentine, talc, quartz and some albite.

  20. Effect of the 1-hexene, the Al-Zr ratio and the temperature in ethylene copolymerization reactions with catalyst systems grafted on silica; Efeito do teor de hexeno-1, da relacao Al-Zr e da temperatura em reacoes de copolimerizacao de eteno, com sistemas cataliticos hibridos suportados em silica

    Energy Technology Data Exchange (ETDEWEB)

    Loureiro, Silvia R.R.; Silveira, Fernando; Galland, Griselda B.; Santos, Joao H.Z. dos [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Inst. de Quimica].


    A series of copolymerization reactions with ethylene-1-hexene was performed with different amount of co-monomer, different aluminium-zirconium ratio and in two different temperature (40 deg C and 60 deg C). The reactions were accomplished by combining (nBuCp){sub 2} ZrCl{sub 2} and Cp{sub 2}ZrCl{sub 2} grafted on silica in different ratio (1:1, 3:1 and 1:3) and immobilization order. The catalyst activity in copolymerization reactions was shown to be dependent on the amount of the co-monomer, the Al-Zr ratio and the temperature. (author)

  1. Influence of Particle Size on Reaction Selectivity in Cyclohexene Hydrogenation and Dehydrogenation over Silica-Supported Monodisperse Pt Particles

    Energy Technology Data Exchange (ETDEWEB)

    Rioux, R. M.; Hsu, B. B.; Grass, M. E.; Song, H.; Somorjai, Gabor A.


    The role of particle size during the hydrogenation/dehydrogenation of cyclohexene (10 Torr C{sub 6}H{sub 10}, 200-600 Torr H{sub 2}, and 273-650 K) was studied over a series of monodisperse Pt/SBA-15 catalysts. The conversion of cyclohexene in the presence of excess H{sub 2} (H{sub 2}:C{sub 6}H{sub 10} ratio = 20-60) is characterized by three regimes: hydrogenation of cyclohexene to cyclohexane at low temperature (< 423 K), an intermediate temperature range in which both hydrogenation and dehydrogenation occur; and a high temperature regime in which the dehydrogenation of cyclohexene dominates (> 573 K). The rate of both reactions demonstrated maxima with temperature, regardless of Pt particle size. For the hydrogenation of cyclohexene, a non-Arrhenius temperature dependence (apparent negative activation energy) was observed. Hydrogenation is structure insensitive at low temperatures, and apparently structure sensitive in the non-Arrhenius regime; the origin of the particle-size dependent reactivity with temperature is attributed to a change in the coverage of reactive hydrogen. Small particles were more active for dehydrogenation and had lower apparent activation energies than large particles. The selectivity can be controlled by changing the particle size, which is attributed to the structure sensitivity of both reactions in the temperature regime where hydrogenation and dehydrogenation are catalyzed simultaneously.

  2. Pyrolysis characteristic of kenaf studied with separated tissues, alkali pulp, and alkali li

    Directory of Open Access Journals (Sweden)

    Yasuo Kojima


    Full Text Available To estimate the potential of kenaf as a new biomass source, analytical pyrolysis was performed using various kenaf tissues, i.e., alkali lignin and alkali pulp. The distribution of the pyrolysis products from the whole kenaf was similar to that obtained from hardwood, with syringol, 4-vinylsyringol, guaiacol, and 4-vinylguaiacol as the major products. The phenols content in the pyrolysate from the kenaf core was higher than that from the kenaf cuticle, reflecting the higher lignin content of the kenaf core. The ratios of the syringyl and guaiacyl compounds in the pyrolysates from the core and cuticle samples were 2.79 and 6.83, respectively. Levoglucosan was the major pyrolysis product obtained from the kenaf alkali pulp, although glycol aldehyde and acetol were also produced in high yields, as previously observed for other cellulosic materials. Moreover, the pathways for the formation of the major pyrolysis products from alkali lignin and alkali pulp were also described, and new pyrolysis pathways for carbohydrates have been proposed herein. The end groups of carbohydrates bearing hemiacetal groups were subjected to ring opening and then they underwent further reactions, including further thermal degradation or ring reclosing. Variation of the ring-closing position resulted in the production of different compounds, such as furans, furanones, and cyclopentenones.

  3. Enhance luminescence by introducing alkali metal ions (R+ = Li+, Na+ and K+) in SrAl2O4:Eu3+ phosphor by solid-state reaction method (United States)

    Prasad Sahu, Ishwar


    In the present article, the role of charge compensator ions (R+ = Li+, Na+ and K+) in europium-doped strontium aluminate (SrAl2O4:Eu3+) phosphors was synthesized by the high-temperature, solid-state reaction method. The crystal structures of sintered phosphors were in a monoclinic phase with space group P21. The trap parameters which are mainly activation energy (E), frequency factor (s) and order of the kinetics (b) were evaluated by using the peak shape method. The calculated trap depths are in the range from 0.76 to 0.84 eV. Photoluminescence measurements showed that the phosphor exhibited emission peak with good intensity at 595 nm, corresponding to 5D0-7F1 (514 nm) orange emission and weak 5D0-7F2 (614 nm) red emission. The excitation spectra monitored at 595 nm show a broad band from 220 to 320 nm ascribed to O-Eu charge-transfer state transition and the other peaks in the range of 350-500 nm originated from f-f transitions of Eu3+ ions. The strongest band at 394 nm can be assigned to 7F0-5L6 transition of Eu3+ ions due to the typical f-f transitions within Eu3+ of 4f6 configuration. The latter lies in near ultraviolet (350-500 nm) emission of UV LED. CIE color chromaticity diagram and thermoluminescence spectra confirm that the synthesized phosphors would emit an orange-red color. Incorporating R+ = Li+, Na+ and K+ as the compensator charge, the emission intensity of SrAl2O4:Eu3+ phosphor can be obviously enhanced and the emission intensity of SrAl2O4:Eu3+ doping Li+ is higher than that of Na+ or K+ ions.

  4. Alkali norite, troctolites, and VHK mare basalts from breccia 14304 (United States)

    Goodrich, Cyrena Anne; Taylor, G. Jeffrey; Keil, Klaus; Kallemeyn, Gregory W.; Warren, Paul H.


    Twelve clasts were separated from breccia 14304 for consortium study: six pristine highlands rocks, two mare basalts, and four nonpristine highlands rocks. The pristine highlands rocks include representatives of the magnesian troctolite-anorthosite and alkali suites, the two most common subgroups of the Mg suite found at the Apollo 14 site. Two troctolite clasts have olivine (~Fo 90) and plagioclase (~An 94) compositions similar to one group of Apolo 14 troctolites. One also contains spinel (Mg' 66-85). Incompatible element abundances in one are similar to those of 14305 troctolites, although the HREE (heavy rare earth elements) pattern is distinct among Apollo 14 troctolites. A dunite clast (~Fo 89) may be an unrepresentative piece of a troctolite. Alkali lithologies include an alkali anorthosite and an alkali norite, which is a rock type not previously described. The alkali norite has a pristine igneous texture and contains inverted pigeonite (Mg' 64), plagioclase (An82), K-feldspar, ternary feldspar, REE-rich phosphates, and silica. It resembles alkali gabbronorites from Apollo 14 and 67975 in mineralogy and mineral compositions. Alkali lithologies and phosphate-bearing magnesian anorthosites from Apollo 14 may have formed from Mg-rich magmas that assimilated various amounts of material rich in P and REE. This material could be a fractionated derivative of urKREEP. another pristine clast from 14304 is an Mg-gabbronorite. The two mare basalt clasts are very high potassium (VHK) basalts. They have 4 mg/g K and K/La ratios of 580 and 700. The parent magmas of VHK basalts could have formed from typical low-Ti, high-Al basaltic magmas by assimilation of K-rich material. This material could also be a fractionated derivative or urKREEP. Nonpristine 14304 clasts include melt-textured anorthosites and an augite-rich poikilitic melt rock. The latter is probably polymict, but its major component must be an Mg-suite gabbro.

  5. Gas-Solid Displacement Reactions for Converting Silica Diatom Frustules into MgO and TiO2

    Energy Technology Data Exchange (ETDEWEB)

    Kalem, Tugba [Iowa State Univ., Ames, IA (United States)


    Technology for the microfabrication of freely moving parts began with a Bell Labs microgear spun by an air jet, and electrostatic silicon micro motors in the mid-1980s. It continued with development work on micropositioning of optics, miniature heat exchangers, small fluidic devices, and chemical reaction chambers. Recently, there has been a great deal of interest centered on the design and manufacture of devices of nanometer proportions and this speculation has spawned a new industry named, nanotechnology. Despite the technological and economic promise of this technology, current commercial micro/mesofabrication methods have largely been based upon two-dimensional processing principles which is not well suited to the low-cost mass production of three-dimensional micro devices with complex geometries and meso/nanoscale features. Diatoms are three dimensional (3D) microstructures from nature that provide a practical alternative for nanotechnology and microfabrication. Diatoms (Figure 1) are single-celled micro algae that form rigid cell walls (frustules) composed of amorphous silica. Their dimensions can range from less than 1 micron to several hundreds of microns. They are distributed throughout the world in aquatic, semi-aquatic and moist habitats, and extremely abundant in freshwater and marine ecosystems. Diatoms are thought to be responsible for up to 25% of the world's net primary production of organic carbon (by transforming of carbon dioxide and water into sugars by photosynthesis). Approximately 105 unique diatom frustule shapes have been claimed to exist in nature. The frustules are composed of two valves that fit together like a petri-dish, connected to each other by one or more girdle bands. The frustule wall consists of a nanoporous assembly of silica nanoparticles. They absorb soluble silica from water even at extremely low concentrations and metabolize and deposit it as an external skeleton. Continued reproduction of a single parent

  6. Silica Nephropathy

    Directory of Open Access Journals (Sweden)

    N Ghahramani


    Full Text Available Occupational exposure to heavy metals, organic solvents and silica is associated with a variety of renal manifestations. Improved understanding of occupational renal disease provides insight into environmental renal disease, improving knowledge of disease pathogenesis. Silica (SiO2 is an abundant mineral found in sand, rock, and soil. Workers exposed to silica include sandblasters, miners, quarry workers, masons, ceramic workers and glass manufacturers. New cases of silicosis per year have been estimated in the US to be 3600–7300. Exposure to silica has been associated with tubulointerstitial disease, immune-mediated multisystem disease, chronic kidney disease and end-stage renal disease. A rare syndrome of painful, nodular skin lesions has been described in dialysis patients with excessive levels of silicon. Balkan endemic nephropathy is postulated to be due to chronic intoxication with drinking water polluted by silicates released during soil erosion. The mechanism of silica nephrotoxicity is thought to be through direct nephrotoxicity, as well as silica-induced autoimmune diseases such as scleroderma and systemic lupus erythematosus. The renal histopathology varies from focal to crescentic and necrotizing glomerulonephritis with aneurysm formation suggestive of polyarteritis nodosa. The treatment for silica nephrotoxicity is non-specific and depends on the mechanism and stage of the disease. It is quite clear that further research is needed, particularly to elucidate the pathogenesis of silica nephropathy. Considering the importance of diagnosing exposure-related renal disease at early stages, it is imperative to obtain a thorough occupational history in all patients with renal disease, with particular emphasis on exposure to silica, heavy metals, and solvents.

  7. Preparation of polyamide 6/silica nanocomposites from silica surface initiated ring-opening anionic polymerization

    Directory of Open Access Journals (Sweden)


    Full Text Available Polyamide 6/silica nanocomposites were synthesized by in situ ring-opening anionic polymerization of ε-caprolactam in the presence of sodium caprolactamate as a catalyst and caprolactam-functionalized silica as an initiator. The initiator precursor, isocyanate-functionalized silica, was prepared by directly reacting commercial silica with excess toluene 2,4-diisocyanate. This polymerization was found to occur in a highly efficient manner at relatively low reaction temperature (170°C and short reaction times (6 h. FTIR spectroscopy was utilized to follow the introduction and consumption of isocyanate groups on the silica surface. Thermogravimetric analysis indicated that the polyamide 6 was successfully grown from the silica surface. Transmission electron microscopy was utilized to image polymer-functionalized silica, showing fine dispersion of silica particles and their size ranging from 20 to 40 nm.

  8. Kinetics of silica polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Weres, O.; Yee, A.; Tsao, L.


    The polymerization of silicic acid in geothermal brine-like aqueous solutions to produce amorphous silica in colloidal form has been studied experimentally and theoretically. A large amount of high quality experimental data has been generated over the temperature rang 23 to 100{sup 0}C. Wide ranges of dissolved silica concentration, pH, and sodium chloride concentration were covered. The catalytic effects of fluoride and the reaction inhibiting effects of aluminum and boron were studied also. Two basic processes have been separately studied: the formation of new colloidal particles by the homogeneous nucleation process and the deposition of dissolved silica on pre-existing colloidal particles. A rigorous theory of the formation of colloidal particles of amorphous silica by homogeneous nucleation was developed. This theory employs the Lothe-Pound formalism, and is embodied in the computer code SILNUC which quantitatively models the homogeneous nucleation and growth of colloidal silica particles in more than enough detail for practical application. The theory and code were extensively used in planning the experimental work and analyzing the data produced. The code is now complete and running in its final form. It is capable of reproducing most of the experimental results to within experimental error. It is also capable of extrapolation to experimentally inaccessible conditions, i.e., high temperatures, rapidly varying temperature and pH, etc.

  9. The calcium-alkali syndrome


    Arroyo, Mariangeli; Fenves, Andrew Z.; Emmett, Michael


    The milk-alkali syndrome was a common cause of hypercalcemia, metabolic alkalosis, and renal failure in the early 20th century. It was caused by the ingestion of large quantities of milk and absorbable alkali to treat peptic ulcer disease. The syndrome virtually vanished after introduction of histamine-2 blockers and proton pump inhibitors. More recently, a similar condition called the calcium-alkali syndrome has emerged as a common cause of hypercalcemia and alkalosis. It is usually caused b...

  10. Natural Alkali Shifts to the Methanol Business

    Institute of Scientific and Technical Information of China (English)


    @@ Inner Mongolia Yuanxing Natural Alkali Co., Ltd. (Natural Alkali SZ: 000683) established in 1997 is a large chemical enterprise with new energy as its leading business and natural gas chemicals and natural alkali chemicals as the supplement business.

  11. Pillaring effects in macroporous carrageenan-silica composite microspheres. (United States)

    Boissière, M; Tourrette, A; Devoisselle, J M; Di Renzo, F; Quignard, F


    The impregnation of a carrageenan gel by a silica sol is an efficient method to form a composite material which can be conveniently activated by CO2 supercritical drying. The textural properties of the solids have been characterized by nitrogen adsorption-desorption at 77 K and their composition by thermogravimetric analysis and EDX microprobe. Morphology was examined by SEM. The silica-carrageenan composites present an open macroporous structure. Silica particles retained inside the gel behaved as pillars between the polysaccharide fibrils and form a stick-and-ball network. The stiffening of the carrageenan gel by silica prevented its shrinkage upon drying. The nature of the alkali cations affected the retention of silica particles inside the gel. In the absence of silica, carrageenan fibrils rearrange under supercritical drying and form an aerogel with cavities in the mesopore range.

  12. Alkali control of high-grade metamorphism and granitization

    Directory of Open Access Journals (Sweden)

    Oleg G. Safonov


    Full Text Available We review petrologic observations of reaction textures from high-grade rocks that suggest the passage of fluids with variable alkali activities. Development of these reaction textures is accompanied by regular compositional variations in plagioclase, pyroxenes, biotite, amphibole and garnet. The textures are interpreted in terms of exchange and net-transfer reactions controlled by the K and Na activities in the fluids. On the regional scale, these reactions operate in granitized, charnockitized, syenitized etc. shear zones within high-grade complexes. Thermodynamic calculations in simple chemical systems show that changes in mineral assemblages, including the transition from the hydrous to the anhydrous ones, may occur at constant pressure and temperature due only to variations in the H2O and the alkali activities. A simple procedure for estimating the activity of the two major alkali oxides, K2O and Na2O, is implemented in the TWQ software. Examples of calculations are presented for well-documented dehydration zones from South Africa, southern India, and Sri Lanka. The calculations have revealed two end-member regimes of alkalis during specific metamorphic processes: rock buffered, which is characteristic for the precursor rocks containing two feldspars, and fluid-buffered for the precursor rocks without K-feldspar. The observed reaction textures and the results of thermodynamic modeling are compared with the results of available experimental studies on the interaction of the alkali chloride and carbonate-bearing fluids with metamorphic rocks at mid-crustal conditions. The experiments show the complex effect of alkali activities in the fluid phase on the mineral assemblages. Both thermodynamic calculations and experiments closely reproduce paragenetic relations theoretically predicted by D.S. Korzhinskii in the 1940s.

  13. Neutral and Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes: Reactivity in Selected Olefin Metathesis Reactions and Immobilization on Silica. (United States)

    Sen, Suman; Schowner, Roman; Imbrich, Dominik A; Frey, Wolfgang; Hunger, Michael; Buchmeiser, Michael R


    The synthesis and single-crystal X-ray structures of the novel molybdenum imido alkylidene N-heterocyclic carbene complexes [Mo(N-2,6-Me2C6H3)(IMesH2)(CHCMe2Ph)(OTf)2] (3), [Mo(N-2,6-Me2C6H3)(IMes)(CHCMe2Ph)(OTf)2] (4), [Mo(N-2,6-Me2C6H3)(IMesH2)(CHCMe2Ph)(OTf){OCH(CF3)2}] (5), [Mo(N-2,6-Me2C6H3)(CH3CN)(IMesH2)(CHCMe2Ph)(OTf)](+)BArF(-) (6), [Mo(N-2,6-Cl2C6H3)(IMesH2)(CHCMe3)(OTf)2] (7) and [Mo(N-2,6-Cl2C6H3)(IMes)(CHCMe3)(OTf)2] (8) are reported (IMesH2=1,3-dimesitylimidazolidin-2-ylidene, IMes=1,3-dimesitylimidazolin-2-ylidene, BArF(-)=tetrakis-[3,5-bis(trifluoromethyl)phenyl] borate, OTf=CF3SO3(-)). Also, silica-immobilized versions I1 and I2 were prepared. Catalysts 3-8, I1 and I2 were used in homo-, cross-, and ring-closing metathesis (RCM) reactions and in the cyclopolymerization of α,ω-diynes. In the RCM of α,ω-dienes, in the homometathesis of 1-alkenes, and in the ethenolysis of cyclooctene, turnover numbers (TONs) up to 100,000, 210,000 and 30,000, respectively, were achieved. With I1 and I2, virtually Mo-free products were obtained (<3 ppm Mo). With 1,6-hepta- and 1,7-octadiynes, catalysts 3, 4, and 5 allowed for the regioselective cyclopolymerization of 4,4-bis(ethoxycarbonyl)-1,6-heptadiyne, 4,4-bis(hydroxymethyl)-1,6-heptadiyne, 4,4-bis[(3,5-diethoxybenzoyloxy)methyl]-1,6-heptadiyne, 4,4,5,5-tetrakis(ethoxycarbonyl)-1,7-octadiyne, and 1,6-heptadiyne-4-carboxylic acid, underlining the high functional-group tolerance of these novel Group 6 metal alkylidenes.

  14. Alkali metal and alkali earth metal gadolinium halide scintillators

    Energy Technology Data Exchange (ETDEWEB)

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.


    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  15. Preparation of polystyrene/silica nanocomposites by radical copolymerization of styrene with silica macromonomer

    Institute of Scientific and Technical Information of China (English)


    A two-stage process has been developed to generate the silica-based macromonomer through surface-modification of silica with polymerizable vinyl groups. The silica surfaces were treated with excess 2,4-toluene diisocynate (TDI), after which the residual isocyanate groups were converted into polymerizable vinyl groups by reaction with hydroxypropylacrylate (HPA). Thus, polystyrene/silica nanocomposites were prepared by conventional radical copolymerization of styrene with silica macromonomer. The main effecting factors, such as ratios of styrene to the macromonomer, together with polymerization time on the copolymerization were studied in detail. FTIR, DSC and TGA were utilized to characterize the nanocomposites. Experimental results revealed that the silica nanoparticles act as cross-linking points in the polystytene/silica nanocomposites, and the glass transition temperatures of the nanocomposites are higher than that of the corresponding pure polystyrene. The glass transition temperatures of nanocomposites increased with the increasing of silica contents, which were further ascertained by DSC.

  16. Synthesis and Gas Transport Properties of Hyperbranched Polyimide–Silica Hybrid/Composite Membranes

    Directory of Open Access Journals (Sweden)

    Masako Miki


    Full Text Available Hyperbranched polyimide–silica hybrids (HBPI–silica HBDs and hyperbranched polyimide–silica composites (HBPI–silica CPTs were prepared, and their general and gas transport properties were investigated to clarify the effect of silica sources and preparation methods. HBPI–silica HBDs and HBPI–silica CPTs were synthesized by two-step polymerization of A2 + B3 monomer system via polyamic acid as precursor, followed by hybridizing or blending silica sources. Silica components were incorporated by the sol-gel reaction with tetramethoxysilane (TMOS or the addition of colloidal silica. In HBPI-silica HBDs, the aggregation of silica components is controlled because of the high affinity of HBPI and silica caused by the formation of covalent bonds between HBPI and silica. Consequently, HBPI-silica HBDs had good film formability, transparency, and mechanical properties compared with HBPI-silica CPTs. HBPI-silica HBD and CPT membranes prepared via the sol-gel reaction with TMOS showed specific gas permeabilities and permselectivities for CO2/CH4 separation, that is, both CO2 permeability and CO2/CH4 selectivity increased with increasing silica content. This result suggests that gas transport can occur through a molecular sieving effect of the porous silica network derived from the sol-gel reaction and/or through the narrow interfacial region between the silica networks and the organic matrix.

  17. H-ZSM-5 Zeolite Synthesis by Sourcing Silica from the Wheat Husk Ash: Characterization and Application as a Versatile Heterogeneous Catalyst in Organic Transformations including Some Multicomponent Reactions

    Directory of Open Access Journals (Sweden)

    Isak Rajjak Shaikh


    Full Text Available ZSM-5 zeolite was synthesized by sourcing silica from wheat husk ash and was converted into its protonated form following careful, conventionally accepted ion-exchange method and calcinations. The H-ZSM-5 zeolite (Si/Al ratio = 30 prepared was appropriately characterized by XRD, FT-IR, SEM, TEM, TG-DTA, CV, and so forth, and evaluated as recyclable catalyst in selective organic transformations including three- and four-component reactions. The catalytic activity of the zeolite sample supposedly relates to increased density of the accessible acid sites.

  18. Copper (0) nanoparticles onto silica: A stable and facile catalyst for one-pot synthesis of 2,2'-arylmethylene bis (3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) via cascade Knoevenagel/ Michael reaction

    Indian Academy of Sciences (India)



    Solid supported copper (0) nanoparticles were prepared by physical adsorption of copper (0)nanoparticles (synthesized through bottom-up approach) on the solid supports such as silica, HAP, cellulose andbasic alumina. Studies comparing these supported catalysts were done with the synthesis of arylmethylene-bis-(3-hydroxy-2-cyclohexene-1-one) via the cascade Knoevenagel/Michael reaction. The highly efficient catalystwas characterized by spectroscopic techniques like XPS, TGA, EDX, SEM, TEM and AAS. The biologicalimportance of arylmethylene-bis-(3-hydroxy-2-cyclohexene-1-one) enforced us to synthesize these compoundscatalytically using solid supported copper (0) nanopartcles.

  19. A new approach for the preparation of well-defined Rh and Pt nanoparticles stabilized by phosphine-functionalized silica for selective hydrogenation reactions. (United States)

    Llop Castelbou, J; Szeto, K C; Barakat, W; Merle, N; Godard, C; Taoufik, M; Claver, C


    In this work, a new methodology for the synthesis of well-defined metallic nanoparticles supported on silica is described. This methodology is based on the surface control provided by SOMC. The nanoparticles are formed via the organometallic approach and are catalytically active in the hydrogenation of p-xylene, 3-hexyne, 4-phenyl-2 butanone, benzaldehyde, and furfural.

  20. "Hydro-metathesis" of olefins: A catalytic reaction using a bifunctional single-site tantalum hydride catalyst supported on fibrous silica (KCC-1) nanospheres

    KAUST Repository

    Polshettiwar, Vivek


    Tantalizing hydrocarbons: Tantalum hydride supported on fibrous silica nanospheres (KCC-1) catalyzes, in the presence of hydrogen, the direct conversion of olefins into alkanes that have higher and lower numbers of carbon atoms (see scheme). This catalyst shows remarkable catalytic activity and stability, with excellent potential of regeneration. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Functionalized silica materials for electrocatalysis

    Indian Academy of Sciences (India)

    Vellaichamy Ganesan


    Electrocatalysis is an important phenomenon which is utilized in metal–air batteries, fuel cells, electrochemical sensors, etc. To increase the efficiency of the electrocatalytic process and to increase the electrochemical accessibility of the immobilized electrocatalysts, functionalized and non-functionalized mesoporous organo-silica (MCM41-type-materials) are used in this study. These materials possess several suitable properties to be durable catalysts and/or catalyst supports. Owing to the uniform dispersion of electrocatalysts (metal complex and/or metal nanoparticles (NPs)) on the functionalized and non-functionalized silica, an enormous increase in the redox current is observed. Long range channels of silica materials with pore diameter of 15–100 Å allowed metal NPs to accommodate in a specified manner in addition to other catalysts. The usefulness of MCM-41-type silica in increasing the efficiency of electrocatalysisis demonstrated by selecting oxygen, carbon dioxide and nitrite reduction reactions as examples

  2. Upgrading platform using alkali metals

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard


    A method for removing sulfur, nitrogen or metals from an oil feedstock. The method involves reacting the oil feedstock with an alkali metal and a radical capping substance. The alkali metal reacts with the metal, sulfur or nitrogen content to form one or more inorganic products and the radical capping substance reacts with the carbon and hydrogen content to form a hydrocarbon phase. The inorganic products may then be separated out from the hydrocarbon phase.

  3. Upgrading platform using alkali metals

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard


    A process for removing sulfur, nitrogen or metals from an oil feedstock (such as heavy oil, bitumen, shale oil, etc.) The method involves reacting the oil feedstock with an alkali metal and a radical capping substance. The alkali metal reacts with the metal, sulfur or nitrogen content to form one or more inorganic products and the radical capping substance reacts with the carbon and hydrogen content to form a hydrocarbon phase. The inorganic products may then be separated out from the hydrocarbon phase.

  4. Aniline incorporated silica nanobubbles

    Indian Academy of Sciences (India)

    M J Rosemary; V Suryanarayanan; Ian Maclaren; T Pradeep


    We report the synthesis of stearate functionalized nanobubbles of SiO2 with a few aniline molecules inside, represented as C6H5NH2@SiO2@stearate, exhibiting fluorescence with red-shifted emission. Stearic acid functionalization allows the materials to be handled just as free molecules, for dissolution, precipitation, storage etc. The methodology adopted involves adsorption of aniline on the surface of gold nanoparticles with subsequent growth of a silica shell through monolayers, followed by the selective removal of the metal core either using sodium cyanide or by a new reaction involving halocarbons. The material is stable and can be stored for extended periods without loss of fluorescence. Spectroscopic and voltammetric properties of the system were studied in order to understand the interaction of aniline with the shell as well as the monolayer, whilst transmission electron microscopy has been used to study the silica shell.

  5. Pathways of birnessite formation in alkali medium

    Institute of Scientific and Technical Information of China (English)

    FENG Xionghan; TAN Wenfeng; LIU Fan; HUANG Qiaoyun; LIU Xiangwen


    Birnessite is a common weathering and oxidation product of manganese-bearing rocks. An O2 oxidation procedure of Mn(OH)2 in the alkali medium has been used to synthesize birnessite. Fast and powder X-ray diffraction (XRD), transmission electron microscopy (TEM), electron diffraction (ED), energy dispersed X-ray analysis (EDAX), infrared spectroscopy (IR) techniques and chemical composition analysis, Eh-pH equilibrium diagram approaches were employed to investigate the reaction process and pathways of birnessite formation. Results showed that the process of the birnessite formation could be divided into four stages: (1) formation stage for hausmannite and feitknechtite, (2) stage of transformation of hausmannite and feitknechtite to buserite, (3) buserite crystal growing stage, and (4) stage of conversion of buserite into birnessite. Mn(OH)2 was mainly present as amorphous state only for a short initial time of oxidation reaction. In the oxidation process, buserite formed following two pathways by recrystallization after dissolution of the intermediates, and the transformations of the minerals depended on the Eh determined by the dissolved O2 concentration on their surfaces. The results are fundamental in further exploration on the mechanism of birnessite formation in the alkali medium. A great practical significance would also be expected with respect to the areas of material sciences.

  6. Synthesis of robust hierarchical silica monoliths by surface-mediated solution/precipitation reactions over different scales: designing capillary microreactors for environmental applications. (United States)

    García-Aguilar, J; Miguel-García, I; Berenguer-Murcia, Á; Cazorla-Amorós, D


    A synthetic procedure to prepare novel materials (surface-mediated fillings) based on robust hierarchical monoliths is reported. The methodology includes the deposition of a (micro- or mesoporous) silica thin film on the support followed by growth of a porous monolithic SiO2 structure. It has been demonstrated that this synthesis is viable for supports of different chemical nature with different inner diameters without shrinkage of the silica filling. The formation mechanism of the surface-mediated fillings is based on a solution/precipitation process and the anchoring of the silica filling to the deposited thin film. The interaction between the two SiO2 structures (monolith and thin film) depends on the porosity of the thin film and yields composite materials with different mechanical stability. By this procedure, capillary microreactors have been prepared and have been proved to be highly active and selective in the total and preferential oxidation of carbon monoxide (TOxCO and PrOxCO).

  7. Adsorption of mercury ions by mercapto-functionalized amorphous silica

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Quintanilla, Damian; Hierro, Isabel del; Fajardo, Mariano; Sierra, Isabel [Universidad Rey Juan Carlos, Departamento de Tecnologia Quimica y Ambiental, E.S.C.E.T, Mostoles, Madrid (Spain); Carrillo-Hermosilla, Fernando [Universidad de Castilla-La Mancha, Departamento de Quimica Inorganica, Organica y Bioquimica, Facultad de Quimicas, Ciudad Real (Spain)


    Amorphous silicas have been functionalized by two different methods. In the heterogeneous route the silylating agent, 3-chloropropyltriethoxysilane, was initially immobilized onto the silica surface to give the chlorinated silica Cl-Sil. In a second reaction, multifunctionalized N,S donor compounds were incorporated to obtain the functionalized silicas, which are denoted as L-Sil-Het (where L=mercaptothiazoline, mercaptopyridine or mercaptobenzothiazole). In the homogeneous route, the functionalization was achieved through a one-step reaction between the silica and an organic ligand containing the chelating functions; this gave the modified silicas denoted as L-Sil-Hom. The functionalized silicas were characterized by elemental analysis, IR spectroscopy and thermogravimetry. These materials were employed as adsorbents for mercury cations from aqueous and acetone solutions at room temperature. The results indicate that, in all cases, mercury adsorption was higher in the modified silicas prepared by the homogeneous method. (orig.)

  8. Modified monolithic silica capillary for preconcentration of catecholamines

    Institute of Scientific and Technical Information of China (English)

    Wei Chang; Tusyo-shi Komazu


    Preconcentration of catecholamines by the modified monolithic silica in the capillary was investigated in this study. In order to achieve a microchip-based method for determining catecholamines in the saliva, the monolithic silica was fabricated in the capillary and the monolithic silica was chemically modified by on-column reaction with phenylboronate. Different modified methods were compared. The concentration conditions were optimized. This study indicates the applicability of the modified monolithic silica capillary when it was used to concentrate catecholamines.

  9. Adding nickel formate in alkali lignin to increase contents of alkylphenols and aromatics during fast pyrolysis. (United States)

    Geng, Jing; Wang, Wen-Liang; Yu, Yu-Xiang; Chang, Jian-Min; Cai, Li-Ping; Shi, Sheldon Q


    The composition of pyrolysis vapors obtained from alkali lignin pyrolysis with the additive of nickel formate was examined using the pyrolysis gas chromatography-mass spectrometry (Py-GC/MS). Characterization of bio-chars was performed using X-ray diffraction (XRD). Results showed that the nickel formate significantly increased liquid yield, simplified the types of alkali lignin pyrolysis products and increased individual component contents. The additive of nickel formate increased contents of alkylphenols and aromatics from alkali lignin pyrolysis. With an increase in temperature, a greater amount of the relative contents can be achieved. The nickel formate was thermally decomposed to form hydrogen, resulting in hydrodeoxygenation of alkali lignin during pyrolysis. It was also found that Ni is in favor of producing alkylphenols. The analysis based on the experimental result provided evidences used to propose reaction mechanism for pyrolysis of nickel formate-assisted alkali lignin.

  10. Covalently grafted, silica gel supported C-protected cysteine or cystine copper complexes - syntheses, structure and possible surface reactions studied by FT-IR spectroscopy (United States)

    Aranyi, A.; Csendes, Z.; Kiss, J. T.; Pálinkó, I.


    In this work the covalent anchoring of C-protected Cu(II)- L-cysteine and Cu(II)- L-cystine complexes onto a surface-modified silica gel is described. Conditions of the syntheses were varied and the obtained structures were studied by classical analytical (titration) as well as spectroscopic (infrared, atomic absorption) methods. It was found that the sulphur atoms in the molecules acted as primary coordination sites, while the other coordinating groups varied depending on whether the complexes were formed under ligand-poor or ligand-excess conditions.

  11. Influence of amorphous silica on the hydration in ultra-high performance concrete

    Energy Technology Data Exchange (ETDEWEB)

    Oertel, Tina, E-mail: [Fraunhofer–Institute for Silicate Research ISC, Neunerplatz 2, 97082 Würzburg (Germany); Inorganic Chemistry I, Universität Bayreuth, Universitätsstr. 30, 95440 Bayreuth (Germany); Helbig, Uta, E-mail: [Crystallography and X-ray Methods, Technische Hochschule Nürnberg Georg Simon Ohm, Wassertorstraße 10, 90489 Nürnberg (Germany); Hutter, Frank [Fraunhofer–Institute for Silicate Research ISC, Neunerplatz 2, 97082 Würzburg (Germany); Kletti, Holger [Building Materials, Bauhaus–Universität Weimar, Coudraystr. 11, 99423 Weimar (Germany); Sextl, Gerhard [Fraunhofer–Institute for Silicate Research ISC, Neunerplatz 2, 97082 Würzburg (Germany); Chemical Technology of Advanced Materials, Julius Maximilian Universität, Röntgenring 11, 97070 Würzburg (Germany)


    Amorphous silica particles (silica) are used in ultra-high performance concretes to densify the microstructure and accelerate the clinker hydration. It is still unclear whether silica predominantly increases the surface for the nucleation of C–S–H phases or dissolves and reacts pozzolanically. Furthermore, varying types of silica may have different and time dependent effects on the clinker hydration. The effects of different silica types were compared in this study by calorimetric analysis, scanning and transmission electron microscopy, in situ X-ray diffraction and compressive strength measurements. The silica component was silica fume, pyrogenic silica or silica synthesized by a wet-chemical route (Stoeber particles). Water-to-cement ratios were 0.23. Differences are observed between the silica for short reaction times (up to 3 days). Results indicate that silica fume and pyrogenic silica accelerate alite hydration by increasing the surface for nucleation of C–S–H phases whereas Stoeber particles show no accelerating effect.

  12. Microstructure and Engineering Properties of Alkali Activated Fly Ash -as an environment friendly alternative to Portland cement

    NARCIS (Netherlands)

    Ma, Y.


    Alkali activated fly ash (AAFA), also named “geopolymer”, has emerged as a novel engineering material in the construction industry. This material is normally formed by the reaction between fly ash and aqueous hydroxide or alkali silicate solution. With proper mix design, AAFA can present comparable

  13. Process optimization of reaction of acid leaching residue of asbestos tailing and sodium hydroxide aqueous solution

    Institute of Scientific and Technical Information of China (English)

    DU GaoXiang; ZHENG ShuiLin; DING Hao


    Silica is the major component of the acid leaching residue of asbestos tailing. The waterglass solution can be prepared by the reaction of the residue with sodium hydroxide aqueous solution. Compared to the high temperature reaction method, this process is environmental friendly and low cost. In this paper, the reaction process of the residue and the sodium hydroxide aqueous solution is optimized. The op-timum reaction process parameters are as follows: the usage of sodium hydroxide is 26.4 g/100 g acid leaching residue, the reaction temperature is 90℃, the reaction time is 1 h, and the ratio of the liq-uid/solid is 2.0. The significance sequence of the process parameters to the alkali leaching reaction effect is the usage of sodium hydroxide > the ratio of the liquid/solid > the reaction time > the reaction temperature. The significance sequence to the leaching ratio of SiO2 is the ratio of the liquid/solid > the usage of sodium hydroxide > the reaction time > the reaction temperature. The significance sequence to the modulus of the sodium silicate is the ratio of the liquid/solid > the usage of sodium hydroxide > the reaction time > the reaction temperature. Under the optimum conditions, the leaching ratio of the SiO2 is 77.5%, and the modulus of the sodium silicate is 3.15. The XRD analysis result indicates that the major components of the alkali leaching residue are serpentine, talc, quartz and some albite.

  14. Olefin metathesis over UV-irradiated silica (United States)

    Tanaka, Tsunehiro; Matsuo, Shigehiro; Maeda, Takashi; Yoshida, Hisao; Funabiki, Takuzo; Yoshida, Satohiro


    Photoirradiated silica evacuated at temperatures higher than 800 K was found to be active for olefin metathesis reactions. The analysis of products shows that the metalacyclobutane intermediate is likely. The instantaneous response of the reaction to the irradiation and the activity change with various UV filter showed that the reaction is induced by UV-excitation of silica. The correlation between the evacuation temperature and the activity showed that the surface free from water molecules plays a role in the reaction and the removal of isolated OH groups strongly relates to the generation of active sites.

  15. Process for recovering alkali metals and sulfur from alkali metal sulfides and polysulfides

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard; Alvare, Javier


    Alkali metals and sulfur may be recovered from alkali monosulfide and polysulfides in an electrolytic process that utilizes an electrolytic cell having an alkali ion conductive membrane. An anolyte solution includes an alkali monosulfide, an alkali polysulfide, or a mixture thereof and a solvent that dissolves elemental sulfur. A catholyte includes molten alkali metal. Applying an electric current oxidizes sulfide and polysulfide in the anolyte compartment, causes alkali metal ions to pass through the alkali ion conductive membrane to the catholyte compartment, and reduces the alkali metal ions in the catholyte compartment. Liquid sulfur separates from the anolyte solution and may be recovered. The electrolytic cell is operated at a temperature where the formed alkali metal and sulfur are molten.

  16. A negative ion source for alkali ions

    NARCIS (Netherlands)

    Vermeer, A.; Zwol, N.A. van


    An ion source is described which delivers negative alkali ions. With this source, which consists of a duoplasmatron and a charge exchange canal with alkali vapour, negative Li, Na and K ions are produced. The oven in which alkali metals are evaporated can reach temperatures up to 575°C.

  17. Alkali binding in hydrated Portland cement paste

    NARCIS (Netherlands)

    Chen, W.; Brouwers, H.J.H.


    The alkali-binding capacity of C–S–H in hydrated Portland cement pastes is addressed in this study. The amount of bound alkalis in C–S–H is computed based on the alkali partition theories firstly proposed by Taylor (1987) and later further developed by Brouwers and Van Eijk (2003). Experimental data

  18. Reaction kinetic model of the surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol on a CuP/Silica suface

    Energy Technology Data Exchange (ETDEWEB)

    Lomnicki, S.; Khachatryan, L.; Dellinger, B. [Louisiana State Univ., Baton Rouge (United States). Dept. of Chemistry


    One of the major challenges in developing predictive models of the surface mediated pollutant formation and fuel combustion is the construction of reliable reaction kinetic mechanisms and models. While the homogeneous, gas-phase chemistry of various light fuels such as hydrogen and methane is relatively well-known large uncertainties exist in the reaction paths of surface mediated reaction mechanisms for even these very simple species. To date, no detailed kinetic consideration of the surface mechanisms of formation of complex organics such as PCDD/F have been developed. In addition to the complexity of the mechanism, a major difficulty is the lack of reaction kinetic parameters (pre-exponential factor and activation energy) of surface reactions, Consequently, numerical studies of the surface-mediated formation of PCDD/F have often been incorporated only a few reactions. We report the development of a numerical multiple-step surface model based on experimental data of surface mediated (5% CuO/SiO2) conversion of 2-monochlorphenol (2-MCP) to PCDD/F under pyrolytic or oxidative conditions. A reaction kinetic model of the catalytic conversion of 2-MCP on the copper oxide catalyst under pyrolytic conditions was developed based on a detailed multistep surface reaction mechanism developed in our laboratory. The performance of the chemical model is assessed by comparing the numerical predictions with experimental measurements. SURFACE CHEMKIN (version 3.7.1) software was used for modeling. Our results confirm the validity of previously published mechanism of the reaction and provides new insight concerning the formation of PCDD/F formation in combustion processes. This model successfully explains the high yields of PCDD/F at low temperatures that cannot be explained using a purely gas-phase mode.

  19. Impact of alkali salts on the kinetics and microstructural development of cementitious systems


    Mota Gassó, Berta


    Supplementary cementitious materials (SCM) lower the environmental impact of cement and concrete but react more slowly than Portland cement, which therefore limits the levels of substitution possible as reasonable early strengths are necessary. One of the main factors affecting the reaction of the SCMs is the alkalinity of the pore solution. However, alkalis do not only affect SCMs, but also the clinker phases. It is generally accepted that alkalis accelerate the hydration of Portland cement ...

  20. Generation of basic centers in high-silica zeolites and their application in gas-phase upgrading of bio-oil. (United States)

    Keller, Tobias C; Rodrigues, Elodie G; Pérez-Ramírez, Javier


    High-silica zeolites have been reported recently as efficient catalysts for liquid- and gas-phase condensation reactions because of the presence of a complementary source of basicity compared to Al-rich basic zeolites. Herein, we describe the controlled generation of these active sites on silica-rich FAU, BEA, and MFI zeolites. Through the application of a mild base treatment in aqueous Na2CO3, alkali-metal-coordinating defects are generated within the zeolite whereas the porous properties are fully preserved. The resulting catalysts were applied in the gas-phase condensation of propanal at 673 K as a model reaction for the catalytic upgrading of pyrolysis oil, for which an up to 20-fold increased activity compared to the unmodified zeolites was attained. The moderate basicity of these new sites leads to a coke resistance superior to traditional base catalysts such as CsX and MgO, and comparable activity and excellent selectivity is achieved for the condensation pathways. Through strategic acid and base treatments and the use of magic-angle spinning NMR spectroscopy, the nature of the active sites was investigated, which supports the theory of siloxy sites as basic centers. This contribution represents a key step in the understanding and design of high-silica base catalysts for the intermediate deoxygenation of crude bio-oil prior to the hydrotreating step for the production of second-generation biofuels.

  1. 高铝粉煤灰中Al2O3与SiO2在碱溶液中的反应行为%Reaction behaviour of Al2O3 and SiO2 in high alumina coal fly ash during alkali hydrothermal process

    Institute of Scientific and Technical Information of China (English)

    蒋周青; 杨静; 马鸿文; 王乐; 马玺


    The reaction behaviours of Al2O3 and SiO2 in high alumina coal fly ash under various alkali hydrothermal conditions were studied. The means of XRD, XRF, FTIR and SEM were used to measure the mineral phase and morphology of the solid samples obtained by different alkali hydrothermal treatments as well as the leaching ratio of SiO2 to Al2O3 in alkali solution. The results showed that with the increase of the hydrothermal treating temperature from 75 to 160 °C, phillipsite-Na, zeolite A, zeolite P, and hydroxysodalite were produced sequentially while the mullite and corundum phase still remained. Zeolite P was massively formed at low-alkali concentration and the hydroxysodalite was predominantly obtained at high-alkali concentration. By the dissolution of aluminosilicate glass and the formation of zeolites together, the leaching efficiency of SiO2 can reach 42.13% with the mass ratio of Al2O3/SiO2 up to 2.19:1.%研究高铝粉煤灰中Al2O3与SiO2组分在NaOH碱液中不同水热条件下的反应行为。采用XRD、XRF、SEM、FTIR等测试方法对高铝粉煤灰碱溶液处理前后的物相组成和形貌变化进行表征,得到粉煤灰Al2O3和SiO2组分的溶出率变化规律。结果表明,高铝粉煤灰经75°C到160°C不同温度碱溶液处理后,颗粒表面硅铝玻璃相消失,依次生成钠型沸石、A型沸石、P型沸石及羟基方钠石,所含刚玉及莫来石相未被完全溶解。在低碱浓度溶液中P型沸石为主要生成相,高碱浓度下羟基方钠石为稳定的相。在铝硅玻璃体溶解和沸石相生成两种反应的共同作用下,粉煤灰中SiO2的溶出率可达42.13%,滤渣中Al2O3/SiO2质量比提高到2.19:1.

  2. Water Content of Lunar Alkali Fedlspar (United States)

    Mills, R. D.; Simon, J. I.; Wang, J.; Alexander, C. M. O'D.; Hauri, E. H.


    Detection of indigenous hydrogen in a diversity of lunar materials, including volcanic glass, melt inclusions, apatite, and plagioclase suggests water may have played a role in the chemical differentiation of the Moon. Spectroscopic data from the Moon indicate a positive correlation between water and Th. Modeling of lunar magma ocean crystallization predicts a similar chemical differentiation with the highest levels of water in the K- and Th-rich melt residuum of the magma ocean (i.e. urKREEP). Until now, the only sample-based estimates of water content of KREEP-rich magmas come from measurements of OH, F, and Cl in lunar apatites, which suggest a water concentration of water content of the magma ocean would have water contents of 320 ppm for the bulk Moon and 1.4 wt % for urKREEP from plagioclase in ferroan anorthosites. Results and interpretation: NanoSIMS data from granitic clasts from Apollo sample 15405,78 show that alkali feldspar, a common mineral in K-enriched rocks, can have approx. 20 ppm of water, which implies magmatic water contents of approx. 1 wt % in the high-silica magmas. This estimate is 2 to 3 orders of magnitude higher than that estimated from apatite in similar rocks. However, the Cl and F contents of apatite in chemically similar rocks suggest that these melts also had high Cl/F ratios, which leads to spuriously low water estimates from the apatite. We can only estimate the minimum water content of urKREEP (+ bulk Moon) from our alkali feldspar data because of the unknown amount of degassing that led to the formation of the granites. Assuming a reasonable 10 to 100 times enrichment of water from urKREEP into the granites produces an estimate of 100-1000 ppm of water for the urKREEP reservoir. Using the modeling of and the 100-1000 ppm of water in urKREEP suggests a minimum bulk silicate Moon water content between 2 and 20 ppm. However, hydrogen loss was likely very significant in the evolution of the lunar mantle. Conclusions: Lunar granites

  3. Effect of Na3PO4 on the Hydration Process of Alkali-Activated Blast Furnace Slag

    Directory of Open Access Journals (Sweden)

    Lukáš Kalina


    Full Text Available In recent years, the utilization of different non-traditional cements and composites has been increasing. Alkali-activated cementitious materials, especially those based on the alkali activation of blast furnace slag, have considerable potential for utilization in the building industry. However, alkali-slag cements exhibit very rapid setting times, which are too short in some circumstances, and these materials cannot be used for some applications. Therefore, it is necessary to find a suitable retarding admixture. It was shown that the sodium phosphate additive has a strong effect on the heat evolution during alkali activation and effectively retards the hydration reaction of alkali-activated blast furnace slag. The aim of the work is the suggestion of a reaction mechanism of retardation mainly based on Raman and X‑ray photoelectron spectroscopy.

  4. Catalytic Conversion of Bio-Oil to Oxygen-Containing Fuels by Acid-Catalyzed Reaction with Olefins and Alcohols over Silica Sulfuric Acid

    Directory of Open Access Journals (Sweden)

    Qingwen Wang


    Full Text Available Crude bio-oil from pine chip fast pyrolysis was upgraded with olefins (1-octene, cyclohexene, 1,7-octadiene, and 2,4,4-trimethylpentene plus 1-butanol (iso-butanol, t-butanol and ethanol at 120 °C using a silica sulfuric acid (SSA catalyst that possesses a good catalytic activity and stability. Gas chromatography-mass spectrometry (GC-MS, Fourier transform infrared spectroscopy (FT-IR and proton nuclear magnetic resonance (1H-NMR analysis showed that upgrading sharply increased ester content and decreased the amounts of levoglucosan, phenols, polyhydric alcohols and carboxylic acids. Upgrading lowered acidity (pH value rose from 2.5 to >3.5, removed the unpleasant odor and increased hydrocarbon solubility. Water content dramatically decreased from 37.2% to about 7.0% and the heating value increased from 12.6 MJ·kg−1 to about 31.9 MJ·kg−1. This work has proved that bio-oil upgrading with a primary olefin plus 1-butanol is a feasible route where all the original heating value of the bio-oil plus the added olefin and alcohol are present in the resulting fuel.

  5. Metal-silica sol-gel materials (United States)

    Stiegman, Albert E. (Inventor)


    The present invention relates to a single phase metal-silica sol-gel glass formed by the co-condensation of a transition metal with silicon atoms where the metal atoms are uniformly distributed within the sol-gel glass as individual metal centers. Any transition metal may be used in the sol-gel glasses. The present invention also relates to sensor materials where the sensor material is formed using the single phase metal-silica sol-gel glasses. The sensor materials may be in the form of a thin film or may be attached to an optical fiber. The present invention also relates to a method of sensing chemicals using the chemical sensors by monitoring the chromatic change of the metal-silica sol-gel glass when the chemical binds to the sensor. The present invention also relates to oxidation catalysts where a metal-silica sol-gel glass catalyzes the reaction. The present invention also relates to a method of performing oxidation reactions using the metal-silica sol-gel glasses. The present invention also relates to organopolymer metal-silica sol-gel composites where the pores of the metal-silica sol-gel glasses are filled with an organic polymer polymerized by the sol-gel glass.

  6. Positron-alkali atom scattering (United States)

    Mceachran, R. P.; Horbatsch, M.; Stauffer, A. D.; Ward, S. J.


    Positron-alkali atom scattering was recently investigated both theoretically and experimentally in the energy range from a few eV up to 100 eV. On the theoretical side calculations of the integrated elastic and excitation cross sections as well as total cross sections for Li, Na and K were based upon either the close-coupling method or the modified Glauber approximation. These theoretical results are in good agreement with experimental measurements of the total cross section for both Na and K. Resonance structures were also found in the L = 0, 1 and 2 partial waves for positron scattering from the alkalis. The structure of these resonances appears to be quite complex and, as expected, they occur in conjunction with the atomic excitation thresholds. Currently both theoretical and experimental work is in progress on positron-Rb scattering in the same energy range.

  7. Electron- and Photon-stimulated Desorption of Alkali Atoms from Lunar Sample and a Model Mineral Surface (United States)

    Yakshinskiy, B. V.; Madey, T. E.


    We report recent results on an investigation of source mechanisms for the origin of alkali atoms in the tenuous planetary atmospheres, with focus on non-thermal processes (photon stimulated desorption (PSD), electron stimulated desorption (ESD), and ion sputtering). Whereas alkaline earth oxides (MgO, CaO) are far more abundant in lunar samples than alkali oxides (Na2O, K2O), the atmosphere of the Moon contains easily measurable concentrations of Na and K, while Ca and Mg are undetected there; traces of Ca have recently been seen in the Moon's atmosphere (10-3 of Na). The experiments have included ESD, PSD and ion sputtering of alkali atoms from model mineral surface (amorphous SiO2) and from a lunar basalt sample obtained from NASA. The comparison is made between ESD and PSD efficiency of monovalent alkalis (Na, K) and divalent alkaline earths (Ba, Ca).The ultrahigh vacuum measurement scheme for ESD and PSD of Na atoms includes a highly sensitive alkali metal detector based on surface ionization, and a time-of-flight technique. For PSD measurements, a mercury arc light source (filtered and chopped) is used. We find that bombardment of the alkali covered surfaces by ultraviolet photons or by low energy electrons (E>4 eV) causes desorption of hot alkali atoms. This results are consistent with the model developed to explain our previous measurements of sodium desorption from a silica surface and from water ice: electron- or photon-induced charge transfer from the substrate to the ionic adsorbate causes formation of a neutral alkali atom in a repulsive configuration, from which desorption occurs. The two-electron charge transfer to cause desorption of divalent alkaline eath ions is a less likely process.The data support the suggestion that PSD by UV solar photons is a dominant source process for alkalis in the tenuous lunar atmosphere.

  8. Performance characterization of rigid polyurethane foam with refined alkali lignin and modified alkali lignin

    Institute of Scientific and Technical Information of China (English)

    LIU Zhi-ming; YU Fei; FANG Gui-zhen; YANG Hui-jun


    The two kinds of rigid polyurethane (PU) foams were prepared with respectively adding the refined alkali lignin and alkali lignin modified by 3-chloro-1,2-epoxypropane to be instead of 15% of the polyether glycol in weight. The indexes of mechanical performance, apparent density, thermal stability and aging resistance were separately tested for the prepared PU foams. The results show that the mechanical property, thermal insulation and thermal stability for PU foam with modified alkali lignin are excellent among two kinds of PU foams and control samples. The additions of the refined alkali lignin and modified alkali lignin to PU foam have little effect on the natural aging or heat aging resistance except for decreasing hot alkali resistance apparently. Additionally, the thermal conductivity of modified alkali lignin PU foam is lowest among two kinds of PU foams and control samples. The alkali lignin PU foam modified by 3-chloro-1,2-epoxypropane could be applied in the heat preservation field.

  9. Surface-crosslinked poly(3-mercaptopropyl)methylsiloxane-coatings on silica as new platform for low-bleed mass spectrometry-compatible functionalized stationary phases synthesized via thiol-ene click reaction. (United States)

    Zimmermann, Aleksandra; Horak, Jeannie; Sievers-Engler, Adrian; Sanwald, Corinna; Lindner, Wolfgang; Kramer, Markus; Lämmerhofer, Michael


    A thin functional film of poly(3-mercaptopropyl)methylsiloxane was coated onto vinyl-modified silica particles (5μm, 100Å pore size) and chemically crosslinked to the surface. Excess of thiol functionalities allow bonding of alkene containing ligands by thiol-ene click reaction in a second step (QN-VII). Besides that a single step surface modification procedure was established in which alkene functional ligands were directly added to the polysiloxane coating solution and thus, after evaporation of the solvent, crosslinking to the vinylized surface and bonding of chromatographic ligand to the thiolated polysiloxane film occur simultaneously in one step (QN-VI). Successful bonding of the polysiloxane film was confirmed for both approaches by (29)Si cross-polarization/magic angle spinning NMR spectra. The new surface functionalization concept can be utilized as a new platform for the preparation of various low-bleed, mass spectrometry-compatible stationary phases with a variety of functional ligands. The concept was demonstrated by thiol-ene click reaction with quinine carbamate and its subsequent use for enantiomer separation by HPLC-UV and HPLC-ESI-QTOF-MS of acidic chiral analytes. Chromatographic enantioselectivities were similar to a comparable brush-type CSP (QN-V0). The greatly reduced background signal in LC-MS, however, comes at expense of somewhat lower chromatographic efficiencies (C-term by factor of 2 larger compared to brush-type CSP). For quantitative analysis in single reaction monitoring (MRM(HR)) in high sensitivity mode, limit of detection and limit of quantification results are comparable for both surface-polymer modified CSPs, with only slightly higher values for the conventional brush-type CSP (QN-V0).

  10. Heterometallic aluminates: alkali metals trapped by an aluminium aryloxide claw. (United States)

    Muñoz, M Teresa; Cuenca, Tomás; Mosquera, Marta E G


    A series of heterometallic aluminium-alkali metal species [AlMMe2{2,6-(MeO)2C6H3O}2]n have been isolated for lithium, sodium and potassium. These compounds can be generated by the reaction of [AlMe2{2,6-(MeO)2C6H3O}]2 with the metallated phenol [M{2,6-(MeO)2C6H3O}]n or through the reaction of the mixture of AlMe3 and the appropriate alkali metal alkyl base with two equivalents of 2,6-dimethoxyphenol. In the heterometallic species obtained, the {AlMe2{2,6-(MeO)2C6H3O}2}(-) moiety is observed and could be described as a claw which fixes the alkali ion by the phenoxide oxygen atoms while the methoxy groups help to stabilize their coordination sphere. All compounds have been characterized by NMR spectroscopy and X-ray diffraction methods. Catalytic studies reveal that these compounds are active in ring-opening polymerization of L-lactide.

  11. Silica in Protoplanetary Disks

    CERN Document Server

    Sargent, B A; Tayrien, C; McClure, M K; Li, A; Basu, A R; Manoj, P; Watson, D M; Bohac, C J; Furlan, E; Kim, K H; Green, J D; Sloan, G C


    Mid-infrared spectra of a few T Tauri stars (TTS) taken with the Infrared Spectrograph (IRS) on board the Spitzer Space Telescope show prominent narrow emission features indicating silica (crystalline silicon dioxide). Silica is not a major constituent of the interstellar medium; therefore, any silica present in the circumstellar protoplanetary disks of TTS must be largely the result of processing of primitive dust material in the disks surrouding these stars. We model the silica emission features in our spectra using the opacities of various polymorphs of silica and their amorphous versions computed from earth-based laboratory measurements. This modeling indicates that the two polymorphs of silica, tridymite and cristobalite, which form at successively higher temperatures and low pressures, are the dominant forms of silica in the TTS of our sample. These high temperature, low pressure polymorphs of silica present in protoplanetary disks are consistent with a grain composed mostly of tridymite named Ada found...

  12. Multifunctional mesoporous silica catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Victor Shang-Yi; Tsai, Chih-Hsiang; Chen, Hung-Ting; Pruski, Marek; Kobayashi, Takeshi


    The present invention provides bifunctional silica mesoporous materials, including mesoporous silica nanoparticles ("MSN"), having pores modified with diarylammonium triflate and perfluoroaryl moieties, that are useful for the acid-catalyzed esterification of organic acids with organic alcohols.

  13. Facile Precursor for Synthesis of Silver Nanoparticles Using Alkali Treated Maize Starch (United States)

    El-Rafie, M. H.; Ahmed, Hanan B.; Zahran, M. K.


    Silver nanoparticles were prepared by using alkali treated maize starch which plays a dual role as reducer for AgNO3 and stabilizer for the produced AgNPs. The redox reaction which takes a place between AgNO3 and alkali treated starch was followed up and controlled in order to obtain spherical shaped silver nanoparticles with mean size 4–6 nm. The redox potentials confirmed the principle role of alkali treatment in increasing the reducibility of starch macromolecules. The measurements of reducing sugars at the end of reaction using dinitrosalicylic acid reagent (DNS) were carried out in order to control the chemical reduction reaction. The UV/Vis spectra show that an absorption peak, occurring due to surface plasmon resonance (SPR), exists at 410 nm, which is characteristic to yellow color of silver nanoparticles solution. The samples have been characterized by transmission electron microscopy (TEM), which reveal the nanonature of the particles. PMID:27433508

  14. Silica extraction from geothermal water (United States)

    Bourcier, William L; Bruton, Carol J


    A method of producing silica from geothermal fluid containing low concentration of the silica of less than 275 ppm includes the steps of treating the geothermal fluid containing the silica by reverse osmosis treatment thereby producing a concentrated fluid containing the silica, seasoning the concentrated fluid thereby producing a slurry having precipitated colloids containing the silica, and separating the silica from the slurry.

  15. Modified monolithic silica capillary for preconcentration of catecholamines

    Institute of Scientific and Technical Information of China (English)


    Preconcentration of catecholamines by the modified monolithic silica in the capillary was investigated in this study. In order to achieve a microchip-based method for determining catecholamines in the saliva,the monolithic silica was fabricated in the capillary and the monolithic silica was chemically modified by on-column reaction with phenylboronate. Different modified methods were compared. The concentration conditions were optimized. This study indicates the applicability of the modified monolithic sili...

  16. A quantitative method for silica flux evaluation (United States)

    Schonewille, R. H.; O'Connell, G. J.; Toguri, J. M.


    In the smelting of copper and copper/nickel concentrates, the role of silica flux is to aid in the removal of iron by forming a slag phase. Alternatively, the role of flux may be regarded as a means of controlling the formation of magnetite, which can severely hinder the operation of a furnace. To adequately control the magnetite level, the flux must react rapidly with all of the FeO within the bath. In the present study, a rapid method for silica flux evaluation that can be used directly in the smelter has been developed. Samples of flux are mixed with iron sulfide and magnetite and then smelted at a temperature of 1250 °C. Argon was swept over the reaction mixture and analyzed continuously for sulfur dioxide. The sulfur dioxide concentration with time was found to contain two peaks, the first one being independent of the flux content of the sample. A flux quality parameter has been defined as the height-to-time ratio of the second peak. The value of this parameter for pure silica is 5100 ppm/min. The effects of silica content, silica particle size, and silicate mineralogy were investigated. It was found that a limiting flux quality is achieved for particle sizes less than 0.1 mm in diameter and that fluxes containing feldspar are generally of a poorer quality. The relative importance of free silica and melting point was also studied using synthetic flux mixtures, with free silica displaying the strongest effect.

  17. A rapid method for the detection of foodborne pathogens by extraction of a trace amount of DNA from raw milk based on amino-modified silica-coated magnetic nanoparticles and polymerase chain reaction. (United States)

    Bai, Yalong; Song, Minghui; Cui, Yan; Shi, Chunlei; Wang, Dapeng; Paoli, George C; Shi, Xianming


    A method based on amino-modified silica-coated magnetic nanoparticles (ASMNPs) and polymerase chain reaction (PCR) was developed to rapidly and sensitively detect foodborne pathogens in raw milk. After optimizing parameters such as pH, temperature, and time, a trace amount of genomic DNA of pathogens could be extracted directly from complex matrices such as raw milk using ASMNPs. The magnetically separated complexes of genomic DNA and ASMNPs were directly subjected to single PCR (S-PCR) or multiplex PCR (M-PCR) to detect single or multiple pathogens from raw milk samples. Salmonella Enteritidis (Gram-negative) and Listeria monocytogenes (Gram-positive) were used as model organisms to artificially contaminate raw milk samples. After magnetic separation and S-PCR, the detection sensitivities were 8 CFU mL(-1) and 13 CFU mL(-1) respectively for these two types of pathogens. Furthermore, this method was successfully used to detect multiple pathogens (S. Enteritidis and L. monocytogenes) from artificially contaminated raw milk using M-PCR at sensitivities of 15 CFU mL(-1) and 25 CFU mL(-1), respectively. This method has great potential to rapidly and sensitively detect pathogens in raw milk or other complex food matrices.

  18. Study of cross-linking reactions induced by gamma rays in hybrid membranes of Bisphenol-A-Polysulfone and precipitated silica; Estudo da formacao de ligacoes cruzadas por irradiacao gama em membranas hibridas de Polissulfona Bisfenol-A e silica precipitada

    Energy Technology Data Exchange (ETDEWEB)

    Furtado Filho, Acacio Antonio M., E-mail: [Laboratorio de Quimica Militar, CTEx, Rio de Janeiro, RJ (Brazil); Gomes, Ailton de S.; Lopes, Lea; Benzi, Marcia R. [Instituto de Macromoleculas Professora Eloisa Mano, UFRJ, Rio de Janeiro, RJ (Brazil)


    In this work the bisphenol-A-polysulfone (PSF) was sulfonated using trimethyl silyl chlorosulfonate [(CH{sub 3}){sub 3}SiSO{sub 3}Cl] as a mild sulfonating agent in a homogeneous solution of dichloroethane. The sulfonation reaction was confirmed by acid-base titration and FTIR-spectroscopy analysis. The hybrid membranes were obtained by casting the sulfonated bisphenol-A-polysulfone (SPSF) and precipitated silica Tixosil{sup R} 333 solutions in N-N-dimethylacetamide. Cross-linking in the hybrid membranes was obtained by irradiation, with doses ranging from 5 to 30 kGy using gamma ray from a {sup 60}Co source. The water uptake and the swelling of the membranes were estimated by measuring the change in weight between dry and wet conditions. The conductivity of the membranes in acid form was measured with the ac impedance technique using a PGSTAT30 frequency response analyzer. The hybrid cross-linked membranes have conductivity close to 10-1{sup -1} at 100% RH and 80 deg C. Electrochemical performances, thermo-mechanical stability and low cost make this cross-linked SPSF hybrid membrane an attractive material for fuel cells using a proton exchange membrane. (author)

  19. Chitosan-Silica Hybrid Porous Membranes


    Pandis, C.; S. Madeira; Matos, J.,; Kyritsis, A.; Mano, J. F.; Ribelles, J.L. Gómez


    Chitosan–silica porous hybrids were prepared by a novel strategy in order to improve the mechanical properties of chitosan (CHT) in the hydrogel state. The inorganic silica phase was introduced by sol–gel reactions in acidic medium inside the pores of already prepared porous scaffolds. In order to make the scaffolds insoluble in acidic media chitosan was cross-linked by genipin (GEN) with an optimum GEN concentration of 3.2 wt.%. Sol–gel reactions took place with Tetraethylorthosilicate (TEOS...

  20. Silica triflate as an efficient reagent for the solvent-free synthesis of coumarins

    Institute of Scientific and Technical Information of China (English)


    Silica triflate, as a new silica-based reagent, can be used for the efficient synthesis of 4-substituted coumarins via a Pechmann reaction under solvent-free reaction conditions. All reactions were performed at 80 ℃ in good to high yields.

  1. Spinel Metal Oxide-Alkali Carbonate-Based, Low-Temperature Thermochemical Cycles for Water Splitting and CO_2 Reduction


    Xu, Bingjun; Bhawe, Yashodhan; Davis, Mark E.


    A manganese oxide-based, thermochemical cycle for water splitting below 1000 °C has recently been reported. The cycle involves the shuttling of Na+ into and out of manganese oxides via the consumption and formation of sodium carbonate, respectively. Here, we explore the combinations of three spinel metal oxides and three alkali carbonates in thermochemical cycles for water splitting and CO_2 reduction. Hydrogen evolution and CO_2 reduction reactions of metal oxides with a given alkali carbona...


    carbon fibers . Several economical and simple processes were developed for obtaining research quantities of silica surfaced carbon filaments. Vat dipping processes were utilized to deposit an oxide such as silica onto the surface and into the micropores of available carbon or graphite base fibers. High performance composite materials were prepared with the surface treated carbon fibers and various resin matrices. The ablative characteristics of these composites were very promising and exhibited fewer limitations than either silica or...treated

  3. Sonochemical synthesis of silica particles and their size control

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hwa-Min [Advanced Materials and Chemical Engineering, Catholic University of Daegu, Gyeongbuk 38430 (Korea, Republic of); Lee, Chang-Hyun [Electronic and Electrical Engineering, Catholic University of Daegu, Gyeongbuk 38430 (Korea, Republic of); Kim, Bonghwan, E-mail: [Electronic and Electrical Engineering, Catholic University of Daegu, Gyeongbuk 38430 (Korea, Republic of)


    Graphical abstract: - Highlights: • Silica particles were easily prepared by an ultrasound-assisted sol–gel method. • The particle size was controlled by the ammonium hydroxide/water molar ratio. • The size-controlled diameter of silica particles ranged from 40 to 400 nm. • The particles were formed in a relatively short reaction time. - Abstract: Using an ultrasound-assisted sol–gel method, we successfully synthesized very uniformly shaped, monodisperse, and size-controlled spherical silica particles from a mixture of ethanol, water, and tetraethyl orthosilicate in the presence of ammonia as catalyst, at room temperature. The diameters of the silica particles were distributed in the range from 40 to 400 nm; their morphology was well characterized by scanning electron microscopy. The silica particle size could be adjusted by choosing suitable concentrations of ammonium hydroxide and water, which in turn determined the nucleation and growth rates of the particles during the reaction. This sonochemical-based silica synthesis offers an alternative way to produce spherical silica particles in a relatively short reaction time. Thus, we suggest that this simple, low-cost, and efficient method of preparing uniform silica particles of various sizes will have practical and wide-ranging industrial applicability.

  4. Silica in higher plants. (United States)

    Sangster, A G; Hodson, M J


    Opaline silica deposits are formed by many vascular (higher) plants. The capacity of these plants for silica absorption varies considerably according to genotype and environment. Plant communities exchange silica between soil and vegetation, especially in warmer climates. Silica deposition in epidermal cell walls offers mechanical and protective advantages. Biogenic silica particles from plants are also implicated in the causation of cancer. Recent techniques are reviewed which may aid in the identification of plant pathways for soluble silica movement to deposition sites and in the determination of ionic environments. Botanical investigations have focused on silicification of cell walls in relation to plant development, using scanning and transmission electron microscopy combined with X-ray microanalysis. Silica deposition in macrohair walls of the lemma of canary grass (Phalaris) begins at inflorescence emergence and closely follows wall thickening. The structure of the deposited silica may be determined by specific organic polymers present at successive stages of wall development. Lowering of transpiration by enclosure of Phalaris inflorescences in plastic bags reduced silica deposition in macrohairs. Preliminary freeze-substitution studies have located silicon, as well as potassium and chloride, in the cell vacuole and wall deposition sites during initial silicification.

  5. Mesoporous Silica from Rice Husk Ash

    Directory of Open Access Journals (Sweden)

    V.R. Shelke


    Full Text Available Mesoporous silica is used as a raw material in several areas: in preparation of catalysts, in inks, as a concrete hardening accelerator, as a component of detergents and soaps, as a refractory constituent etc. Sodium silicate is produced by reacting rice hull ash (RHA with aqueous NaOH and silica is precipitated from the sodium silicate by acidification. In the present work, conversion of about 90% of silica contained in RHA into sodium silicate was achieved in an open system at temperatures of about 100 °C. The results showed that silica obtained from RHA is mesoporous, has a large surface area and small particle size. Rice Husk is usually mixed with coal and this mixture is used for firing boilers. The RHA therefore, usually contains carbon particles. Activated carbon embedded on silica has been prepared using the carbon already present in RHA. This carbon shows good adsorption capacity. ©2010 BCREC UNDIP. All rights reserved(Received: 25th April 2010, Revised: 17th June 2010, Accepted: 24th June 2010[How to Cite: V.R. Shelke, S.S. Bhagade, S.A. Mandavgane. (2010. Mesoporous Silica from Rice Husk Ash. Bulletin of Chemical Reaction Engineering and Catalysis, 5 (2: 63-67. doi:10.9767/bcrec.5.2.793.63-67][DOI:

  6. Nanosized alkali-metal-doped ethoxotitanate clusters. (United States)

    Chen, Yang; Trzop, Elzbieta; Makal, Anna; Sokolow, Jesse D; Coppens, Philip


    The synthesis and crystallographic characterization of alkali-metal-doped ethoxotitanate clusters with 28 and 29 Ti atoms as well as a new dopant-free Ti28 cluster are presented. The light-metal-doped polyoxotitanate clusters in which the alkali-metal atom is the critical structure-determining component are the largest synthesized so far. Calculations show that doping with light alkali atoms narrows the band gap compared with the nondoped crystals but does not introduce additional energy levels within the band gap.

  7. Synergistic capture mechanisms for alkali and sulfur species from combustion. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Peterson, T.W.; Shadman, F.; Wendt, J.O.L.; Mwabe, P.O.


    Experimental work was carried out on a 17 kW, 600 cm long, gas laboratory combustor, to investigate the post flame reactive capture of alkali species by kaolinite. Emphasis was on alkali/sorbent interactions occurring in flue gas at temperatures above the alkali dewpoint and on the formation of water insoluble reaction products. Time-temperature studies were carried out by injecting kaolinite at different axial points along the combustor. The effect of chlorine and sulfur on alkali capture was investigated by doping the flame with SO{sub 2} and Cl{sub 2} gases to simulate coal flame environments. Particle time and temperature history was kept as close as possible to that which would ordinarily be found in a practical boiler. Experiments designed to extract apparent initial reaction rates were carried using a narrow range, 1-2 {mu}m modal size sorbent, while, a coarse, multi size sorbent was used to investigate the governing transport mechanisms. The capture reaction has been proposed to be between alkali hydroxide and activated kaolinite, and remains so in the presence of sulfur and chlorine. The presence of sulfur reduces sodium capture by under 10% at 1300{degree}C. Larger reductions at lower temperatures are attributed to the elevated dewpoint of sodium ({approximately}850{degree}C) with subsequent reduction in sorbent residence time in the alkali gas phase domain. Chlorine reduces sodium capture by 30% across the temperature range covered by the present experiments. This result has been linked to thermodynamic equilibria between sodium hydroxide, sodium chloride and water.

  8. Petrogenesis of cogenetic silica-oversaturated and -undersaturated syenites of Abu Khruq ring complex, South Eastern Desert, Egypt (United States)

    Mogahed, Moustafa M.


    The upper Cretaceous Abu Khruq ring complex (ARC) is located in the South Eastern Desert of Egypt displays concentric zonation of syenitic rocks from quartz-rich syenite at the margin, through alkali feldspar syenite to nepheline syenite in the centre. The syenitic rocks occur with nepheline monzogabbro, volcanic rocks (phonolite and trachyte) and the quartz- and nepheline-bearing pegmatites. Rocks of contrasting composition (mafic and salic) exhibit sophisticate geometric relationships. The nepheline monzogabbroic rocks have pillowy xenoliths forms within the salic (nepheline syenite and quartz alkali feldspar syenite) rocks, suggesting synchronous emplacement of the mafic and salic magmas. Clinopyroxene analysis of mafic and salic plutonic rocks of the ARC revealed that the overall pyroxene trend suggesting that fractionation involved a late, progressive increase in Na, in a reaction of the type Ca Mg Fe2+↔Na Fe3+. The chemistry of the analysed amphiboles are compositionally similar to those from typical differentiated peralkaline suites. Geochemically, the complex is enriched in the LILE, HFSE and REE. The concentrations of the compatible elements (V, Sr and Ba) generally decrease with increasing silica, consistent with fractional crystallization. A generalised increase in the Nb/Ta from the nepheline monzogabbro to nepheline syenite compositions is attributed to titanite fractionation. All the rock samples show relative increment of the LREE content than the HREE indicating weak to steep fractionated REE patterns (La/Yb) from 9.43 to 10.86, and thus retaining the geochemical characteristics of anorogenic suites. The magma sources of ARC are not derived from normal primitive mantle. The early stages of differentiation involved extensive olivine and pyroxene fractionation, the fractionation of amphibole, titanite, magnetite, apatite and feldspar may have been involved in the genesis of the salic differentiated compositions. The deviation towards silica

  9. Synthesis of 4A molecular sieves from gangue with high iron and silica contents by iron removal and alkali melting activation%高铁高砂煤矸石除铁及碱融活化合成4A分子筛

    Institute of Scientific and Technical Information of China (English)

    孔德顺; 吴红; 毕迎鑫


    高铁高砂的劣质煤矸石经酸浸除铁和纯碱碱融活化处理后,除铁率达到96.8%,高岭石及石英砂被完全活化,煤矸石生成了可溶于碱液的中间产物霞石(NaAlSiO4)及活性偏高岭石,将其再进行水热晶化得到了4A分子筛.用XRF、XRD、SEM等对原矿、预处理产物和产品进行了检测.结果表明:产品为较纯净的4A分子筛,粒径小于2 μm,干基产品的钙离子交换量为295.5 mg CaCO3/g.%Poor quality gangue with high iron and silica contents was treated to remove iron impurity by acid leaching and activated by sodium carbonate melting , the iron removal ratio was up to 96.8%. Kaolinite and silica were activated completely,and gangue turned into intermediate product nepheline (NaAlSiO4 ) and active metakaolinite,4A molecular sieve s were obtained by hydrothermal crystallization. Green ore, pretreated material, and products were characterized by XRF, XRD and SEM etc.. Results showed that the products were pure 4A molecular sieve with particle size less than 2 μm and the Ca2+ ion exchange capacity of dry product was 295.5 mg CaCO3/g.

  10. Relaxation of quadrupole orientation in an optically pumped alkali vapour

    Energy Technology Data Exchange (ETDEWEB)

    Bernabeu, E.; Tornos, J.


    The relaxation of quadrupole orientation (alignment) in an optically pumped alkali vapour is theoretically studied by taking into account the relaxation processes by alkali-buffer gas, alkali-alkali with spin exchange and alkali-cell wall (diffusion process) collisions. The relaxation transients of the quadrupole orientation are obtained by introducing a first-order weak-pumping approximation (intermediate pumping) less restrictive than the usually considered (zeroth order) one.

  11. Milk Alkali and Hydrochlorothiazide: A Case Report

    Directory of Open Access Journals (Sweden)

    Babar Parvez


    Full Text Available Hypercalcemia is a relatively common clinical problem in both outpatient and inpatient settings. Primary pathophysiology is the entry of calcium that exceeds its excretion into urine or deposition in bone into circulation. Among a wide array of causes of hypercalcemia, hyperparathyroidism and malignancy are the most common, accounting for greater than 90 percent of cases. Concordantly, there has been a resurgence of milk-alkali syndrome associated with the ingestion of large amounts of calcium and absorbable alkali, making it the third leading cause of hypercalcemia (Beall and Scofield, 1995 and Picolos et al., 2005. This paper centers on a case of over-the-counter calcium and alkali ingestion for acid reflux leading to milk alkali with concordant use of thiazide diuretic for hypertension.

  12. Silica Refractory Bricks

    Institute of Scientific and Technical Information of China (English)

    Yu Lingyan; Peng Xigao


    @@ 1.Scope This standard specifies the classification,technical requirements,test methods,quality appraisal procedures,packing,marking,transportation,storage,and quality certificate of silica refractory bricks.This standard is applicable to silica refractory bricks with single weight≤40 kg.

  13. Crystalline Silica Primer (United States)



    Crystalline silica is the scientific name for a group of minerals composed of silicon and oxygen. The term crystalline refers to the fact that the oxygen and silicon atoms are arranged in a threedimensional repeating pattern. This group of minerals has shaped human history since the beginning of civilization. From the sand used for making glass to the piezoelectric quartz crystals used in advanced communication systems, crystalline silica has been a part of our technological development. Crystalline silica's pervasiveness in our technology is matched only by its abundance in nature. It's found in samples from every geologic era and from every location around the globe. Scientists have known for decades that prolonged and excessive exposure to crystalline silica dust in mining environments can cause silicosis, a noncancerous lung disease. During the 1980's, studies were conducted that suggested that crystalline silica also was a carcinogen. As a result of these findings, crystalline silica has been regulated under the Occupational Safety and Health Administration's (OSHA) Hazard Communication Standard (HCS). Under HCS, OSHAregulated businesses that use materials containing 0.1% or more crystalline silica must follow Federal guidelines concerning hazard communication and worker training. Although the HCS does not require that samples be analyzed for crystalline silica, mineral suppliers or OSHAregulated

  14. Economic assessment of biodiesel production: Comparison of alkali and biocatalyst processes

    Energy Technology Data Exchange (ETDEWEB)

    Jegannathan, Kenthorai Raman [Department of Biotechnology, School of Biotechnology and Health sciences, Karunya University, Coimbatore, 641114 (India); Eng-Seng, Chan; Ravindra, Pogaku [Centre of Materials and Minerals, School of Engineering and Information Technology, University Malaysia Sabah, 88999 Kotakinabalu, Sabah (Malaysia)


    This study deals with the economic assessment of biodiesel production using three catalytic processes (1) alkali (2) soluble enzyme and (3) immobilized enzyme. All the processes were considered to be operated at batch mode with a production capacity of 10{sup 3} tonne. Biodiesel production cost using alkali catalyst process was found to be lowest ($ 1166.67/tonne) compared to soluble lipase catalyst ($ 7821.37/tonne) and immobilized lipase catalyst ($ 2414.63/tonne) process. The higher production cost was due to the higher cost of the enzyme and the higher reaction time of enzymatic process. However, reuse of immobilized catalyst decreased the production cost drastically unlike soluble enzyme catalyst. (author)

  15. An exploratory study of alkali sulfate aerosol formation during biomass combustion

    DEFF Research Database (Denmark)

    Løj, Lusi Hindiyarti; Frandsen, Flemming; Livbjerg, Hans;


    It is still in discussion to what extent alkali sulfate aerosols in biomass combustion are formed in the gas phase by a homogeneous mechanism or involve heterogeneous or catalyzed reactions. The present study investigates sulfate aerosol formation based on calculations with a detailed gas phase...... mechanism. The modeling predictions are compared to data from laboratory experiments and entrained flow reactor experiments available in the literature. The analysis support that alkali sulfate aerosols are formed from homogeneous nucleation following a series of steps occurring in the gas phase. The rate...

  16. Oxidation of the Boltysh deposit shale with atmosperic oxygen in a water-alkali medium

    Energy Technology Data Exchange (ETDEWEB)

    Proskuryakov, V.A.; Soloveichik, Z.V.; Yakovlev, V.I.


    Conditions for obtaining organic acids from Boltysh oil shale containing 43.12 percent organic matter were studied by oxidizing the shale with air in a water-alkali medium at different temperatures, oxidation times, and alkali consumptions. Maximum yield of 42.6 percent of high molecular acids was obtained at 175/sup 0/C; the yield of dibasic acids increased to 22 percent with increasing temperature. The degree of oxidation of shale kerogen increased from 55.6 to 79.6 percent with increase in oxidation time from 1 to 5 hours, the reaction proceeding stepwise from shale kerogen to high-molecular acids to dibasic acids.

  17. Alkali-metalated forms of thiacalix[4]arenes. (United States)

    Zeller, Jürgen; Radius, Udo


    The alkali metal salts [TCALi4] (1), [TCANa4] (2), and [TCALK4] (3) of fully deprotonated p-tert-butyltetrathiacalix[4]arene (H(4)TCA) are readily available from the reactions of thiacalix[4]arene and n-BuLi, NaH, or KH as deprotonating reagents. Crystals of the sodium salts 2 and the potassium salt 3 suitable for X-ray diffraction were obtained in the form of the pyridine solvates [(TCA)2Na8.8py] (2.8py) and [(TCA)2K(8).8py] (3.8py). These molecules are dimers in the solid state but are structurally not related. In addition, the reaction of H(4)TCA and lithium hydroxide afforded the structurally characterized complex [(TCA)Li5(OH).4THF] (4). The molecular structure of 4 as well as the structures of 2.8py and 3.8py reveal a close relationship to the corresponding alkali metal salts of the calix[4]arenes.

  18. A bioinspired strategy for surface modification of silica nanoparticles (United States)

    Tian, Jianwen; Zhang, Haoxuan; Liu, Meiying; Deng, Fengjie; Huang, Hongye; Wan, Qing; Li, Zhen; Wang, Ke; He, Xiaohui; Zhang, Xiaoyong; Wei, Yen


    Silica nanoparticles have become one of the most promising nanomaterials for a vast of applications. In this work, a novel strategy for surface modification of silica nanoparticles has been developed for the first time via combination of mussel inspired chemistry and Michael addition reaction. In this procedure, thin polydopamine (PDA) films were first coated on the bare silica nanoparticles via self-polymerization of dopamine in alkaline condition. And then amino-containing polymers were introduced onto the PDA coated silica nanoparticles through Michael addition reaction, that are synthesized from free radical polymerization using poly(ethylene glycol) methyl methacrylate (PEGMA) and N-(3-aminopropyl) methacrylamide (NAPAM) as monomers and ammonium persulfate as the initiator. The successful modification of silica nanoparticles was evidenced by a series of characterization techniques. As compared with the bare silica nanoparticles, the polymers modified silica nanoparticles showed remarkable enhanced dispersibility in both aqueous and organic solution. This strategy is rather simple, effective and versatile. Therefore, it should be of specific importance for further applications of silica nanoparticles and will spark great research attention of scientists from different fields.

  19. Pure zeolite synthesis from silica extracted from coal fly ashes

    Energy Technology Data Exchange (ETDEWEB)

    Moreno, N.; Querol, X.; Plana, F.; Andres, J.M.; Janssen, M.; Nugteren, H. [CSIC, Barcelona (Spain). Inst. Earth Science ' Jaume Almera'


    Pure zeolites can be synthesised from silica extracted from fly ash by alkaline leaching. If the process is optimised the solid residue arising from this extraction may also contain a relatively high content of zeolitic material mixed with residual fly ash components. Both the pure and the impure zeolitic material have a high potential for application in waste-water and flue gas-cleaning technologies. The silica extraction potential of 23 European coal fly ashes covering most of the possible fly ash types is investigated in this study. Optimisation of leaching processes, by varying temperature, time and alkali/fly ash rates, permitted extraction yields up to 140 g of SiO{sub 2} per kg using a single step process, but the extraction yields may reach up to 210 g kg{sup -1} by applying thermal pre-treatments prior to the extraction. The solid residue arising from the silica extraction experiments shows a high NaP1 zeolite content. A high Si/Al ratio of the glass matrix, the occurrence of easily soluble silica phases in the original fly ash and a high reactive surface area were found to be the major parameters influencing silica extraction. High purity 4A and X zeolitic material was obtained by combining the silica extracts from the Meirama fly ash and a waste solution from the Al-anodising industry. The results allowed conversion of the silica extraction yields to an equivalent 630 g of pure 4A-X zeolite per kg of fly ash with a cation exchange capacity of 4.7 meq g{sup -1}.

  20. Optimization of silica silanization by 3-aminopropyltriethoxysilane. (United States)

    Howarter, John A; Youngblood, Jeffrey P


    Thin films of 3-aminopropyltriethoxysilane (APTES) are commonly used to promote adhesion between silica substrates and organic or metallic materials with applications ranging from advanced composites to biomolecular lab-on-a-chip. Unfortunately, there is confusion as to which reaction conditions will result in consistently aminated surfaces. A wide range of conflicting experimental methods are used with researchers often assuming the creation of smooth self-assembled monolayers. A range of film morphologies based on the film deposition conditions are presented here to establish an optimized method of APTES film formation. The effect of reaction temperature, solution concentration, and reaction time on the structure and morphology was studied for the system of APTES on silica. Three basic morphologies were observed: smooth thin film, smooth thick film, and roughened thick film.

  1. Device and method for upgrading petroleum feedstocks and petroleum refinery streams using an alkali metal conductive membrane

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard; Alvare, Javier


    A reactor has two chambers, namely an oil feedstock chamber and a source chamber. An ion separator separates the oil feedstock chamber from the source chamber, wherein the ion separator allows alkali metal ions to pass from the source chamber, through the ion separator, and into the oil feedstock chamber. A cathode is at least partially housed within the oil feedstock chamber and an anode is at least partially housed within the source chamber. A quantity of an oil feedstock is within the oil feedstock chamber, the oil feedstock comprising at least one carbon atom and a heteroatom and/or one or more heavy metals, the oil feedstock further comprising naphthenic acid. When the alkali metal ion enters the oil feedstock chamber, the alkali metal reacts with the heteroatom, the heavy metals and/or the naphthenic acid, wherein the reaction with the alkali metal forms inorganic products.

  2. Controlled Reactions between Ultracold Alkali and Metastable Helium Atoms

    CERN Document Server

    Flores, Adonis Silva; Knoop, Steven


    In an ultracold, optically trapped mixture of $^{87}$Rb and metastable triplet $^4$He atoms we have studied trap loss for different spin-state combinations, for which interspecies Penning ionization is the main two-body loss process. We observe long trapping lifetimes for the purely quartet spin-state combination, indicating strong suppression of Penning ionization loss by at least two orders of magnitude. For the other spin-mixtures we observe short lifetimes that depend linearly on the doublet character of the entrance channel. We compare the extracted loss rate coefficient with recent predictions of multichannel quantum-defect theory for reactive collisions involving a strong exothermic loss channel and find near-universal loss for doublet scattering. Our work demonstrates control of reactive collisions by internal atomic state preparation, which also implies magnetic field tunability.

  3. Palm Ash as an Alternative Source for Silica Production

    Directory of Open Access Journals (Sweden)

    Pa Faizul Che


    Full Text Available Agricultural wastes such as palm ash and rice husk have a possibility to be used as a useful renewable source for the production of silica (SiO2. Extensive researches have been carried out to extract silica from agricultural wastes such as rice husk, due to silica as a useful raw material for industrial application. In this study, the environmentally benign and economically effective process to produce SiO2 materials from palm ash has been established by using citric acid leaching, not the conventional strong acids. Results showed that silica can be extracted from palm ash using the citric acid leaching method under the optimum extracting conditions with 700 °C of solution temperature, 60 minutes of reaction time and concentration of citric acid of more than 2 %. The purity of silica extracted is more than 90 %.

  4. Supported -pyrrolidine-2-carboxylic acid-4-hydrogen sulphate on silica gel as an economical and efficient catalyst for the one-pot preparation of -acetamido ketones via a four-component condensation reaction

    Indian Academy of Sciences (India)

    Arash Ghorbani-Choghamarani; Parisa Zamani


    An efficient, one-pot, four-component condensation of aldehydes, acetophenone (or propiophenone), acetyl chloride and acetonitrile in the presence of catalytic amounts of -pyrrolidine-2-carboxylic acid-4-hydrogen sulphate (supported on silica gel), a green and non-toxic catalyst, is described for the preparation of -acetamido ketones in good to excellent yields.

  5. Kinetics of silica-phase transitions

    Energy Technology Data Exchange (ETDEWEB)

    Duffy, C.J.


    In addition to the stable silica polymorph quartz, several metastable silica phases are present in Yucca Mountain. The conversion of these phases to quartz is accompanied by volume reduction and a decrease in the aqueous silica activity, which may destabilize clinoptilolite and mordenite. The primary reaction sequence for the silica phases is from opal or glass to disordered opal-CT, followed by ordering of the opal-CT and finally by the crystallization of quartz. The ordering of opal-CT takes place in the solid state, whereas the conversion of opal-CT takes place through dissolution-reprecipitation involving the aqueous phase. It is proposed that the rate of conversion of opal-CT to quartz is controlled by diffusion of defects out of a disordered surface layer formed on the crystallizing quartz. The reaction rates are observed to be dependent on temperature, pressure, degree of supersaturation, and pH. Rate equations selected from the literature appear to be consistent with observations at Yucca Mountain.

  6. Preparation and characterization of carbosilane denddmer-bonded silica gel and its use in LC

    Institute of Scientific and Technical Information of China (English)

    Chen Guowen; Zhao Shigui; Feng Shengyu


    Divergently synthesized carbosilane dendrimers generations 1(G1) and 2 (G2) with allyl end groups were bonded onto silica gel.Reactions between the dendrimers and acid-processed silica gel took place,with toluene reflux and organic base as catalyst.Chemically bonded silica gel was characterized by transmission electron microscopy (TEM),infrared (IR),and other methods.The chemically modified silica gels were packed into high-pressure liquid chromatography (HPLC) column and their separation characters were evaluated.G2-bonded silica gel was effective in separating homologous compounds of alcohol, alkyl-substituted benzene,N-substituted benzene,metacrylic acid ester and phthalate.

  7. Mechanical and microstructural properties of alkali-activated fly ash geopolymers. (United States)

    Komljenović, M; Bascarević, Z; Bradić, V


    This paper investigates the properties of geopolymer obtained by alkali-activation of fly ash (FA), i.e. the influence of characteristics of the representative group of FA (class F) from Serbia, as well as that of the nature and concentration of various activators on mechanical and microstructural properties of geopolymers. Aqueous solutions of Ca(OH)(2), NaOH, NaOH+Na(2)CO(3), KOH and sodium silicate (water glass) of various concentrations were used as alkali activators. It was established that the nature and concentration of the activator was the most dominant parameter in the alkali-activation process. In respect of physical characteristics of FA, the key parameter was fineness. The geopolymer based on FA with the highest content of fine particles (<43 microm), showed the highest compressive strength in all cases. Regardless of FA characteristics, nature and concentration of the activator, the alkali-activation products were mainly amorphous. The formation of crystalline phases (zeolites) occurred in some cases, depending on the reaction conditions. The highest compressive strength was obtained using sodium silicate. Together with the increase of sodium silicate SiO(2)/Na(2)O mass ratio, the atomic Si/Al ratio in the reaction products was also increased. Under the experimental conditions of this investigation, high strength was directly related to the high Si/Al ratio.

  8. Selection of non-adsorbing alkali components

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.D.; Natesan, K.; Swift, W.M.


    This project consists of three phases of laboratory experimental study. In phase I (screening), eight candidate materials, 304SS (serves as a base material for comparison), Hastelloy C-276, Hastelloy X, Haynes No. 188, Allonized 304SS, Pt-coated 304SS, and ceramic-coated 304SS, will be subjected to atmospheric TGA study under the simulated PFBC (oxidizing) environment with and without alkali vapor doping. Each candidate material will be evaluated for its resistance toward alkali-vapor capture. In addition, a post-test metallographic characterization of the sample will be performed to obtain a better understanding of the alkali capture mechanism and material behavior. The material(s) with little or no alkali-vapor adsorption will be selected as the promising material(s) for the Phase II study. In Phase II, the promising material(s) will be further tested in the TGA under elevated pressure to simulate the PFBC environment (in terms of temperature, pressure, and gas composition). The effect of pressure on the extent of alkali-vapor adsorption will be evaluated, and the test samples will be metallographically characterized. The most promising candidate material(s) will be identified and recommended for further tesfing in the actual PFBC environment. In Phase III, four materials will be selected from the eight candidate materials screened in the PFBC environment and will be evaluated for their alkali-vapor capture by atmospheric TGA under the coal gasification fuel gas (reducing) environment. The tested samples will also be metallographically characterized. The most promising material(s) will be identified and recommended for further testing in the actual coal gasification environment.

  9. Selection of non-adsorbing alkali components

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.D.; Natesan, K.; Swift, W.M.


    This project consists of three phases of laboratory experimental study. In phase I (screening), eight candidate materials, 304SS (serves as a base material for comparison), Hastelloy C-276, Hastelloy X, Haynes No. 188, Allonized 304SS, Pt-coated 304SS, and ceramic-coated 304SS, will be subjected to atmospheric TGA study under the simulated PFBC (oxidizing) environment with and without alkali vapor doping. Each candidate material will be evaluated for its resistance toward alkali-vapor capture. In addition, a post-test metallographic characterization of the sample will be performed to obtain a better understanding of the alkali capture mechanism and material behavior. The material(s) with little or no alkali-vapor adsorption will be selected as the promising material(s) for the Phase II study. In Phase II, the promising material(s) will be further tested in the TGA under elevated pressure to simulate the PFBC environment (in terms of temperature, pressure, and gas composition). The effect of pressure on the extent of alkali-vapor adsorption will be evaluated, and the test samples will be metallographically characterized. The most promising candidate material(s) will be identified and recommended for further tesfing in the actual PFBC environment. In Phase III, four materials will be selected from the eight candidate materials screened in the PFBC environment and will be evaluated for their alkali-vapor capture by atmospheric TGA under the coal gasification fuel gas (reducing) environment. The tested samples will also be metallographically characterized. The most promising material(s) will be identified and recommended for further testing in the actual coal gasification environment.

  10. Microstructural and Mechanical Properties of Alkali Activated Colombian Raw Materials

    Directory of Open Access Journals (Sweden)

    Maria Criado


    Full Text Available Microstructural and mechanical properties of alkali activated binders based on blends of Colombian granulated blast furnace slag (GBFS and fly ash (FA were investigated. The synthesis of alkali activated binders was conducted at 85 °C for 24 h with different slag/fly ash ratios (100:0, 80:20, 60:40, 40:60, 20:80, and 0:100. Mineralogical and microstructural characterization was carried out by means of X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FTIR, Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX and Nuclear magnetic resonance (NMR. Mechanical properties were evaluated through the compressive strength, modulus of elasticity and Poisson’s ratio. The results show that two different reaction products were detected in the slag/fly ash mixtures, a calcium silicate hydrate with Al in its structure (C-A-S-H gel and a sodium aluminosilicate hydrate (N-A-S-H gel with higher number of polymerized species and low content in Ca. It was found that with the increase of the amount of added slag, the amount of C-A-S-H gel increased and the amount of N-A-S-H gel decreased. The matrix was more dense and compact with almost absence of pores. The predominance of slag affected positively the compressive strength, Young’s modulus and Poisson’s ratio, with 80% slag and 20% fly ash concrete being the best mechanical performance blend.

  11. Molten salt synthesis of mullite nanowhiskers using different silica sources

    Institute of Scientific and Technical Information of China (English)

    Tao Yang; Peng-long Qiu; Mei Zhang; Kuo-Chih Chou; Xin-mei Hou; Bai-jun Yan


    Mullite nanowhiskers with Al-rich structure were prepared by molten salt synthesis at 1000°C for 3 h in air using silica, amor-phous silica, and ultrafine silica as the silica sources. The phase and morphology of the synthesized products were investigated by X-ray dif-fraction, scanning electron microscopy, energy dispersive spectroscopy, and transmission electron microscopy. A thermogravimetric and differential thermal analysis was carried out to determine the reaction mechanism. The results reveal that the silica sources play an important role in determining the morphology of the obtained mullite nanowhiskers. Clusters and disordered arrangements are obtained using common silica and amorphous silica, respectively, whereas the use of ultrafine silica leads to highly ordered mullite nanowhiskers that are 80−120 nm in diameter and 20−30μm in length. Considering the growth mechanisms, mullite nanowhiskers in the forms of clusters and highly ordered arrangements can be attributed to heterogeneous nucleation, whereas disordered mullite nanowhiskers are obtained by homogenous nuclea-tion.

  12. Synthesis of silica nanosphere from homogeneous and heterogeneous systems

    Indian Academy of Sciences (India)

    N Venkatathri


    Silica nanosphere was synthesized using homogeneous and heterogeneous systems, respectively. In homogeneous system, silica spheres were synthesized without cetyltrimethylammonium bromide (CTABr), which gave bimodal particle size and lower yield (77%). To improve the yield, CTABr was added and found that the yield was very high (100%). The particle was in nm range, but the particle sizes are bimodal. To avoid it, reaction in heterogeneous system using CTABr was carried out. Nanosized silica sphere with uniform size (yield, 94%) was observed. Homogeneous system contains a mixture of ethanol, water, aqueous ammonia and tetraethylorthosilicate (TEOS). In the case of heterogeneous system, only ethanol was absent.

  13. Silica containing highly porous alumina ceramic (United States)

    Svinka, R.; Svinka, V.; Zake, I.


    Porous alumina ceramic were produced by slip casting of aqueous alumina slurry with added small amount of metallic aluminium powder. Pores form in result of chemical reaction of aluminum with water by hydrogen gas evolution reaction and solidification of suspension. Porosity of such materials sintered at a temperature of 1600 - 1750°C varies from 60 to 90%. Pore size distribution and mechanical strength of these materials depend largely on the grain size of used raw materials. The major part of pores in the materials produced without additive of silica are larger than 10 ±m, but with 5 - 10 wt.% additive of silica in the raw mix pore size decreases considerably. The sintering shrinkage decreases to 2.5%. Coefficient of thermal expansion equally decreases from 8.9-10-6 K-1 to 7.1 10-6 K-1 and classification temperature increases to 1600°C, while deformation at high temperature decreases considerably.

  14. Plackett-Burman experimental design for bacterial cellulose-silica composites synthesis. (United States)

    Guzun, Anicuta Stoica; Stroescu, Marta; Jinga, Sorin Ion; Voicu, Georgeta; Grumezescu, Alexandru Mihai; Holban, Alina Maria


    Bacterial cellulose-silica hybrid composites were prepared starting from wet bacterial cellulose (BC) membranes using Stöber reaction. The structure and surface morphology of hybrid composites were examined by FTIR and SEM. The SEM pictures revealed that the silica particles are attached to BC fibrils and are well dispersed in the BC matrix. The influence of silica particles upon BC crystallinity was studied using XRD analysis. Thermogravimetric (TG) analysis showed that the composites are stable up to 300°C. A Plackett-Burman design was applied in order to investigate the influence of process parameters upon silica particle sizes and silica content of BC-silica composites. The statistical model predicted that it is possible for silica particles size to vary the synthesis parameters in order to obtain silica particles deposed on BC membranes in the range from 34.5 to 500 nm, the significant parameters being ammonia concentration, reaction time and temperature. The silica content also varies depending on process parameters, the statistical model predicting that the most influential parameters are water-tetraethoxysilane (TEOS) ratio and reaction temperature. The antimicrobial behavior on Staphylococcus aureus of BC-silica composites functionalized with usnic acid (UA) was also studied, in order to create improved surfaces with antiadherence and anti-biofilm properties.

  15. Positronium impact ionization of Alkali atoms

    CERN Document Server

    Ghosh, D


    Target ionization processes of alkali atoms by Positronium impact are investigated. Calculations are performed in the frame work of model potential formalism using the Coulomb distorted eikonal approximation. Interesting qualitative features are noted both in the scattered Ps and the ejected electron distributions in differential as well as double differential levels of the collision cross sections.

  16. Chlorate reduction in the brine circuit of a chlor-alkali electrolysis. Chlorat-Reduktion im Solekreislauf einer Chlor-Alkali-Elektrolyse

    Energy Technology Data Exchange (ETDEWEB)

    Rodermund, R.


    The influence of reactant concentrations and temperature on the rate and selectivity of the chlorate/hydrochloric acid reaction was determined experimentally. A model equation system was derived on the basis of a reaction mechanism describing the reaction between chlorate and hydrochloric acid at high H/sup +/ and Cl/sup -/ concentrations in the temperature range between 40 and 90/sup 0/C. The reaction of chlorate and hydrochloric acid was found to be sufficient to maintain a low chlorate level in the brine circuit of a chlor-alkali electrolysis. ClO/sub 2/ formation is negligible if suitable reaction conditions are chosen. Further, a model equation based on Henry's law was established for the solubility of ClO/sub 2/ in mixed solutions of HCl and NaCl in the temperature range of 40 to 90/sup 0/C.

  17. Theory of metal atom-water interactions and alkali halide dimers (United States)

    Jordan, K. D.; Kurtz, H. A.


    Theoretical studies of the interactions of metal atoms with water and some of its isoelectronic analogs, and of the properties of alkali halides and their aggregates are discussed. Results are presented of ab initio calculations of the heats of reaction of the metal-water adducts and hydroxyhydrides of Li, Be, B, Na, Mg, and Al, and of the bond lengths and angles an; the heats of reaction for the insertion of Al into HF, H2O, NH3, H2S and CH3OH, and Be and Mg into H2O. Calculations of the electron affinities and dipole moments and polarizabilities of selected gas phase alkali halide monomers and dimers are discussed, with particular attention given to results of calculations of the polarizability of LiF taking into account electron correlation effects, and the polarizability of the dimer (LiF)2.

  18. Selective and regular localization of accessible Pt nanoparticles inside the walls of an ordered silica: Application as a highly active and well-defined heterogeneous catalyst for propene and styrene hydrogenation reactions

    KAUST Repository

    Boualleg, Malika


    We describe here an original methodology related to the "build-the-bottle-around-the-ship" approach yielding a highly ordered silica matrix containing regularly distributed Pt nanoparticles (NPs) located inside the silica walls, Pt@{walls}SiO2. The starting colloidal solution of crystalline Pt nanoparticles was obtained from Pt(dba)2 (dba = dibenzylidene acetone) and 3-chloropropylsilane. The resulting nanoparticles (diameter: 2.0 ± 0.4 nm determined by HRTEM) resulted hydrophilic. The NPs present in the THF colloidal solution were incorporated inside the walls of a highly ordered 2D hexagonal mesoporous silica matrix via sol-gel process using a templating route with tetraethylorthosilicate, TEOS, as the silica source, and block copolymer (EthyleneOxide) 20(PropyleneOxide)70(EthyleneOxide)20 (Pluronic P123) as the structure-directing agent. Low-temperature calcination of the crude material at 593 K led to the final solid Pt@{walls}SiO2. Characterization by IR, HRTEM, BF-STEM and HAADF-STEM, SAXS, WAXS, XRD, XPS, H2 chemisorption, etc. of Pt@{walls}SiO2 confirmed the 2D hexagonal structuration and high mesoporosity (870 m2/g) of the material as well as the presence of stable 2-nm-sized crystalline Pt(0) NPs embedded inside the walls of the silica matrix. The material displayed no tendency to NPs sintering or leaching (Pt loading 0.3 wt.%) during its preparation. Pt@{walls}SiO2 was found to be a stable, selective and highly active hydrogenation catalyst. The catalytic performances in propene hydrogenation were tested under chemical regime conditions in a tubular flow reactor (278 K, propene/H2/He = 20/16/1.09 cm3/min, P tot = 1 bar) and were found superior to those of an homologous solid containing Pt NPs along its pore channels Pt@{pores}SiO2 and to those of a classical industrial catalysts Pt/Al2O3, (TOF = 2.3 s-1 vs. TOF = 0.90 and 0.92 s-1, respectively, calculated per surface platinum atoms). Pt@{walls}SiO2 also catalyzes fast and selective styrene

  19. Layer-by-layer synthesis of mechanically robust solvent-permeable silica nanoshells. (United States)

    Whitaker, Kathryn A; Furst, Eric M


    A layer-by-layer (LbL) synthesis of mechanically robust micrometer-diameter nanoshell silica was developed. Silica was templated onto polstyrene latex particles using a modified Stöber synthesis. Each subsequent silica layer was deposited after adsorbing cationic polymer poly(allylamine) hydrochloride. The silica shell grew approximately 30 nm for each reaction step. The polystyrene-silica core-shell particles were calcined at 500 °C to remove the latex core. The synthesis was adapted to nonspherical shapes using anisotropic polystyrene dicolloids as templates. The silica nanoshells were functionalized to render them organophilic or fluorescent. The rates at which water, ethanol, and aqueous sucrose solution (60% w/w) permeate the silica shells were compared using spectrophotometry and conductivity measurements. The rate of solvent uptake ranged between under 1 h to over 1 week depending on the surface chemistry of the nanoshells.

  20. Fractals of Silica Aggregates

    Institute of Scientific and Technical Information of China (English)

    ZhinhongLi; DongWu; Yuhansun; JunWang; YiLiu; BaozhongDong; Zhinhong


    Silica aggregates were prepared by base-catalyzed hydrolysis and condensation of alkoxides in alcohol.Polyethylene glycol(PEG) was used as organic modifier.The sols were characterized using Small Angle X-ray Scattering (SAXS) with synchrotron radiation as X-ray source.The structure evolution during the sol-gel process was determined and described in terms of the fractal geometry.As-produced silica aggregates were found to be mass fractals.The fractl dimensions spanned the regime 2.1-2.6 corresponding to more branched and compact structures.Both RLCA and Eden models dominated the kinetic growth under base-catalyzed condition.

  1. Structural and Magnetic Diversity in Alkali-Metal Manganate Chemistry: Evaluating Donor and Alkali-Metal Effects in Co-complexation Processes. (United States)

    Uzelac, Marina; Borilovic, Ivana; Amores, Marco; Cadenbach, Thomas; Kennedy, Alan R; Aromí, Guillem; Hevia, Eva


    By exploring co-complexation reactions between the manganese alkyl Mn(CH2SiMe3)2 and the heavier alkali-metal alkyls M(CH2SiMe3) (M=Na, K) in a benzene/hexane solvent mixture and in some cases adding Lewis donors (bidentate TMEDA, 1,4-dioxane, and 1,4-diazabicyclo[2,2,2] octane (DABCO)) has produced a new family of alkali-metal tris(alkyl) manganates. The influences that the alkali metal and the donor solvent impose on the structures and magnetic properties of these ates have been assessed by a combination of X-ray, SQUID magnetization measurements, and EPR spectroscopy. These studies uncover a diverse structural chemistry ranging from discrete monomers [(TMEDA)2 MMn(CH2SiMe3)3] (M=Na, 3; M=K, 4) to dimers [{KMn(CH2SiMe3)3 ⋅C6 H6}2] (2) and [{NaMn(CH2SiMe3)3}2 (dioxane)7] (5); and to more complex supramolecular networks [{NaMn(CH2SiMe3)3}∞] (1) and [{Na2Mn2 (CH2SiMe3)6 (DABCO)2}∞] (7)). Interestingly, the identity of the alkali metal exerts a significant effect in the reactions of 1 and 2 with 1,4-dioxane, as 1 produces coordination adduct 5, while 2 forms heteroleptic [{(dioxane)6K2Mn2 (CH2SiMe3)4(O(CH2)2OCH=CH2)2}∞] (6) containing two alkoxide-vinyl anions resulting from α-metalation and ring opening of dioxane. Compounds 6 and 7, containing two spin carriers, exhibit antiferromagnetic coupling of their S=5/2 moments with varying intensity depending on the nature of the exchange pathways.

  2. Synthesis and Selective Coloration of Monoaza Crown Ethers Bearing Picrylamino-type Side Arms for Alkali Metal Salts and Methylamine

    Institute of Scientific and Technical Information of China (English)

    Wei ZENG; Zhi Hua MAO; Mi GONG; Chun Chun ZHANG; Sheng Ying QIN; Jun SU


    N-pivot lariat ethers with picrylamino group as a chromophore (1, 2 and 3) have been prepared by reaction of N-(4-aminoaryl)monoaza crown ethers with picryl chrolide, and the selective coloration of 1, 2 and 3 for alkali metal salts and amines has been studied by UV-Vis spectra.

  3. Local structure of alkalis in mixed-alkali borate glass to elucidate the origin of mixed-alkali effect

    Directory of Open Access Journals (Sweden)

    Yomei Tokuda


    Full Text Available We report the structural analysis of Na+ and Cs+ in sodium cesium borate crystals and glasses using 23Na and 133Cs magic-angle spinning nuclear magnetic resonance (MAS NMR spectroscopy. The composition dependence of NMR spectra of the borate was similar to that of the silicate: (1 the peak position of cesium borate crystals shifted to upfield for structures with larger Cs+ coordination numbers, (2 the MAS NMR spectra of xNa2O-yCs2O-3B2O3 (x = 0, 0.25, 0.5, 0.75, 1.0, x + y = 1 glass showed that the average coordination number (CN of both the alkali cations decreases with increasing Cs+/(Na+ + Cs+ ratio. However, the degree of decrement in borates is much smaller than that in silicates. We have considered that the small difference in CN is due to 4-coordinated B, because it is electrically compensated by the alkali metal ions resulting in the restriction of having various coordinations of O to alkali metal.

  4. Thin supported silica membranes

    NARCIS (Netherlands)

    Zivkovic, Tijana


    This thesis discusses several transport-related aspects relevant for the application of thin supported silica membranes for gas separation and nanofiltration. The influence of support geometry on overall membrane performance is investigated. Planar (i.e., flat plate), tubular, and multichannel suppo

  5. Drug silica nanocomposite: preparation, characterization and skin permeation studies. (United States)

    Pilloni, Martina; Ennas, Guido; Casu, Mariano; Fadda, Anna Maria; Frongia, Francesca; Marongiu, Francesca; Sanna, Roberta; Scano, Alessandra; Valenti, Donatella; Sinico, Chiara


    The aim of this work was to evaluate silica nanocomposites as topical drug delivery systems for the model drug, caffeine. Preparation, characterization, and skin permeation properties of caffeine-silica nanocomposites are described. Caffeine was loaded into the nanocomposites by grinding the drug with mesoporous silica in a ball mill up to 10 h and the efficiency of the process was studied by XRPD. Formulations were characterized by several methods that include FTIR, XRPD, SEM and TEM. The successful loading of caffeine was demonstrated by XRPD and FTIR. Morphology was studied by SEM that showed particle size reduction while TEM demonstrated formation of both core-shell and multilayered caffeine-silica structures. Solid-state NMR spectra excluded chemical interactions between caffeine and silica matrix, thus confirming that no solid state reactions occurred during the grinding process. Influence of drug inclusion in silica nanocomposite on the in vitro caffeine diffusion into and through the skin was investigated in comparison with a caffeine gel formulation (reference), using newborn pig skin and vertical Franz diffusion cells. Results from the in vitro skin permeation experiments showed that inclusion into the nanocomposite reduced and delayed caffeine permeation from the silica nanocomposite in comparison with the reference, independently from the amount of the tested formulation.

  6. Improved hydrogen desorption from lithium hydrazide by alkali metal hydride

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Liang, E-mail: [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan); Miyaoka, Hiroki [Institute for Sustainable Sciences and Development, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan); Ichikawa, Takayuki; Kojima, Yoshitsugu [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan)


    Highlights: •LiH can dramatically improve the hydrogen desorption properties of LiNHNH{sub 2}. •KH doping had positive effect in promoting the hydrogen desorption properties of LiNHNH{sub 2}–LiH mixture. •The reaction mechanism between LiNHNH{sub 2} and LiH was studied and discussed. -- Abstract: Lithium hydrazide (LiNHNH{sub 2}), which is a white solid with 8.0 mass% of theoretical hydrogen content, was synthesized from a reaction between anhydrous hydrazine and n-butyllithium in diethyl ether. The thermodynamic properties of this compound and its detailed decomposition pathways had been investigated in our previous work. However, a number of undesired gaseous products such as hydrazine (N{sub 2}H{sub 4}) and ammonia (NH{sub 3}) were generated during the thermal decomposition of LiNHNH{sub 2}. In this work, alkali metal hydride was used to suppress the impurities in the desorbed hydrogen and improved the hydrogen desorption properties. The reaction mechanism between LiNHNH{sub 2} and LiH was also studied and discussed in this paper.

  7. Removal of Retired Alkali Metal Test Systems

    Energy Technology Data Exchange (ETDEWEB)

    Brehm, W. F.; Church, W. R.; Biglin, J. W.


    This paper describes the successful effort to remove alkali metals, alkali metal residues, and piping and structures from retired non-radioactive test systems on the Hanford Site. These test systems were used between 1965 and 1982 to support the Fast Flux Test Facility and the Liquid Metal Fast Breeder Reactor Program. A considerable volume of sodium and sodium-potassium alloy (NaK) was successfully recycled to the commercial sector; structural material and electrical material such as wiring was also recycled. Innovative techniques were used to safely remove NaK and its residues from a test system that could not be gravity-drained. The work was done safely, with no environmental issues or significant schedule delays.

  8. Infrared spectra of FHF - in alkali halides (United States)

    Chunnilall, C. J.; Sherman, W. F.


    The bifluoride ion, FHF -, has been substitutionally isolated within single crystal samples of several different alkali halides. Infrared spectra of these crystals have been studied for sample temperatures down to 8K when half-bandwidths of less than 1 cm -1 have been observed. (Note that at room temperature ν 3 is observed to have a half-bandwidth of about 40 cm -1). The frequency shifts and half-bandwidth changes caused by cooling are considered together with the frequency shifts caused by pressures up to 10 k bar. The low temperature spectra clearly indicate that FHF - is a linear symmetrical ion when substitutionally isolated within alkali halides of either the NaCl or CsCl structure.

  9. Selective porous gates made from colloidal silica nanoparticles

    Directory of Open Access Journals (Sweden)

    Roberto Nisticò


    Full Text Available Highly selective porous films were prepared by spin-coating deposition of colloidal silica nanoparticles on an appropriate macroporous substrate. Silica nanoparticles very homogenous in size were obtained by sol–gel reaction of a metal oxide silica precursor, tetraethyl orthosilicate (TEOS, and using polystyrene-block-poly(ethylene oxide (PS-b-PEO copolymers as soft-templating agents. Nanoparticles synthesis was carried out in a mixed solvent system. After spin-coating onto a macroporous silicon nitride support, silica nanoparticles were calcined under controlled conditions. An organized nanoporous layer was obtained characterized by a depth filter-like structure with internal porosity due to interparticle voids. Permeability and size-selectivity were studied by monitoring the diffusion of probe molecules under standard conditions and under the application of an external stimulus (i.e., electric field. Promising results were obtained, suggesting possible applications of these nanoporous films as selective gates for controlled transport of chemical species in solution.

  10. Synthesis of Ag@Silica Nanoparticles by Assisted Laser Ablation (United States)

    González-Castillo, Jr.; Rodriguez, E.; Jimenez-Villar, E.; Rodríguez, D.; Salomon-García, I.; de Sá, Gilberto F.; García-Fernández, T.; Almeida, DB; Cesar, CL; Johnes, R.; Ibarra, Juana C.


    This paper reports the synthesis of silver nanoparticles coated with porous silica (Ag@Silica NPs) using an assisted laser ablation method. This method is a chemical synthesis where one of the reagents (the reducer agent) is introduced in nanometer form by laser ablation of a solid target submerged in an aqueous solution. In a first step, a silicon wafer immersed in water solution was laser ablated for several minutes. Subsequently, an AgNO3 aliquot was added to the aqueous solution. The redox reaction between the silver ions and ablation products leads to a colloidal suspension of core-shell Ag@Silica NPs. The influence of the laser pulse energy, laser wavelength, ablation time, and Ag+ concentration on the size and optical properties of the Ag@Silica NPs was investigated. Furthermore, the colloidal suspensions were studied by UV-VIS-NIR spectroscopy, X-Ray diffraction, and high-resolution transmission electron microscopy (HRTEM).

  11. Ion Pairing in Alkali Nitrate Electrolyte Solutions. (United States)

    Xie, Wen Jun; Zhang, Zhen; Gao, Yi Qin


    In this study, we investigate the thermodynamics of alkali nitrate salt solutions, especially the formation of contact ion pairs between alkali cation and nitrate anion. The ion-pairing propensity shows an order of LiNO3 activity coefficients and suggest that the empirical "law of matching water affinity" is followed by these alkali nitrate salt solutions. The spatial patterns of contact ion pairs are different in the three salt solutions studied here: Li(+) forms the contact ion pair with only one oxygen of the nitrate while Na(+) and K(+) can also be shared by two oxygens of the nitrate. In reproducing the salt activity coefficient using Kirkwood-Buff theory, we find that it is essential to include electronic polarization for Li(+) which has a high charge density. The electronic continuum correction for nonpolarizable force field significantly improves the agreement between the calculated activity coefficients and their experimental values. This approach also improves the performance of the force field on salt solubility. From these two aspects, this study suggests that electronic continuum correction can be a promising approach to force-field development for ions with high charge densities.

  12. Catalysis by alkali and alkaline-earth metal ions in nucleophilic attack of methoxide ion on crown ethers bearing an intra-annular acetoxy group

    NARCIS (Netherlands)

    Cacciapaglia, Roberta; Lucente, Silvia; Mandolini, Luigi; Doorn, van Arie R.; Reinhoudt, David N.; Verboom, Willem


    Rates of reaction of methoxide ion with crown ethers bearing an intra-annular acetoxy group are markedly enhanced by alkali and alkaline-earth metal bromides as a result of much stronger interactions of the metal ions with transition states than with reactants. Rates of reactions of methoxide ion w

  13. Novel, inorganic composites using porous, alkali-activated, aluminosilicate binders (United States)

    Musil, Sean

    Geopolymers are an inorganic polymeric material composed of alumina, silica, and alkali metal oxides. Geopolymers are chemical and fire resistant, can be used as refractory adhesives, and are processed at or near ambient temperature. These properties make geopolymer an attractive choice as a matrix material for elevated temperature composites. This body of research investigated numerous different reinforcement possibilities and variants of geopolymer matrix material and characterized their mechanical performance in tension, flexure and flexural creep. Reinforcements can then be chosen based on the resulting properties to tailor the geopolymer matrix composites to a specific application condition. Geopolymer matrix composites combine the ease of processing of polymer matrix composites with the high temperature capability of ceramic matrix composites. This study incorporated particulate, unidirectional fiber and woven fiber reinforcements. Sodium, potassium, and cesium based geopolymer matrices were evaluated with cesium based geopolymer showing great promise as a high temperature matrix material. It showed the best strength retention at elevated temperature, as well as a very low coefficient of thermal expansion when crystallized into pollucite. These qualities made cesium geopolymer the best choice for creep resistant applications. Cesium geopolymer binders were combined with unidirectional continuous polycrystalline mullite fibers (Nextel(TM) 720) and single crystal mullite fibers, then the matrix was crystallized to form cubic pollucite. Single crystal mullite fibers were obtained by the internal crystallization method and show excellent creep resistance up to 1400°C. High temperature flexural strength and flexural creep resistance of pollucite and polycrystalline/single-crystal fibers was evaluated at 1000-1400°C.

  14. Reinforcement of Natural Rubber by Precipitated Silica: the Influence of Processing Temperature

    NARCIS (Netherlands)

    Sarkawi, S.S.; Dierkes, W.K.; Noordermeer, J.W.M.


    The thermal history, and in particular the mixing dump temperature, is a parameter of paramount importance in mixing rubber and silica with a silane coupling agent in order to achieve proper silanization of silica and to avoid premature scorch reactions. The influence of the mixing dump temperature

  15. Reinforcement of natural rubber by precipitated silica: the influence of processing temperature

    NARCIS (Netherlands)

    Sarkawi, S.S.; Dierkes, W.K.; Noordermeer, J.W.M.


    The thermal history and in particular the mixing dump temperature is a parameter of paramount importance in mixing rubber and silica with a silane coupling agent in order to achieve proper silanization of silica and to avoid premature scorch reactions. In this work, the influence of mixing dump temp

  16. In situ generated silica in natural rubber latex via the sol–gel technique and properties of the silica rubber composites

    Energy Technology Data Exchange (ETDEWEB)

    Poompradub, Sirilux, E-mail: [Department of Chemical Technology, Faculty of Science, Chulalongkorn University, 254 Phayathai Road, Bangkok 10330 (Thailand); Thirakulrati, Mantana [Program in Petrochemistry and Polymer Science, Faculty of Science, Chulalongkorn University, 254 Phayathai Road, Bangkok 10330 (Thailand); Prasassarakich, Pattarapan [Department of Chemical Technology, Faculty of Science, Chulalongkorn University, 254 Phayathai Road, Bangkok 10330 (Thailand)


    Natural rubber (NR) composites reinforced by silica generated in situ within the NR matrix were prepared by the sol–gel process using tetraethoxysilane (TEOS) as the silica precursor. The effect of the TEOS content, water: TEOS mole ratio, reaction time and temperature on the in situ silica content formed in the NR latex were investigated. The results indicated that the suitable condition to produce a high silica content (54 parts by weight per hundred parts of rubber (phr)) in the rubbery matrix was the use of 200 phr TEOS and a water: TEOS mole ratio of 28.9:1 at room temperature for 24 h. The curing, mechanical, and thermal properties of the composite materials were also investigated. Increasing the in situ silica content increased the cure time and improved the mechanical properties of the composite. Compared to the NR vulcanizates filled with the commercial (ex situ formed) silica, the mechanical and thermal properties of the in situ silica composite material were significantly improved. Transmission electron microscopy revealed that the in situ formed silica particles were well distributed within the NR matrix, in contrast to the clumping of the ex situ formed commercial silica within the NR matrix. - Highlights: • High in situ silica content in NR latex was obtained up to 54 phr. • A good dispersion of in situ silica filling into the rubbery matrix. • Comparison of silica generated in the rubber matrix using solid, solution and latex NR substrates. • A good reinforcement effect of in situ silica was observed on the NR vulcanizate. • Sol–gel method is an alternative way to develop a novel composite material.

  17. The different poisoning behaviors of various alkali metal containing compounds on SCR catalyst (United States)

    Du, Xuesen; Yang, Guangpeng; Chen, Yanrong; Ran, Jingyu; Zhang, Li


    Alkali metals are poisonous to the metal oxide catalyst for NO removal. The chemical configuration of alkali containing substance and interacting temperature can affect the poisoning profile. A computational method based on Frontier Molecular Orbital analysis was proposed to determine the reacting behavior of various alkali-containing substances with SCR catalyst. The results reveal that the poisoning reactivities of various substances can be ranked as: E (MOH) > E (M2SO4) > E(MCl) > E(MNO3) > E(MHSO4). The experimental activity tests of the catalysts calcined at stepped temperatures show that NaOH can react with the catalyst below 200 °C. NaCl and NaNO3 start to react with the catalyst at a temperature between 300 and 400 °C. Unlike MOH, MCl and MNO3, which can produce volatile or decomposable species for the anions after reacting with the catalyst, M2SO4 and MHSO4 will leave both cations and anions on the catalyst surface. The sulfate ions left on the catalyst can generate active acid sites for NH3 adsorption. The experimental results also show that Na2SO4 and NaHSO4 will not lower the NO conversion. The after-reaction influences of various alkali metals were studied using theoretical and experimental methods. The theoretical results show that the acidity decreases with doping of alkali metal. Experiments show a consistent result that the NO conversion decreases as undoped >LiCl > NaCl > KCl.

  18. Dimethylsilanone generation from pyrolysis of polysiloxanes filled with nanosized silica and ceria/silica

    CERN Document Server

    Kulyk, Kostiantyn; Gatchell, Michael; Alexander, John D; Borysenko, Mykola; Palianytsia, Borys; Larsson, Mats; Kulik, Tetiana


    Polydimethylsiloxane (PDMS) is a widely used organosilicon polymer often employed in formulations with fine oxide particles for various high temperature applications. Although PDMS is considered to be thermally stable and chemically inert, it is not always clear how the oxide filler influences its thermoresistance, decomposition chemistry and what reactive products are formed in the underlying thermal reactions. In this work we use temperature programmed desorption mass spectrometry (TPD MS) to study the pyrolysis of PDMS and its composites with nanosized silica and ceria/silica. Our results suggest that the elusive organosilicon compound - dimethylsilanone is generated from PDMS over a broad temperature range (in some cases starting at 70${\\deg}$C). The presence of nano-oxides catalyzed this process. Ions characteristic of the fragmentation of dimethylsilanone under electron ionization were assigned with the aid of DFT structure calculations. Possible reaction mechanisms for generating dimethylsilanone were ...

  19. The influence of chlorine on the fate and activity of alkali metals during the gasification of wood

    Energy Technology Data Exchange (ETDEWEB)

    Struis, R.; Scala, C. von; Schuler, A.; Stucki, S. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)


    Chlorine clearly inhibits the CO{sub 2}-gasification reaction of charcoal at 800{sup o}C. From this and other observations the picture emerges that the reduction in the gasification reactivity of the charcoal is intimately related to the deactivation of the catalytically active alkali metals residing in the wood due to the formation of the chloride salt. It is argued that the heavy metal chlorides will likely transfer the chlorine to the indigenous alkali metals during the pyrolysis stage of the wood. The fate of the thus formed alkali metal chlorides can then be either their removal from the sample (evaporation), or, when present at the gasification stage, re-activation (i.e., de-chlorination) under our gasification conditions. (author) 3 figs., 4 refs.

  20. Alkali-activated binders/geopolymer and an application to environmental engineering

    Directory of Open Access Journals (Sweden)

    Nida Chaimoon


    Full Text Available For environmental reason, new binders that can be used as Portland cement replacement materials are being needed. Recently, alkali-activated binders (AAB and geopolymer have found increasing interest. As several research reports have showed that the two new binders are likely to have high potential to be developed and become an alternative to OPC. However, confusion in the classification of both binders is still there. This paper reviews knowledge about AAB and geopolymer including historical background, reaction mechanisms and reaction products. The similarities and differences of both binders are discussed. The application to environmental engineering on hazardous waste management using stabilization/solidification is also described.

  1. Hydrothermal synthesis of mixed rare earth-alkali metal or ammonium fluorides

    Institute of Scientific and Technical Information of China (English)

    由芳田; 黄世华; 时秋峰


    The recent results on hydrothermal synthesis of mixed rare earth-alkali or ammonium fluorides were presented. The initial ratios of the starting materials, pH value and reaction temperature were the critical factors for obtaining the single-phase product. Four main types of complex rare earth fluorides, AREF4, A2REF5, ARE2F7 and ARE3F10 (A=Na+, K+, Rb+, NH4+), appeared in the primary hydrothermal reactions. The correlation between cation sizes and the formation of mixed rare earth fluorides under mild hydro...

  2. Thermalization of different alkali and alkali-earth elements at the TRI{mu}P facility

    Energy Technology Data Exchange (ETDEWEB)

    Shidling, P.D., E-mail: P.Shidling@rug.n [Kernfysisch Versneller Instituut, University of Groningen, Zernikelaan 25, 9747 AA Groningen (Netherlands); Giri, G.S.; Hoek, D.J. van der; Jungmann, K.; Kruithof, W.L.; Onderwater, C.J.G.; Santra, B.; Sohani, M.; Versolato, O.O.; Willmann, L.; Wilschut, H.W. [Kernfysisch Versneller Instituut, University of Groningen, Zernikelaan 25, 9747 AA Groningen (Netherlands)


    Radioactive isotopes produced by the in-flight method are converted into low-energy ions with a thermal ionizer (TI) ion catcher, the operation of which is based on a hot cavity ion source. The extraction efficiency of the TI for different alkali and alkali-earth elements has been studied and compared to a model based on diffusion only. The model describes the stationary limit, i.e. the extraction efficiency, as well as the dynamic response of the TI output when the primary beam is switched on and off.

  3. Progress of the Application of Mesoporous Silica-Supported Heteropolyacids in Heterogeneous Catalysis and Preparation of Nanostructured Metal Oxides

    Directory of Open Access Journals (Sweden)

    Heyong He


    Full Text Available Mesoporous silica molecular sieves are a kind of unique catalyst support due to their large pore size and high surface area. Several methods have been developed to immobilize heteropolyacids (HPAs inside the channels of these mesoporous silicas. The mesoporous silica-supported HPA materials have been widely used as recyclable catalysts in heterogeneous systems. They have shown high catalytic activities and shape selectivities in some reactions, compared to the parent HPAs in homogeneous systems. This review summarizes recent progress in the field of mesoporous silica-supported HPAs applied in the heterogeneous catalysis area and preparation of nanostructured metal oxides using HPAs as precursors and mesoporous silicas as hard templates.

  4. Carbonation Characteristics of Alkali-Activated Blast-Furnace Slag Mortar

    Directory of Open Access Journals (Sweden)

    Keum-Il Song


    Full Text Available Alkali-activated ground granulated blast-slag (AAS is the most obvious alternative material for ordinary Portland cement (OPC. However, to use it as a structural material requires the assessment and verification of its durability. The most important factor for a durability evaluation is the degree of carbonation resistance, and AAS is known to show lower performance than OPC. A series of experiments was conducted with a view to investigate the carbonation characteristics of AAS binder. As a consequence, it was found that the major hydration product of AAS was calcium silicate hydrate (CSH, with almost no portlandite, unlike the products of OPC. After carbonation, the CSH of AAS turned into amorphous silica gel which was most likely why the compressive strength of AAS became weaker after carbonation. An increase of the activator dosage leads AAS to react more quickly and produce more CSH, increasing the compaction, compressive strength, and carbonation resistance of the microstructure.

  5. Fabrication of SWNT/silica composites by the sol-gel process. (United States)

    Babooram, Keshwaree; Narain, Ravin


    Single-walled carbon nanotubes (SWNTs) have successfully been incorporated into a silica matrix using the sol-gel process. The SWNTs were first functionalized with 3-aminopropyltriethoxysilane (APTES) through an amide linkage formed between the carboxylic acid groups already present on their surface and the amino group on APTES. The silane moieties were then used to form silica with and without the presence of tetramethylorthosilicate (TMOS) in a sol-gel reaction. The addition of TMOS was found to influence the molecular arrangement of the SWNT in the silica matrix and also to retard the degradation of the silica-SWNT composite.

  6. An alternative picture of alkali-metal-mediated metallation: cleave and capture chemistry. (United States)

    Mulvey, Robert E


    This perspective article takes an alternative look at alkali-metal-mediated chemistry (exchange of a relatively inert C-H bond for a more reactive C-metal bond by a multicomponent reagent usually containing an alkali metal and a less electropositive metal such as magnesium or zinc). It pictures that the cleavage of selected C-H bonds can be accompanied by the capturing of the generated anion by the multi (Lewis acid)-(Lewis base) character of the residue of the bimetallic base. In this way small atoms or molecules (hydrides, oxygen-based anions) as well as sensitive organic anions (of substituted aromatic compounds, ethers or alkenes) can be captured. Cleave and capture reactions which occur in special positions on the organic substrate are also included.

  7. Alkali ion migration between stacked glass plates by corona discharge treatment (United States)

    Kawaguchi, Keiga; Suzuki, Toshio; Ikeda, Hiroshi; Sakai, Daisuke; Funatsu, Shiro; Uraji, Keiichiro; Yamamoto, Kiyoshi; Harada, Kenji; Nishii, Junji


    Corona discharge reflects the spatial migration of alkali ions over a gap between two glass plates. This study examined stacked glass plates containing different alkali ions treated with the corona discharge plasma generated by applied voltage of 4.5 kV at 200 °C. Protons generated at the anode electrode penetrate into the potassium-ion-containing upper glass plate, which is located 5 mm below the anode electrode. Potassium ions intruded into the lower glass plate containing sodium ions placed on the cathode electrode, even over a 1 mm gap separating the plates. Finally, the sodium ion discharged on the cathode electrode. The hydrogen atmosphere was effective at inhibiting the potassium ion reaction with ambient gases during the spatial migration between the two glass plates.

  8. Alkali Induced Morphology and Property Improvements of TiO2 by Hydrothermal Treatment

    Institute of Scientific and Technical Information of China (English)

    HE Qiong; WEN Xianming; MA Peihua; DENG Xiaochuan


    Alkali induced morphology and property improvements of TiO2 by hydrothermal reaction were investigated.The products were characterized by SEM,TEM,XRD,TG,EDX,FT-IR and DRS.The results indicate that,with the phase transformation from anatase to rutile,the morphologies changed from high aggregated particles to nanofibers with the diameter of about 100 nm and the length up to several tens of micrometers,meanwhile the process is controllable by manipulating the nature of the alkali,alkalinity and hydrothermal temperature.DRS analysis shows the property improvement of the nanofibers in the UV-Vis light absorption compared with the raw materials,implying the products have potential application in photocatalysis.

  9. Electrochemistry of ytterbium (III) in molten alkali metal chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Smolenski, V.; Novoselova, A. [Institute of High-Temperature Electrochemistry, Ural Division, Russian Academy of Science, Ekaterinburg, 620219 (Russian Federation); Osipenko, A. [Research Institute of Atomic Reactors, Dimitrovgrad-10, Ulyanovsk Region, 433010 (Russian Federation); Caravaca, C. [High Level Waste Unit, Nuclear Fission Division, CIEMAT, Madrid, 28040 (Spain); Cordoba, G. de [High Level Waste Unit, Nuclear Fission Division, CIEMAT, Madrid, 28040 (Spain)], E-mail:


    This work presents the electrochemical study of Yb(III) ions in molten alkali metal chlorides in the temperature range 723-1073 K. Transient electrochemical techniques such as linear sweep, cyclic and square wave voltammetry, and potentiometry at zero current have been used to investigate the reduction mechanism, transport parameters and thermodynamic properties of the reaction YbCl{sub 2} + 1/2Cl{sub 2} = YbCl{sub 3} The results obtained show that the reduction reaction Yb(III) + e{sup -} {r_reversible} Yb(II) is reversible being controlled by the rate of the mass transfer. The diffusion coefficient of [YbCl{sub 6}]{sup 3-} complex ions has been determined at different temperatures in the fused eutectic LiCl-KCl, the equimolar NaCl-KCl and the CsCl media. The apparent standard potential of the soluble-soluble redox system Yb(III)/Yb(II) has been obtained by cyclic voltammetry. The influence of the nature of the solvent on the electrochemical and thermodynamic properties of ytterbium compounds is discussed.

  10. Silica reinforced triblock copolymer gels

    DEFF Research Database (Denmark)

    Theunissen, E.; Overbergh, N.; Reynaers, H.


    The effect of silica and polymer coated silica particles as reinforcing agents on the structural and mechanical properties of polystyrene-poly(ethylene/butylene)-polystyrene (PS-PEB-PS) triblock gel has been investigated. Different types of chemically modified silica have been compared in order...... to evaluate the influence of the compatibility between gel and filler. Time-resolved SANS and small-angle X-ray scattering (SAXS) shows that the presence of silica particles affects the ordering of the polystyrene domains during gelsetting. The scattering pattern of silica-reinforced gels reveals strong...... a viscoclastic rubber to a plastic fluid and from a plastic fluid to a viscoelastic liquid are shifted to more elevated temperatures when silica is added to the triblock copolymer gel. (C) 2004 Elsevier Ltd. All rights reserved....

  11. Mesoporous Structure Control of Silica in Room-Temperature Synthesis under Basic Conditions

    Directory of Open Access Journals (Sweden)

    Jeong Wook Seo


    Full Text Available Various types of mesoporous silica, such as continuous cubic-phase MCM-48, hexagonal-phase MCM-41, and layer-phase spherical silica particles, have been synthesized at room temperature using cetyltrimethylammonium bromide as a surfactant, ethanol as a cosurfactant, tetraethyl orthosilicate as a silica precursor, and ammonia as a condensation agent. Special care must be taken both in the filtering of the resultant solid products and in the drying process. In the drying process, further condensation of the silica after filtering was induced. As the surfactant and cosurfactant concentrations in the reaction mixture increased and the NH3 concentration decreased, under given conditions, continuous cubic MCM-48 and layered silica became the dominant phases. A cooperative synthesis mechanism, in which both the surfactant and silica were involved in the formation of mesoporous structures, provided a good explanation of the experimental results.

  12. Janus Silica Hollow Spheres Prepared via Interfacial Biosilicification. (United States)

    Sheng, Li; Chen, Hong; Fu, Wenxin; Li, Zhibo


    A poly(ethylene glycol)-b-poly(L-lysine)-b-poly(styrene) (PEG-PLL-PS) triblock copolymer, which contains a cationic PLL block as the middle block, is synthesized via a combination of ring-opening polymerization (ROP) and atom-transfer radical polymerization (ATRP). The PEG-PLL-PS (ELS) triblock is employed as a macromolecular surfactant to form a stable oil-in-water (O/W) emulsion, which is subsequently used as the template to prepare Janus silica hollow spheres (JHS) via a one-pot biosilicification reaction. For the emulsion template, the middle PLL block assembles at the O/W interface and directs the biomimetic silica synthesis in the presence of phosphate buffer and silicic acid precursors. This biosilicification process takes place only in the intermediate layer between water and the organic interior phase, leading to the formation of silica JHSs with hydrophobic PS chains tethered to the inner surface and PEG attached to the outer surface. The three-layer JHSs, namely, PEG/silica-polylysine/PS composites, were verified by electron microscopy. Upon further breaking these JHSs into species, polymer-grafted Janus silica nanoplates (JPLs) can be obtained. Our studies provide an efficient one-step method for preparing hybrid silica Janus structures within minutes.

  13. In situ silica-EPDM nanocomposites obtained via reactive processing

    NARCIS (Netherlands)

    Miloskovska, Elena; Hristova-Bogaerds, Denka; van Duin, Martin; de With, Gijsbertus


    In situ rubber nanocomposites prepared via reactive batch mixing and via reactive extrusion were studied. Materials produced via reactive batch mixing showed a significantly higher silica content for a similar reaction time as compared to previously prepared in situ nanocomposites using a diffusion

  14. Formation of silica iron oxide glasses (United States)

    Al-Bawab, Abeer F.

    The microemulsion-gel method was developed as an alternative process in the production of room temperature glasses. This method is based on the formation of a microemulsion, to which is added a metal alkoxide that undergoes hydrolysis and condensation to form an oxide network, which is dried into glass. The goal of this work is to understand the sol-gel process upon addition of hydrate metal salts. The thermal transitions of the silica containing ferric nitrate hydrate were examined by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Using infrared (IR) spectroscopy and X-ray diffraction (XRD). The glasses with a less than 30 mol % iron nitrate were amorphous, while those higher concentration were crystalline. Based on XRD the thermal transitions did not alter the crystallinity. The IR spectra indicated the existence of Si-O-Fe bonds. Thermal analysis indicated similar transitions as exhibited by pure iron nitrate with minor modifications due to interactions with the silica. The reaction between tetraethoxysilane and chloral hydrate in ethanol was followed by NMR of the sp{29}Si nucleus at two different pHs. The sp{29}Si NMR spectra were similar to those reported for the reactions in alcohol between tetraethoxysilane and water of low pH, and for the reactions in the presence of inorganic hydrate. At pH 4, monomene silicon species were detected where at pH 2 the reaction was sufficiently rapid that multi hydroxy monomers were not detected as expected from the catalysts. The reaction proceeded without adding water. The reaction between aluminum chloride and methoxydimethyloctylsilane was investigated at room temperature using NMR and IR spectroscopy in addition to a molecular weight determination from the freezing point reduction in benzene. The structure as deduced from the experimental results was found to be a dimer containing two silicon atoms and two aluminum atoms of which the latter were tetrahedrally coordinated.

  15. Biologically Inspired Flagella-Templated Silica Nanotubes (United States)

    Jo, Wonjin

    The desire and need for various types of nanostructures have been met with challenges of feasibility, reproducibility, and long fabrication time. To work towards improved bottom-up methods of nanofabrication, bacterial flagella are particularly attractive bio-templates for nanotubes due to their tubular structures and small inner and outer diameters. In this work, flagella isolated from Salmonella typhimurium are used as bio-templates to fabricate silica mineralized nanotubes. The process involves as well-controlled hydrolysis and condensation reaction with aminopropyltriethoxysilane (APTES), followed by the addition of tetraethoxysilane (TEOS). By controlling the concentration of TEOS and the reaction time, a simple and precise method is developed for creating silica-mineralized flagella nanotubes (SMFNs) with various thicknesses of the silica layer. In addition, the SMFNs are further modified to multifunctional nanotubes by coating metal nanoparticles (NPs) or metal oxide NPs such as gold, palladium, and iron oxide. The metallized SMFNs are achieved through reactions including reductive metallization or oxidative hydrolysis. The results from these studies provide evidence for the complete coating of SMFNs with uniform metal NP sizes and high surface area coverage. The metallized SMFNs are found to be electrically conductive along their network structures. The current-voltage characteristics show remarkably improved electrical conductivities depending on the types of metal NPs loading and SMFN networks concentration. The biologically inspired SMFNs with metal loading will allow have controlled electrical properties that can lead to the potential of creating unique and precise nanoelectronic materials. Lastly, the randomly entangled SMFNs are characterized to demonstrate their capabilities for hydrophilic and hydrophobic surface applications.

  16. Precipitation and Crystallization Kinetics in Silica Gardens. (United States)

    Glaab, Fabian; Rieder, Julian; Klein, Regina; Choquesillo-Lazarte, Duane; Melero-Garcia, Emilio; García-Ruiz, Juan-Manuel; Kunz, Werner; Kellermeier, Matthias


    Silica gardens are extraordinary plant-like structures resulting from the complex interplay of relatively simple inorganic components. Recent work has highlighted that macroscopic self-assembly is accompanied by the spontaneous formation of considerable chemical gradients, which induce a cascade of coupled dissolution, diffusion, and precipitation processes occurring over timescales as long as several days. In the present study, this dynamic behavior was investigated for silica gardens based on iron and cobalt chloride by means of two synchrotron-based techniques, which allow the determination of concentration profiles and time-resolved monitoring of diffraction patterns, thus giving direct insight into the progress of dissolution and crystallization phenomena in the system. On the basis of the collected data, a kinetic model is proposed to describe the relevant reactions on a fundamental physicochemical level. The results show that the choice of the metal cations (as well as their counterions) is crucial for the development of silica gardens in both the short and long term (i.e. during tube formation and upon subsequent slow equilibration), and provide important clues for understanding the properties of related structures in geochemical and industrial environments.

  17. Basic Functionalization of Hexagonal Mesoporous Silica

    Institute of Scientific and Technical Information of China (English)


    3-Aminopropyltricthoxysilanc (AM), 3-cthyldiaminopropyltrimcthoxysilane (ED) and 3-piperazinylpropyltriethoxysilanc (PZ), were used to chemically couple with the silanol groups of calcined hexagonal and hexagonal-like mesoporous silica SBA-3 and HMS, respectively, to produce functionalised alkaline mesoporous materials. The inerease in the dosage of organosilanes, or in reaction temperature, or in the humidity (i.e., water content) of support, is favorable to the grafting of functional molecules on the surface. When functionalization conditions are the same, the order of loadings on SBA-3 and DDA-HMS is ED>AM>PZ. However, on ODA-HMS, the loading of AM is similar to that of ED.

  18. Fabrication of Mesoporous Silica Shells on Solid Silica Spheres Using Anionic Surfactants and Their Potential Application in Controlling Drug Release

    Directory of Open Access Journals (Sweden)

    Mansour Al-Hoshan


    Full Text Available In this work, mesoporous shells were constructed on solid silica cores by employing anionic surfactante. A co-structure directing agent (CSDA has assisted the electrostatic interaction between negatively charged silica particles and the negatively charged surfactant molecules. Synthetic parameters such as reaction time and temperature had a significant impact on the formation of mesoporous silica shelld and their textural properties such as surface area and pore volume. Core-mesoporous shell silica spheres were characterized by small angle X-ray scattering, transmission electron microscopy, and N2 adsorption–desorption analysis. The synthesized particles have a uniformly mesoporous shell of 34–65 nm and possess a surface area of ca. 7–324 m2/g, and pore volume of ca. 0.008–0.261 cc/g. The core-mesoporous shell silica spheres were loaded with ketoprofen drug molecules. The in vitro drug release study suggested that core-mesoporous shell silica spheres are a suitable nanocarrier for drug molecules offering the possibility of having control over their release rate.

  19. Fabrication of mesoporous silica shells on solid silica spheres using anionic surfactants and their potential application in controlling drug release. (United States)

    El-Toni, Ahmed Mohamed; Khan, Aslam; Ibrahim, Mohamed Abbas; Al-Hoshan, Mansour; Labis, Joselito Puzon


    In this work, mesoporous shells were constructed on solid silica cores by employing anionic surfactante. A co-structure directing agent (CSDA) has assisted the electrostatic interaction between negatively charged silica particles and the negatively charged surfactant molecules. Synthetic parameters such as reaction time and temperature had a significant impact on the formation of mesoporous silica shelld and their textural properties such as surface area and pore volume. Core-mesoporous shell silica spheres were characterized by small angle X-ray scattering, transmission electron microscopy, and N(2) adsorption–desorption analysis. The synthesized particles have a uniformly mesoporous shell of 34–65 nm and possess a surface area of ca. 7–324 m2/g, and pore volume of ca. 0.008–0.261 cc/g. The core-mesoporous shell silica spheres were loaded with ketoprofen drug molecules. The in vitro drug release study suggested that core-mesoporous shell silica spheres are a suitable nanocarrier for drug molecules offering the possibility of having control over their release rate.

  20. Control of silicification by genetically engineered fusion proteins: Silk–silica binding peptides (United States)

    Zhou, Shun; Huang, Wenwen; Belton, David J.; Simmons, Leo O.; Perry, Carole C.; Wang, Xiaoqin; Kaplan, David L.


    In the present study, an artificial spider silk gene, 6mer, derived from the consensus sequence of Nephila clavipes dragline silk gene, was fused with different silica-binding peptides (SiBPs), A1, A3 and R5, to study the impact of the fusion protein sequence chemistry on silica formation and the ability to generate a silk–silica composite in two different bioinspired silicification systems: solution–solution and solution– solid. Condensed silica nanoscale particles (600–800 nm) were formed in the presence of the recombinant silk and chimeras, which were smaller than those formed by 15mer-SiBP chimeras [1], revealing that the molecular weight of the silk domain correlated to the sizes of the condensed silica particles in the solution system. In addition, the chimeras (6mer-A1/A3/R5) produced smaller condensed silica particles than the control (6mer), revealing that the silica particle size formed in the solution system is controlled by the size of protein assemblies in solution. In the solution–solid interface system, silicification reactions were performed on the surface of films fabricated from the recombinant silk proteins and chimeras and then treated to induce β-sheet formation. A higher density of condensed silica formed on the films containing the lowest β-sheet content while the films with the highest β-sheet content precipitated the lowest density of silica, revealing an inverse correlation between the β-sheet secondary structure and the silica content formed on the films. Intriguingly, the 6mer-A3 showed the highest rate of silica condensation but the lowest density of silica deposition on the films, compared with 6mer-A1 and -R5, revealing antagonistic crosstalk between the silk and the SiBP domains in terms of protein assembly. These findings offer a path forward in the tailoring of biopolymer–silica composites for biomaterial related needs. PMID:25462851

  1. An Experimental Study of the Liesegang Phenomenon and Crystal Growth in Silica Gels. (United States)

    Sharbaugh, Amandus H., III; Sharbaugh, Amandus H., Jr.


    Reports on a 30-year-old longitudinal study of reactions in gels. Described are reactions and crystal growth in silica gels and diffusion studies of the Liesegang ring formation. Color photographs showing the reactions and graphs upon the diffusions are presented. (YP)

  2. Silica Micro Encapsulation

    Energy Technology Data Exchange (ETDEWEB)

    Mitchell, P.; Whitbread-Jordan, M. [KEECO (United Kingdom)


    The article explains how Silica Micro Encapsulation (SME) water treatment technology may be transferred from metal mining to coal mining operations. KEECO has been developing a unique solution for treating acid rock drainage in the metal sulphide mining sector and following trials in metal mining operations (described in the article), is preparing to transfer the technology to the coal industry. SME technology comprises metal precipitation and encapsulation accomplished with proprietary chemical, KB-1, and a group of patented chemical dosing systems, the K-series, to dose KB-1 into contaminated liquid wastes as a dry powder. 4 figs., 4 tabs.

  3. ZBLAN, Silica Fiber Comparison (United States)


    This graph depicts the increased signal quality possible with optical fibers made from ZBLAN, a family of heavy-metal fluoride glasses (fluorine combined zirconium, barium, lanthanum, aluminum, and sodium) as compared to silica fibers. NASA is conducting research on pulling ZBLAN fibers in the low-g environment of space to prevent crystallization that limits ZBLAN's usefulness in optical fiber-based communications. In the graph, a line closer to the black theoretical maximum line is better. Photo credit: NASA/Marshall Space Flight Center

  4. Silica ecosystem for synergistic biotransformation (United States)

    Mutlu, Baris R.; Sakkos, Jonathan K.; Yeom, Sujin; Wackett, Lawrence P.; Aksan, Alptekin


    Synergistical bacterial species can perform more varied and complex transformations of chemical substances than either species alone, but this is rarely used commercially because of technical difficulties in maintaining mixed cultures. Typical problems with mixed cultures on scale are unrestrained growth of one bacterium, which leads to suboptimal population ratios, and lack of control over bacterial spatial distribution, which leads to inefficient substrate transport. To address these issues, we designed and produced a synthetic ecosystem by co-encapsulation in a silica gel matrix, which enabled precise control of the microbial populations and their microenvironment. As a case study, two greatly different microorganisms: Pseudomonas sp. NCIB 9816 and Synechococcus elongatus PCC 7942 were encapsulated. NCIB 9816 can aerobically biotransform over 100 aromatic hydrocarbons, a feat useful for synthesis of higher value commodity chemicals or environmental remediation. In our system, NCIB 9816 was used for biotransformation of naphthalene (a model substrate) into CO2 and the cyanobacterium PCC 7942 was used to provide the necessary oxygen for the biotransformation reactions via photosynthesis. A mathematical model was constructed to determine the critical cell density parameter to maximize oxygen production, and was then used to maximize the biotransformation rate of the system.

  5. High-Order Dispersion Coefficients for Alkali-metal Atoms

    Institute of Scientific and Technical Information of China (English)

    KANG Shuai; DING Chi-Kun; CHEN Chang-Yong; WU Xue-Qing


    High-order dispersion coefficients C9,C11,C12,and C13 for the ground-state alkali-metals were calculated by combining the l-dependent model potential of alkali-metal atoms and linear variation method based on B-spline basis functions.The results were compared.

  6. Durability of Alkali Activated Blast Furnace Slag (United States)

    Ellis, K.; Alharbi, N.; Matheu, P. S.; Varela, B.; Hailstone, R.


    The alkali activation of blast furnace slag has the potential to reduce the environmental impact of cementitious materials and to be applied in geographic zones where weather is a factor that negatively affects performance of materials based on Ordinary Portland Cement. The scientific literature provides many examples of alkali activated slag with high compressive strengths; however research into the durability and resistance to aggressive environments is still necessary for applications in harsh weather conditions. In this study two design mixes of blast furnace slag with mine tailings were activated with a potassium based solution. The design mixes were characterized by scanning electron microscopy, BET analysis and compressive strength testing. Freeze-thaw testing up to 100 freeze-thaw cycles was performed in 10% road salt solution. Our findings included compressive strength of up to 100 MPa after 28 days of curing and 120 MPa after freeze-thaw testing. The relationship between pore size, compressive strength, and compressive strength after freeze-thaw was explored.

  7. Laser Spectroscopy of bi-alkali molecules (United States)

    Dutta, Sourav; Altaf, A.; Lorenz, J.; Elliott, D.; Chen, Yong


    We report a study of laser spectroscopy of bi-alkali molecules, such as Li2, Rb2 and LiRb (work is in progress). We have constructed a dual-species (Li/Rb) heat pipe oven with a side viewport. The molecular fluorescence is excited by a dye laser with Rh6G dye (operating between 564 nm and 610 nm) and various home-made diode lasers (operating near 635 nm and 665 nm). The fluorescence is recorded using a .5ex1 -.1em/ -.15em.25ex4 m monochromator with a 0.1 nm (˜ 3 cm-1) spectral resolution. Transitions to the X^1σg^+ in Li2 and Rb2 have been measured and studies on LiRb are in progress. Molecular parameters, such as force constant, may be obtained from the analysis of the data (which agree with previously known values to within ˜ 3%). Using the known values of dissociation energy De and harmonic frequency φe for the alkali dimers, we also demonstrate that simple calculations with Morse potential approximation can be used to estimate the molecular transition wavelengths to within a few (1-3) nanometers from the experimentally measured values. Such information will aid in creating cold molecules via photoassociation in a dual species magneto-optical trap (LiRb in our case).

  8. Alkali metal cation doped Al-SBA-15 for carbon dioxide adsorption. (United States)

    Zukal, Arnošt; Mayerová, Jana; Čejka, Jiří


    Mesoporous aluminosilicate adsorbents for carbon dioxide were prepared by the grafting of aluminium into SBA-15 silica using an aqueous solution of aluminium chlorohydrate. As the ion exchange sites are primarily associated with the presence of tetrahedrally coordinated aluminium, extra-framework aluminium on the SBA-15 surface was inserted into the silica matrix by a treatment with an aqueous solution of NH(4)OH. Synthesized mesoporous aluminosilicate preserving all the characteristic features of a mesoporous molecular sieve was finally modified by the alkali metal cation exchange. To examine carbon dioxide adsorption on prepared materials, adsorption isotherms in the temperature range from 0 °C to 60 °C were measured. Based on the known temperature dependence of adsorption isotherms, isosteric adsorption heats giving information on the surface energetics of CO(2) adsorption were calculated and discussed. The comparison of carbon dioxide isotherms obtained on aluminosilicate SBA-15, aluminosilicate SBA-15 containing cations Na(+) and K(+) and activated alumina F-200 reveals that the doping with sodium or potassium cations dramatically enhances adsorption in the region of equilibrium pressures lower than 10 kPa. Therefore, synthesized aluminosilicate adsorbents doped with Na(+) or K(+) cations are suitable for carbon dioxide separation from dilute gas mixtures.

  9. Petrographic atlas characterisation of aggregates regarding potential reactivity to alkalis : RILEM TC 219-ACS recommended guidance AAR-1.2, for use with the RILEM AAR-1.1 petrographic examination method

    CERN Document Server

    Ribeiro, Maria; Broekmans, Maarten; Sims, Ian


    This RILEM AAR 1.2 Atlas is complementary to the petrographic method described in RILEM AAR 1.1. It is designed and intended to assist in the identification of alkali-reactive rock types in concrete aggregate by thin-section petrography. Additional issues include: • optical thin-section petrography conforming to RILEM AAR 1.1 is considered the prime assessment method for aggregate materials, being effective regarding cost and time. Unequivocal identification of minerals in very-fine grained rock types may however require use of supplementary methods. • the atlas adheres to internationally adopted schemes for rock classification and nomenclature, as recommended in AAR 1.1. Thus, rock types are classified as igneous, sedimentary or metamorphic based upon mineral content, microstructure and texture/fabric. • in addition, the atlas identifies known alkali-reactive silica types in each rock type presented. It also identifies consistent coincidence between certain lithologies and silica types; however, it ref...

  10. IRMPD Action Spectroscopy of Alkali Metal Cation-Cytosine Complexes: Effects of Alkali Metal Cation Size on Gas Phase Conformation

    NARCIS (Netherlands)

    Yang, B.; Wu, R.R.; Polfer, N.C.; Berden, G.; Oomens, J.; Rodgers, M.T.


    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both simi

  11. Effect of alkali cations on heterogeneous photo-Fenton process mediated by Prussian blue colloids. (United States)

    Liu, Shou-Qing; Cheng, Shi; Feng, Lian-Rong; Wang, Xiao-Mei; Chen, Zhi-Gang


    This article evaluates Prussian blue (iron hexacyanoferrate) colloids as a heterogeneous photo-Fenton catalyst for the degradation of Rhodamine B. The emphasis is laid on the effects of alkali metal cations on the photo-Fenton process. The facts show that alkali cations strongly affect the degradation rate of organic species. The degradation rates of Rhodamine B, Malachite Green, and Methyl Orange in the presence of KCl, KNO(3), and K(2)SO(4), respectively, are faster than their degradation rates in the presence of the corresponding sodium salts. The average degradation rates of Rhodamine B in 0.2 M KCl, NaCl, RbCl, and CsCl solution, decline in sequence, and the rate in KCl solution is greater than that without any salt added deliberately. Thus, potassium ions accelerate the degradation rate, but sodium, rubidium, and cesium ions slow the rate. The order of the rates is R(K)>R>R(Na)>R(Rb)>R(Cs), which is consistent with that of the voltammetric oxidation currents of Prussian blue in the corresponding cation solutions. This phenomenon is attributed to the molecular recognition of the microstructure in Prussian blue nanoparticles to the alkali cations. The reaction mechanism of the photo-Fenton process has also been explored.

  12. Ab Initio Molecular Dynamics of Dimerization and Clustering in Alkali Metal Vapors. (United States)

    Chaban, Vitaly V; Prezhdo, Oleg V


    Alkali metals are known to form dimers, trimers, and tetramers in their vapors. The mechanism and regularities of this phenomenon characterize the chemical behavior of the first group elements. We report ab initio molecular dynamics (AIMD) simulations of the alkali metal vapors and characterize their structural properties, including radial distribution functions and atomic cluster size distributions. AIMD confirms formation of Men, where n ranges from 2 to 4. High pressure sharply favors larger structures, whereas high temperature decreases their fraction. Heavier alkali metals maintain somewhat larger fractions of Me2, Me3, and Me4, relative to isolated atoms. A single atom is the most frequently observed structure in vapors, irrespective of the element and temperature. Due to technical difficulties of working with high temperatures and pressures in experiments, AIMD is the most affordable method of research. It provides valuable understanding of the chemical behavior of Li, Na, K, Rb, and Cs, which can lead to development of new chemical reactions involving these metals.

  13. Strength and durability performance of alkali-activated rice husk ash geopolymer mortar. (United States)

    Kim, Yun Yong; Lee, Byung-Jae; Saraswathy, Velu; Kwon, Seung-Jun


    This paper describes the experimental investigation carried out to develop the geopolymer concrete based on alkali-activated rice husk ash (RHA) by sodium hydroxide with sodium silicate. Effect on method of curing and concentration of NaOH on compressive strength as well as the optimum mix proportion of geopolymer mortar was investigated. It is possible to achieve compressive strengths of 31 N/mm(2) and 45 N/mm(2), respectively for the 10 M alkali-activated geopolymer mortar after 7 and 28 days of casting when cured for 24 hours at 60°C. Results indicated that the increase in curing period and concentration of alkali activator increased the compressive strength. Durability studies were carried out in acid and sulfate media such as H2SO4, HCl, Na2SO4, and MgSO4 environments and found that geopolymer concrete showed very less weight loss when compared to steam-cured mortar specimens. In addition, fluorescent optical microscopy and X-ray diffraction (XRD) studies have shown the formation of new peaks and enhanced the polymerization reaction which is responsible for strength development and hence RHA has great potential as a substitute for ordinary Portland cement concrete.

  14. Recovery of alkali and alumina from Bayer red mud by the calcification-carbonation method (United States)

    Zhu, Xiao-feng; Zhang, Ting-an; Wang, Yan-xiu; Lü, Guo-zhi; Zhang, Wei-guang


    Red mud produced in the Bayer process is a hazardous solid waste because of its high alkalinity; however, it is rich in valuable components such as titanium, iron, and aluminum. In this study, a novel calcification-carbonation method was developed to recover alkali and alumina from Bayer red mud under mild reaction conditions. Batch experiments were performed to evaluate the potential effects of important parameters such as temperature, amount of CaO added, and CO2 partial pressure on the recovery of alkali and alumina. The results showed that 95.2% alkali and 75.0% alumina were recovered from red mud with decreases in the mass ratios of Na2O to Fe2O3 and of Al2O3 to Fe2O3 from 0.42 and 0.89 to 0.02 and 0.22, respectively. The processed red mud with less than 0.5wt% Na2O can potentially be used as a construction material.

  15. Alkali ion migration between stacked glass plates by corona discharge treatment

    Energy Technology Data Exchange (ETDEWEB)

    Kawaguchi, Keiga [Research Institute for Electronic Science, Hokkaido University, N20 W10, Kita-ku, Sapporo, Hokkaido 001-0020 (Japan); Suzuki, Toshio [Research Center, Asahi Glass Co., Ltd., 1150 Hazawa-cho, Kanagawa-ku, Yokohama, Kanagawa 221-8755 (Japan); Ikeda, Hiroshi [Art, Science and Technology Center for Cooperative Research, Kyushu University, 6-1 Kasuga-koen, Kasuga, Fukuoka 816-8580 (Japan); Sakai, Daisuke [Department of Electrical and Electronic Engineering, Kitami Institute of Technology, 165 Koen-cho, Kitami, Hokkaido 090-8507 (Japan); Funatsu, Shiro; Uraji, Keiichiro [Production Technology Center, Asahi Glass Co., Ltd., 1-1 Suehiro-cyo, Tsurumiku, Yokohama, Kanagawa 230-0045 (Japan); Yamamoto, Kiyoshi [Research Center, Asahi Glass Co., Ltd., 1150 Hazawa-cho, Kanagawa-ku, Yokohama, Kanagawa 221-8755 (Japan); Harada, Kenji [Department of Computer Science, Kitami Institute of Technology, 165 Koen-cho, Kitami, Hokkaido 090-8507 (Japan); Nishii, Junji, E-mail: [Research Institute for Electronic Science, Hokkaido University, N20 W10, Kita-ku, Sapporo, Hokkaido 001-0020 (Japan)


    Highlights: • Two stacked glass plates with a 1 mm gap were treated by corona discharge. • Spatial migration of alkali ion over the gap was demonstrated. • Hydrogen gas was necessary for uniform migration. • Surface modification was done with this process without high temperature or vacuum. - Abstract: Corona discharge reflects the spatial migration of alkali ions over a gap between two glass plates. This study examined stacked glass plates containing different alkali ions treated with the corona discharge plasma generated by applied voltage of 4.5 kV at 200 °C. Protons generated at the anode electrode penetrate into the potassium-ion-containing upper glass plate, which is located 5 mm below the anode electrode. Potassium ions intruded into the lower glass plate containing sodium ions placed on the cathode electrode, even over a 1 mm gap separating the plates. Finally, the sodium ion discharged on the cathode electrode. The hydrogen atmosphere was effective at inhibiting the potassium ion reaction with ambient gases during the spatial migration between the two glass plates.

  16. Antidegradation and reinforcement effects of phenyltrimethoxysilane- or N-[3-(trimethoxysilyl)propyl]aniline-modified silica particles in natural rubber composites

    Energy Technology Data Exchange (ETDEWEB)

    Tunlert, Apinya [Program in Petrochemistry and Polymer Science, Chulalongkorn University, Bangkok 10330 (Thailand); Prasassarakich, Pattarapan [Department of Chemical Technology, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand); Poompradub, Sirilux, E-mail: [Department of Chemical Technology, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand); Center for Petroleum, Petrochemical and Advanced Material, Chulalongkorn University Bangkok 10330 (Thailand)


    The modification of silica particles with phenyltrimethoxysilane or N-[3-(trimethoxysilyl)propyl]aniline via a sol–gel reaction was performed in order to improve the dispersion of silica and antidegradation in natural rubber (NR). The functional groups on the modified silica surface were characterized by Fourier transform infrared spectroscopy, while the morphology was evaluated by scanning and transmission electron microscopy. The surface properties and antioxidant activity of the modified silica particles were determined by the water contact angle and 2, 2-diphenyl-1-picrylhydrazyl assay, respectively. The modified silica particles exhibited a higher hydrophobicity and a decreased interfacial adhesion energy compared with the unmodified silica particles. The modified silica particles were then incorporated into NR. The better dispersion of the modified silica particles than the unmodified ones in the NR matrix resulted in improved mechanical properties in terms of the modulus at 300% elongation (2.9 ± 0.02 MPa), hardness (52.5 ± 0.2 Shore A), abrasion resistance (241 ± 8 mm{sup 3}) and compression set (20.2 ± 0.6%). In addition, the inclusion of the modified silica particles in the NR matrix gave a high initial temperature of decomposition and retarded the ozone-induced degradation compared with the NR filled with unmodified silica particles. - Highlights: • Silica was surface modified with PhTMS or ATMS via a sol–gel reaction. • Modified silica showed a decreased interfacial adhesion energy. • Modified silica showed an enhanced free radical scavenging activity. • Modified silica improved the mechanical properties, thermal stability and ozone resistance in NR vulcanizates.

  17. Influence of alkali promoters in the selective hydrogenation of 3-methyl-2-butenal over Ru/SiO{sub 2} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Waghray, A.; Wang, Jian; Oukaci, R.; Blackmond, D.G. [Univ. of Pittsburgh, PA (United States)


    The addition of potassium as a promoter to a Ru/SiO{sub 2} catalyst resulted in a striking shift in product selectivity in the hydrogenation of 3-methyl-2-butenal. The rate of hydrogenation of the C=O bond to produce the unsaturated alcohol increased concomitant with a decrease in the rate of C=C hydrogenation. IR spectroscopy showed a strong perturbation of the C=O bond for the alkali-promoted catalyst, and volumetric chemisorption and TPD results suggested that the alkali species blocked adsorption at low-coordination Ru sites. These adsorption and reaction studies suggest that polarization of the adsorbed substrate at the C=O bond is responsible for the significant shift in product selectivity upon alkali promotion. This work combines spectroscopic tools with the use of the catalytic reaction itself as a probe of catalyst surface chemistry. 40 refs., 6 figs., 3 tabs.

  18. The detection of cholera toxin based on agglutination reaction with amplification of silica nanoparticles%纳米二氧化硅颗粒免疫凝聚用于霍乱毒素的检测研究

    Institute of Scientific and Technical Information of China (English)

    余红伟; 王源升; 李瑜; 蒋健晖; 吴海龙; 魏徵; 沈国励; 俞汝勤


    提出了一种基于SiO2纳米颗粒免疫凝集反应的压电传感器对霍乱毒素的直接检测,研究发现待测物霍乱毒素会同时被晶振表面固定的霍乱毒素抗体和检测体系中SiO:标记的霍乱毒素抗体识别,引起检测体系中的SiO:在传感界面上特异性凝集,从而引起晶振表面的巨大质量变化和检测介质密度和粘度变化。实验结果表明,该方法修饰的探针能够有效地对霍乱毒素进行检测。%A simple piezoelectric immunoagglutination assay technique has been developed for direct detection of cholera toxin. It was based on the specific agglutination of cholera toxin antibody-coated silica nanoparticles in the presence of cholera toxin. The antibody modified on the probe surface would combine with antibody-coated nanoparticles in the presence of antigen (cholera toxin) when the surface agglutinationreaction took place, which couples both the mass effect and the viscoelastic effect acting on the probe. The results indicated that the probe signal can be observably multiplied.

  19. Silaffins in Silica Biomineralization and Biomimetic Silica Precipitation

    Directory of Open Access Journals (Sweden)

    Carolin C. Lechner


    Full Text Available Biomineralization processes leading to complex solid structures of inorganic material in biological systems are constantly gaining attention in biotechnology and biomedical research. An outstanding example for biomineral morphogenesis is the formation of highly elaborate, nano-patterned silica shells by diatoms. Among the organic macromolecules that have been closely linked to the tightly controlled precipitation of silica in diatoms, silaffins play an extraordinary role. These peptides typically occur as complex posttranslationally modified variants and are directly involved in the silica deposition process in diatoms. However, even in vitro silaffin-based peptides alone, with and without posttranslational modifications, can efficiently mediate biomimetic silica precipitation leading to silica material with different properties as well as with encapsulated cargo molecules of a large size range. In this review, the biomineralization process of silica in diatoms is summarized with a specific focus on silaffins and their in vitro silica precipitation properties. Applications in the area of bio- and nanotechnology as well as in diagnostics and therapy are discussed.

  20. Styrene grafted natural rubber reinforced by in situ silica generated via sol–gel technique

    Energy Technology Data Exchange (ETDEWEB)

    Sittiphan, Torpong [Program of Petrochemistry and Polymer Sciences, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand); Prasassarakich, Pattarapan [Department of Chemical Technology, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand); Poompradub, Sirilux, E-mail: [Department of Chemical Technology, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand)


    Highlights: • Sol–gel reaction by NR latex was the absence of use of organic solvent and base catalyst. • Well dispersed in situ formed silica particles in the rubber matrix were obtained. • In situ silica was better to improve mechanical properties of rubber vulcanizates. -- Abstract: The filling of styrene graft natural rubber (ST-GNR) with in situ formed silica was performed using the sol–gel reaction via the latex solution method. The mechanical properties of ST-GNR/NR vulcanizate were improved when using the in situ formed silica to levels higher than those obtained with the commercial ex situ formed silica filled ST-GNR/NR vulcanizates at a comparable silica content of 12 parts by weight per hundred parts of rubber. Transmission electron microscopy analysis revealed that the in situ silica particles were small (∼40 nm diameter) and well dispersed, while the commercial silica particles were larger (∼60 nm diameter) and markedly agglomerated in the rubbery matrix. The mechanical properties of the composites prepared via both the solid rubber and latex solution methods were comparable.

  1. Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Yi, Tanghong; Chen, Wei; Cheng, Lei; Bayliss, Ryan D.; Lin, Feng; Plews, Michael R.; Nordlund, Dennis; Doeff, Marca M.; Persson, Kristin A.; Cabana, Jordi


    Reversible intercalation reactions provide the basis for modern battery electrodes. Despite decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials AxK1–xFeF3 (A = Li, Na). By starting with KFeF3, approximately 75% of K+ ions were subsequently replaced by Li+ and Na+ through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopy confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. This study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.

  2. Hydride encapsulation by molecular alkali-metal clusters. (United States)

    Haywood, Joanna; Wheatley, Andrew E H


    The sequential treatment of group 12 and 13 Lewis acids with alkali-metal organometallics is well established to yield so-called ''ate' complexes, whereby the Lewis-acid metal undergoes nucleophilic attack to give an anion, at least one group 1 metal acting to counter this charge. However, an alternative, less well recognised, reaction pathway involves the Lewis acid abstracting hydride from the organolithium reagent via a beta-elimination mechanism. It has recently been shown that in the presence of N,N'-bidentate ligands this chemistry can be harnessed to yield a new type of molecular main-group metal cluster in which the abstracted LiH is effectively trapped, with the hydride ion occupying an interstitial site in the cluster core. Discussion focuses on the development of this field, detailing advances in our understanding of the roles of Lewis acid, organolithium, and amine substrates in the syntheses of these compounds. Structure-types are discussed, as are efforts to manipulate cluster geometry and composition as well as hydride-coordination. Embryonic mechanistic studies are reported, as well as attempts to generate hydride-encapsulation clusters under catalytic control.

  3. Characterization of silica particles prepared via urease-catalyzed urea hydrolysis and activity of urease in sol-gel silica matrix

    Energy Technology Data Exchange (ETDEWEB)

    Kato, Katsuya, E-mail: [National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimoshidami, Moriyama-ku, Nagoya 463-8560 (Japan); Nishida, Masakazu [National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimoshidami, Moriyama-ku, Nagoya 463-8560 (Japan); Ito, Kimiyasu; Tomita, Masahiro [Division of Chemistry for Materials, Graduate School of Engineering, Mie University, 1577 Kurimamachiya-cho, Tsu, Mie 514-8570 (Japan)


    Highlights: Black-Right-Pointing-Pointer Silica precipitation occurred via urease-catalytic reactions. Black-Right-Pointing-Pointer Higher urease activity for silica synthesis enables mesostructure of silica-urease composites. Black-Right-Pointing-Pointer Urease encapsulating in silica matrix retained high activity. - Abstract: Urease templated precipitation of silica synthesized by sol-gel chemistry produces a composite material allowing high urease activity. This study investigates the structural properties of the composite material that allow for the retention of the urease hydrolysis activity. Scanning (SEM) and transmission (TEM) electron microscopy reveal that the composite has a mesoporous structure composed of closely packed spherical structures {approx}20-50 nm in diameter. Brunauer-Emmett-Teller (BET) analysis revealed that the surface area and pore volume of the composite prepared under the conditions of 50 mM urea and 25 Degree-Sign C is relatively high (324 m{sup 2}/g and 1.0 cm{sup 3}/g). These values are equivalent to those of usual mesoporous silica materials synthesized from the self-assembly of triblock copolymers as organic templates. In addition, after encapsulating in a sol-gel silica matrix, urease retained high activity ({approx}90% of the activity compared with native urease). Our results suggest a new method for synthesizing mesoporous silica materials with highly tunable pore sizes and shapes under mild conditions.

  4. Thermoluminescence of alkali halides and its implications

    Energy Technology Data Exchange (ETDEWEB)

    Gartia, R.K., E-mail: [Physics Department, Manipur University, Imphal 795003 (India); Rey, L. [Aerial-CRT-parc d' Innovation, B.P. 40443, F-67412 Illkirch Cedex (France); Tejkumar Singh, Th. [Physics Department, Manipur University, Imphal 795003 (India); Basanta Singh, Th. [Luminescence Dating Laboratory, Manipur University, Imphal 795003 (India)


    Trapping levels present in some alkali halides namely NaCl, KCl, KBr, and KI are determined by deconvolution of the thermoluminescence (TL) curves. Unlike most of the studies undertaken over the last few decades, we have presented a comprehensive picture of the phenomenon of TL as an analytical technique capable of revealing the position of the trapping levels present in the materials. We show that for all practical purposes, TL can be described involving only the three key trapping parameters, namely, the activation energy (E), the frequency factor (s), and the order of kinetics (b) even for complex glow curves having a number of TL peaks. Finally, based on these, we logically infer the importance of TL in development and characterization of materials used in dosimetry, dating and scintillation.

  5. Controlled in-situ dissolution of an alkali metal

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Jeffrey Donald; Dooley, Kirk John; Tolman, David Donald


    A method for the controllable dissolution of one or more alkali metals from a vessel containing a one or more alkali metals and/or one or more partially passivated alkali metals. The vessel preferably comprising a sodium, NaK or other alkali metal-cooled nuclear reactor that has been used. The alkali metal, preferably sodium, potassium or a combination thereof, in the vessel is exposed to a treatment liquid, preferably an acidic liquid, more preferably citric acid. Preferably, the treatment liquid is maintained in continuous motion relative to any surface of unreacted alkali metal with which the treatment liquid is in contact. The treatment liquid is preferably pumped into the vessel containing the one or more alkali metals and the resulting fluid is extracted and optionally further processed. Preferably, the resulting off-gases are processed by an off-gas treatment system and the resulting liquids are processed by a liquid disposal system. In one preferred embodiment, an inert gas is pumped into the vessel along with the treatment liquid.

  6. Mistletoe alkali inhibits peroxidation in rat liver and kidney

    Institute of Scientific and Technical Information of China (English)

    Zheng-Ming Shi; Ping Feng; Dong-Qiao Jiang; Xue-Jiang Wang


    AIM: To explore the antioxidant and free radical scavenger properties of mistletoe alkali (MA).METHODS: The antioxidant effect of mistletoe alkali on the oxidative stress induced by carbon tetrachloride (CCl4) in rats was investigated. The rats were divided into four groups (n = 8): CCl4-treated group (1 mL/kg body weight), MA -treated group (90 mg/kg), CCl4+MA-treated group and normal control group. After 4 wk of treatment,the level of malondialdehyde (MDA), a lipid peroxidation product (LPO) was measured in serum and homogenates of liver and kidney. Also, the level of glutathione (GSH),and activities of glutathione reductase (GR), glutathione peroxidase (GSPx), superoxide dismutase (SOD), and glutathione-S-transferase (GST) in liver and kidney were determined. Scavenging effects on hydroxyl free radicals produced in vitro by Fenton reaction were studied by ESR methods using 5,5-dimethyl-1-pyrroline-N-oxidesource. Urinary 8-hydroxydeoxyguanosine (8-OHdG) was determined by competitive ELISA.RESULTS: In CCl4-treated group, the level of LPO in serum of liver and kidney was significantly increased compared to controls. The levels of GSH and enzyme activities of SOD, GSPx and GR in liver and kidney were significantly decreased in comparison with controls. In CCl4+MA-treated group, the changes in the levels of LPO in serum of liver and kidney were not statistically significant compared to controls. The levels of SOD, GSPx and GR in liver and kidney were significantly increased in comparison with controls. There was a significant difference in urinary excretion of 8-OHdG between the CCl4-treated and MA-treated groups.CONCLUSION: Oxidative stress may be a major mechanism for the toxicity of CCl4. MA has a protective www.wjgnet.comeffect against CCl4 toxicity by inhibiting the oxidative damage and stimulating GST activities. Thus, clinical application of MA should be considered in cases with carbon tetrachloride-induced injury.

  7. Biogenic nanostructured silica

    Institute of Scientific and Technical Information of China (English)


    Silicon is by far the most abundant element in the earth crust and also is an essential element for higher plants, yet its biology and mechanisms in plant tolerance of biotic and abiotic stresses are poorly understood. Based on the molecular mechanisms of the biosilicification in marine organisms such as diatoms and sponges, the cell wall template-mediated self-assembly of nanostructured silica in marine organisms and higher plants as well as the related organic molecules are discussed. Understanding of the templating and structure-directed effects of silicon-processing organic molecules not only offers the clue for synthesizing silicon-based materials, but also helps to recognize the anomaly of silicon in plant biology.

  8. Extraction of Alkali Ions Investigated by Conductometric and pH Measurements

    Directory of Open Access Journals (Sweden)

    L. Kalvoda


    Full Text Available Extraction of alkali ions from aqueous solutions of chlorides and hydroxides into a lipophilic liquid membrane composed of tetraethyl p-tert-butylcalix[4]arene tetraacetate (TBT solution in hexane was investigated by means of measurements of changes in the electrolytic conductivity and pH-value of the aqueous solution. Hydrolysis of the TBT ionophore resulting in the release of the ethyl groups was proposed as the main reaction process, leading to disturbance of the known preference of TBT for sodium ions. 

  9. Highly dispersed iron species created on alkali-treated zeolite for ammonia SCR

    Institute of Scientific and Technical Information of China (English)

    Jing Ma; Duan Weng; Xiaodong Wu; Zhichun Si; Zhenwei Wu


    Alkaline treatment using sodium hydroxide was introduced to obtain a hierarchical pore structure in H-ZSM-5 zeolite. Fe-exchanged zeolite catalysts were prepared by impregnation on the original and alkali-treated zeolites, and were evaluated for NOx reduction by NH3, NO oxidation, and NH3 oxidation reactions. The highly dispersed iron species as active sites can be obtained by controlling the pore structure and particle size of zeolite. Therefore, the Fe/ZSM-5 catalyst treated mildly by sodium hydroxide before iron exchange, which contains amounts of highly dispersed Fe species, obtains over 80% NOx conversion at a wide temperature range of 250-500 1C.


    Allison, A. C.; Harington, J. S.; Birbeck, M.


    Effects of silica, diamond dust, and carrageenan on mouse macrophages were studied by phase-contrast cine-micrography, electron microscopy, histochemical techniques for lysosomal enzymes and measurements of the release of lysosomal enzymes into the culture medium. All added materials were rapidly taken up into phagosomes, to which lysosomes became attached. In all cases lysosomal enzymes were discharged into the phagosomes to form secondary lysosomes. Within 24 hr most of the silica particles and enzyme had escaped from the secondary lysosomes and lysosomal enzymes were found in the culture media. Most macrophages were killed by this time. With nontoxic particles (diamond dust, aluminium-coated silica, or silica in the presence of the protective agent polyvinyl-pyridine-N-oxide, PVPNO) ingested particles and lysosomal enzymes were retained within the secondary lysosomes for a much longer time, and cytotoxic effects were considerably delayed or absent altogether. It is concluded that silica particles are toxic because they are efficiently taken up by macrophages and can then react relatively rapidly with the membranes surrounding the secondary lysosomes. The particles and lytic enzymes can then escape into the cytoplasm, producing general damage, and thence into the culture medium. It is suggested that hydrogen bonding of silicic acid with lipid and protein constituents of the membrane accounts for the induced permeability. Protective agents such as PVPNO are retamed in lysosomes and preferentially form hydrogen bonds with silicic acid. Carrageenan is demonstrable within macrophages by its metachromatic reaction. It brings about release of enzymes from secondary lysosomes, but much more slowly than does silica. Silica released from killed macrophages is as cytotoxic as the original preparation. It is suggested that repeated cycles of macrophage killing in vivo leads to the mobilization of fibroblasts and fibrogenesis characterizing the disease silicosis. PMID

  11. Chemical thermodynamics of silica: a critique on its geothermometer

    Energy Technology Data Exchange (ETDEWEB)

    Verma, Mahendra P. [Instituto de Investigaciones Electricas, Dept. de Geotermia, Cuernavaca (Mexico)


    The chemical thermodynamic concepts used in the calculation of solubility data of silica (quartz) are presented taking into account the PVT characteristics of water. The temperature-dependence trends between the thermodynamically calculated and the experimental quartz solubility data are very similar, but the values are widely different at high temperatures. The experimental solubility, especially along the saturation curve at high temperature and thermodynamic data for silica need to be reevaluated in order to use silica chemistry to understand geological processes. There could exist a wide range of values for silica solubility at a specified temperature, depending upon the amount of water in the reaction vessel. Thus the silica contents in geothermal fluid, in general, cannot be used as a geothermometer to estimate the reservoir temperature. The derivation of a silica geothermometer needs an extra assumption about the total amount of water in the system. The solubility data for the two extreme cases, i.e. when the vessel (bomb) is completely filled with water and when there is just enough water to make the total specific volume equal to the critical volume of water at room temperature (25degC), are considered here. These lie on the two respective straight lines of log (SiO{sub 2}(ppm)) against temperature (K). The equations for the two straight lines are log (SiO{sub 2} (ppm)) = 0.0179 T (K)-4.3214 and log SiO{sub 2} (ppm) = 0.0088 T (K)-1.6513, respectively. In the case of the well M-19A at Cerro Prieto, the silica concentration in the reservoir liquid is higher than the experimental solubility, but is lower than the calculated solubility value. (Author)

  12. 21 CFR 582.1711 - Silica aerogel. (United States)


    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Silica aerogel. 582.1711 Section 582.1711 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam...

  13. 21 CFR 182.1711 - Silica aerogel. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Silica aerogel. 182.1711 Section 182.1711 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam...

  14. 21 CFR 584.700 - Hydrophobic silicas. (United States)


    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Hydrophobic silicas. 584.700 Section 584.700 Food... DRINKING WATER OF ANIMALS Listing of Specific Substances Affirmed as GRAS § 584.700 Hydrophobic silicas. (a) Product. Amorphous fumed hydrophobic silica or precipitated hydrophobic silica (CAS Reg. No....

  15. A contribution to the surface characterization of alkali metal sulfates

    Energy Technology Data Exchange (ETDEWEB)

    Fantauzzi, Marzia; Rigoldi, Americo; Elsener, Bernhard; Atzei, Davide; Rossi, Antonella, E-mail:


    Highlights: • Full electronic characterization of alkali metals sulfates by X-ray photoelectron spectroscopy and X-ray induced Auger electron spectroscopy. • Curve-fitting of SKLL signals makes possible to clarify the role of the cation in the series of alkali metal sulfates. • Differences in the binding energies and Auger parameter are discussed in terms of the electronic properties and the polarizability of the cation. • The line intensities are analyzed and a thorough quantitative analysis is presented. - Abstract: The analytical characterization of surfaces of sulfur-bearing samples that present sulfides, polysulfides and/or elemental sulfur as reaction products can be difficult by simply relying on the binding energy of the S2p X-ray photoelectron signals, due to the small chemical shifts. In such cases the Auger parameter concept can be used to distinguish among different chemical states, but this requires a model to curve fit complex Auger SKLL signals in order to resolve the contributions arising from sulfur in different chemical states on the surface. With this scope a detailed X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger electron spectroscopy (XAES) surface analytical study of the group IA sulfates is presented in this paper. Sulfates were chosen as model compounds for curve fitting the X-ray induced SKLL spectra since in these compounds sulfur is present in a unique chemical state. For the first time the multicomponent SKLL spectra are fitted with model functions consisting of an intense {sup 1}D and a low intensity {sup 1}S contribution with constant energy difference of 8 eV. It was found that the kinetic energy of the SK{sub 2,3}L{sub 2,3} ({sup 1}D) line increases from 2105.1 ± 0.1 to 2107.5 ± 0.2 eV whereas the corresponding S2p{sub 3/2} binding energy decreases from 169.5 ± 0.1 eV for Li{sub 2}SO{sub 4} to 167.8 ± 0.1 eV for Cs{sub 2}SO{sub 4}. Shifts to lower binding energy values are observed also for S2p, S2s and O1

  16. Pi resonance of chemisorbed alkali atoms on noble metals. (United States)

    Borisov, A G; Sametoglu, V; Winkelmann, A; Kubo, A; Pontius, N; Zhao, J; Silkin, V M; Gauyacq, J P; Chulkov, E V; Echenique, P M; Petek, H


    We have performed a joint experimental and theoretical study of the unoccupied electronic structure of alkali adsorbates on the (111) surfaces of Cu and Ag. Combining angle- and time-resolved two-photon photoemission spectroscopy with wave packet propagation calculations we show that, along with the well known sigma resonance oriented along the surface normal, there exist long-lived alkali-localized resonances oriented parallel to the surface (pi symmetry). These new resonances are stabilized by the projected band gap of the substrate and emerge primarily from the mixing of the p and d Rydberg orbitals of the free alkali atom modified by the interaction with the surface.

  17. Important role of alkali atoms in A4C60


    Gunnarsson, O.; Erwin, S. C.; Koch, E.; Martin, R. M.


    We show that hopping via the alkali atoms plays an important role for the t1u band of A4C60 (A=K, Rb), in strong contrast to A3C60. Thus the t1u band is broadened by more than 40 % by the presence of the alkali atoms. The difference between A4C60 and A3C60 is in particular due to the less symmetric location of the alkali atoms in A4C60.

  18. Effect of gamma irradiation on the texture, acidity and catalytic activity of silica-aluminium and silica-magnesia catalysts (United States)

    Youssef, A. M.; Samra, S. E.; Ahmed, Awad I.

    The textural properties of non-irradiated and γ-irradiated silica-aluminium and silica-magnesia catalysts were determined from nitrogen adsorption. The acidities of these catalysts were measured by the chemisorption of pyridine. Cracking of cumene and dehydration of isopropanol were investigated on non-irradiated and γ-irradiated catalysts. Irradiation with γ-rays enhanced sintering, i.e. decreased the surface area and increased pore size. For silica-magnesia, γ-irradiation enhanced crystallization of Forsterite and Enstatite. The surface acidity decreased upon γ-irradiation and consequently the activity of the catalysts towards cracking of cumene and dehydration of isopropanol was reduced. The former reaction is structure-sensitive, while the latter is structure-insensitive.

  19. Microwave assisted alkali-catalyzed transesterification of Pongamia pinnata seed oil for biodiesel production. (United States)

    Kumar, Ritesh; Kumar, G Ravi; Chandrashekar, N


    In this study, microwave assisted transesterification of Pongamia pinnata seed oil was carried out for the production of biodiesel. The experiments were carried out using methanol and two alkali catalysts i.e., sodium hydroxide (NaOH) and potassium hydroxide (KOH). The experiments were carried out at 6:1 alcohol/oil molar ratio and 60°C reaction temperature. The effect of catalyst concentration and reaction time on the yield and quality of biodiesel was studied. The result of the study suggested that 0.5% sodium hydroxide and 1.0% potassium hydroxide catalyst concentration were optimum for biodiesel production from P. pinnata oil under microwave heating. There was a significant reduction in reaction time for microwave induced transesterification as compared to conventional heating.

  20. Alkali activation of recovered fuel-biofuel fly ash from fluidised-bed combustion: Stabilisation/solidification of heavy metals. (United States)

    Yliniemi, Juho; Pesonen, Janne; Tiainen, Minna; Illikainen, Mirja


    Recovered fuel-biofuel fly ash from a fluidized bed boiler was alkali-activated and granulated with a sodium-silicate solution in order to immobilise the heavy metals it contains. The effect of blast-furnace slag and metakaolin as co-binders were studied. Leaching standard EN 12457-3 was applied to evaluate the immobilisation potential. The results showed that Ba, Pb and Zn were effectively immobilised. However, there was increased leaching after alkali activation for As, Cu, Mo, Sb and V. The co-binders had minimal or even negative effect on the immobilisation. One exception was found for Cr, in which the slag decreased leaching, and one was found for Cu, in which the slag increased leaching. A sequential leaching procedure was utilized to gain a deeper understanding of the immobilisation mechanism. By using a sequential leaching procedure it is possible fractionate elements into watersoluble, acid-soluble, easily-reduced and oxidisable fractions, yielding a total 'bioavailable' amount that is potentially hazardous for the environment. It was found that the total bioavailable amount was lower following alkali activation for all heavy metals, although the water-soluble fraction was higher for some metals. Evidence from leaching tests suggests the immobilisation mechanism was chemical retention, or trapping inside the alkali activation reaction products, rather than physical retention, adsorption or precipitation as hydroxides.

  1. Synthesis and exchange properties of sulfonated poly(phenylene sulfide) with alkali metal ions in organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Son, Won Keun [Chungnam National Univ., Taejon (Korea, Republic of); Kim, Sang Hern [Taejon National Univ., Taejon (Korea, Republic of); Park, Soo Gil [Chungbuk National Univ., Cheongju (Korea, Republic of)


    Sulfonated poly(phenylene sulfide) (SPPS) polymers were prepared by sulfonation of poly[methyl[4-(phenylthio)phenyl] sulfonium trifluoromethanesulfonate] (PPST) with fumic sulfonic acid (10% SO{sub 3}-H{sub 2}SO{sub 4}) and demethylation with aqueous NaOH solution. The equilibrium constants of ion exchange reactions between alkali metal cations (Li{sup +}, Na{sup +}, and K{sup +}) and SPPS ion exchanger in organic solvents such as in organic solvents such as tetrahydrofuran (THF) and dioxane were measured. The equilibrium constants of ion exchange reactions increased as the polarity of the solvent increased, and the reaction temperature decreased. The equilibrium constants of the ion exchange reaction (K{sub eq}) also increased in the order of Li{sup +}, Na{sup +}, and K{sup +}. To elucidate the spontaneity of the exchange reaction in organic solvents, the enthalpy, entropy, and Gibbs free energy were calculated. The enthalpy of reaction ranged from -0.88 to -1.33 kcal/mol, entropy ranged from 1.42 to 4.41 cal/Kmol, and Gibbs free energy ranged from -1.03 to -2.55 kcal/mol. Therefore, the exchange reactions were spontaneous because the Gibbs free energies were negative. The SPPS ion exchanger and alkali metal ion bounding each other produced good ion exchange capability in organic solvents.

  2. Effect of silica gel on the cohesion, properties and biological performance of brushite cement. (United States)

    Alkhraisat, Mohammad Hamdan; Rueda, Carmen; Jerez, Luis Blanco; Tamimi Mariño, Faleh; Torres, Jesus; Gbureck, Uwe; Lopez Cabarcos, Enrique


    The cohesion of calcium phosphate cements can be improved by the addition of substances to either the solid or liquid phase during the setting reaction. This study reports the effect of silica gel on brushite cement cohesion. The cement was prepared using a mixture of beta-tricalcium phosphate (beta-TCP) and monocalcium phosphate monohydrate as the solid phase, while the liquid phase comprised carboxylic acids silica gel. This cement presents a shorter final setting time (FST), better cohesion and higher amount of unreacted beta-TCP than the cement prepared without silica gel. Furthermore, in vivo experiments using rabbits as an animal model showed that after 8 weeks of implantation cements modified with silica gel showed a similar new bone formation volume and more remaining graft in comparison with unmodified cements. Thus, the silica gel could be efficiently applied to reduce cement disintegration and to decrease the resorption rate of brushite cements.

  3. Preparation and characterization of silk/silica hybrid biomaterials by sol-gel crosslinking process

    Energy Technology Data Exchange (ETDEWEB)

    Hou Aiqin, E-mail: [National Engineering Research Center for Dyeing and Finishing of Textiles, Donghua University, 3H, 2999 North Renmin Road, Songjiang, Shanghai 201620 (China); Chen Huawei [National Engineering Research Center for Dyeing and Finishing of Textiles, Donghua University, 3H, 2999 North Renmin Road, Songjiang, Shanghai 201620 (China)


    The silk/silica hybrid biomaterials are synthesized by sol-gel crosslinking process. The chemical and morphological structures of silk/silica hybrids are investigated with micro-FT-IR spectra, X-ray diffraction, SEM, AFM, and DSC. The results show that the crosslinking reactions among inorganic nano-particles, fibroin and 2,4,6-tri[(2-epihydrin-3-bimethyl-ammonium)propyl]-1,3,5-triazine chloride (Tri-EBAC) take place during sol-gel process. The silk/silica hybrids form new molecular structures containing not only organic fibroin but also inorganic nano-silica particles. The inorganic particles are bounded to the fibroin through covalent bonds. The silk/silica hybrids can form excellent film with very even nanometer particles. The thermal properties of organic/inorganic hybrid are improved.

  4. Preparation of silica coatings heavily doped with spiropyran using perhydropolysilazane as the silica source and their photochromic properties. (United States)

    Yamano, Akihiro; Kozuka, Hiromitsu


    Silica coatings doped with spiropyran (SP) were prepared using xylene solutions of perhydropolysilazane (PHPS) as the silica source, where the SP-doped PHPS coatings were prepared by spin-coating and the PHPS-to-silica conversion was achieved by exposing the coatings to the vapor from aqueous ammonia at room temperature. The films could be heavily doped with SP at SP/(SP + PHPS) mass ratio as high as 0.2. The as-deposited SP-doped PHPS films were transparent and light-yellow, which turned to red as the PHPS-to-silica conversion proceeded, where the absorbance at 500 nm increased. When the films were stored in air in the dark for 73 h after the exposure treatment, the absorbance at 500 nm further increased, where the film turned from red to dark red. The SP-doped silica coatings thus obtained showed reversible photochromic reaction, where the absorbance at 500 nm decreased and increased when the films were irradiated with visible and ultraviolet light, respectively. The pencil hardness of the films was higher than 9H at a load of 1 kg, while significant amount of SP was leached out when the films were soaked in xylene.

  5. Kinetics of Coloration in Photochromic Tungsten(VI) Oxide/Silicon Oxycarbide/Silica Hybrid Xerogel: Insight into Cation Self-diffusion Mechanisms. (United States)

    Adachi, Kenta; Tokushige, Masataka; Omata, Kaoru; Yamazaki, Suzuko; Iwadate, Yoshiaki


    Silicon oxycarbide/silica composites with well-dispersed tungsten(VI) oxide (WO3) nanoparticles were obtained as transparent hybrid xerogels via an acid-catalyzed sol-gel process (hydrolysis/condensation polymerization) of 3-(triethoxysilyl)propyl methacrylate (TESPMA) and tetraethoxysilane (TEOS). The self-diffusion mechanism of alkali-metal cations and the kinetics of the photochromic coloration process in the WO3/TESPMA/TEOS hybrid xerogel systems have been systematically investigated. Under continuous UV illumination, a gradual color change (colorless → blue) corresponding to the reduction of W(6+) into W(5+) states in WO3 nanoparticles can be confirmed from the WO3/TESPMA/TEOS hybrid xerogels containing alkali-metal sulfates, although no coloration of the hybrid xerogel without alkali-metal sulfate was observed. The coloration behavior depended exclusively on a variety of alkali-metal cations present in the hybrid xerogel system. Furthermore, a detailed analysis of the self-diffusion mechanism confirmed that the alkali-metal cations electrostatically interact with a layer of unreacted silanol groups on the TESPMA/TEOS matrix surface, and subsequently pass through the interconnected pore network of the hybrid xerogel. More interestingly, in the context of an Arrhenius analysis, we found a good coincidence between the activation energies for alkali-metal cation self-diffusion and UV-induced coloration in the WO3/TESPMA/TEOS hybrid xerogel system containing the corresponding alkali-metal sulfate. It is experimentally obvious that the photochromic properties are dominated by the diffusion process of alkali-metal cations in the WO3/TESPMA/TEOS hybrid xerogel system. Such hybrid materials with cation-controlled photochromic properties will show promising prospects in applications demanding energy-efficient "smart windows" and "smart glasses".

  6. Silica exposure and systemic vasculitis.


    Mulloy, Karen B


    Work in Department of Energy (DOE) facilities has exposed workers to multiple toxic agents leading to acute and chronic diseases. Many exposures were common to numerous work sites. Exposure to crystalline silica was primarily restricted to a few facilities. I present the case of a 63-year-old male who worked in DOE facilities for 30 years as a weapons testing technician. In addition to silica, other workplace exposures included beryllium, various solvents and heavy metals, depleted uranium, a...

  7. Novel nanocomposites from spider silk–silica fusion (chimeric) proteins (United States)

    Wong Po Foo, Cheryl; Patwardhan, Siddharth V.; Belton, David J.; Kitchel, Brandon; Anastasiades, Daphne; Huang, Jia; Naik, Rajesh R.; Perry, Carole C.; Kaplan, David L.


    Silica skeletal architectures in diatoms are characterized by remarkable morphological and nanostructural details. Silk proteins from spiders and silkworms form strong and intricate self-assembling fibrous biomaterials in nature. We combined the features of silk with biosilica through the design, synthesis, and characterization of a novel family of chimeric proteins for subsequent use in model materials forming reactions. The domains from the major ampullate spidroin 1 (MaSp1) protein of Nephila clavipes spider dragline silk provide control over structural and morphological details because it can be self-assembled through diverse processing methods including film casting and fiber electrospinning. Biosilica nanostructures in diatoms are formed in aqueous ambient conditions at neutral pH and low temperatures. The R5 peptide derived from the silaffin protein of Cylindrotheca fusiformis induces and regulates silica precipitation in the chimeric protein designs under similar ambient conditions. Whereas mineralization reactions performed in the presence of R5 peptide alone form silica particles with a size distribution of 0.5–10 μm in diameter, reactions performed in the presence of the new fusion proteins generate nanocomposite materials containing silica particles with a narrower size distribution of 0.5–2 μm in diameter. Furthermore, we demonstrate that composite morphology and structure could be regulated by controlling processing conditions to produce films and fibers. These results suggest that the chimeric protein provides new options for processing and control over silica particle sizes, important benefits for biomedical and specialty materials, particularly in light of the all aqueous processing and the nanocomposite features of these new materials. PMID:16769898

  8. Structure and electronic properties of alkali-C60 nanoclusters. (United States)

    Rabilloud, Franck


    I investigated the structural and electronic properties of both Na(n)C(60) and Li(n)C(60) (n alkali atoms over the C(60) surface is analyzed. The hypotheses for either an homogeneous coating of the C(60) surface by the alkali atoms or the growth of an alkali droplet not wetting the fullerene surface are discussed. Lithium atoms are found to coat homogeneously the fullerene on the C(60) surface via pentagonal sites, contrary to sodium atoms, which prefer to form 4-atom islands on the surface. The charge transfer, the energetics, and the dipole moments are discussed in relation with available results. The adsorption of alkali atoms on the C(60) surface considerably enhances the capacity of C(60) to accept electrons. The arrangement of lithium atoms seems more favorable for the hydrogen storage than that of sodium atoms.

  9. Hall Determination of Atomic Radii of Alkali Metals (United States)

    Houari, Ahmed


    I will propose here an alternative method for determining atomic radii of alkali metals based on the Hall measurements of their free electron densities and the knowledge of their crystal structure. (Contains 2 figures.)

  10. Electric field-induced softening of alkali silicate glasses

    Energy Technology Data Exchange (ETDEWEB)

    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.

  11. A Novel Eco-Alkali Chemistry in Newspaper Flotation Deinking

    Directory of Open Access Journals (Sweden)

    Ivana Plazonic


    Full Text Available Performance and efficiency of fresh offset-printed daily Croatian newspaper deinked by novel chemistry, named Eco-alkali, were investigated in this study. Eco-alkali is naturally gained alkali prepared from domestic by-product wood fly ash collected after hardwood ignition. Brightness, opacity and effective residual ink concentration (ERIC as optical properties were evaluated for the deinked pulp before and after flotation. Lingering ink particles and their total surface area were measured by image analysis method. Experimental results are compared to the pulp deinked with worldwide accepted method INGEDE Method 11 using identical steps through the whole deinking process. The findings obtained from present work, especially removing particle efficiency results before flotation, indicated that eco-alkali have potential to be used in flotation deinking of newspapers.

  12. Acid/alkali gated photochromism of two diarylperfluorocyclopentenes

    Institute of Scientific and Technical Information of China (English)

    CHEN; ZiHui; ZHAO; ShengMin; LI; ZhongYu; ZHANG; Zhi; ZHANG; FuShi


    Two novel diarylfuorocyclopentenes, which underwent gated photochromism, were synthesized. It was found that the photochromic property of these diarylethenes could be switched by alternative addition of acids/alkalis, which could provide a new design strategy toward chemical threshold photoreaction.

  13. Near atomically smooth alkali antimonide photocathode thin films

    CERN Document Server

    Feng, Jun; Nasiatka, James; Schubert, Susanne; Smedley, John; Padmore, Howard


    Nano-roughness limits the emittance of electron beams that can be generated by high efficiency photocathodes, such as the thermally reacted alkali antimonide thin films. However there is an urgent need for photocathodes that can produce an order of magnitude or more lower emittance than present day systems in order to increase the transverse coherence width of the electron beam. In this paper we demonstrate a method for producing alkali antimonide cathodes with near atomic smoothness with high reproducibility.

  14. Estimating the hydration enthalpies of neutral alkali metal atoms. (United States)

    Stace, A J


    Using existing data on the ionization energies of alkali metal atoms in small clusters of water, a thermodynamic cycle is proposed from which the hydration enthalpies of the neutral metal atoms can be estimated. Where comparisons are possible, the results are in reasonable agreement with those obtained using both experimental and ab initio methods. Application of the thermodynamic cycle to neutral alkali metal atoms solvated in ammonia yields solvation enthalpies that are significantly lower than those obtained for water.

  15. Photoemission spectroscopy study of a multi-alkali photocathode

    CERN Document Server

    Ettema, A R H


    In this paper a photoemission study of the highest core levels of the elements and the electron escape barrier (work function) in a multi-alkali photocathode are presented. The core levels indicate that the alkali atoms are in an oxidized state and therefore the compound Na sub 2 KSb can be regarded as an ionic semiconductor. The measured escape barrier of the Cs sub 2 O surface layer is determined as 2.3 eV.

  16. Alkali absorption and citrate excretion in calcium nephrolithiasis (United States)

    Sakhaee, K.; Williams, R. H.; Oh, M. S.; Padalino, P.; Adams-Huet, B.; Whitson, P.; Pak, C. Y.


    The role of net gastrointestinal (GI) alkali absorption in the development of hypocitraturia was investigated. The net GI absorption of alkali was estimated from the difference between simple urinary cations (Ca, Mg, Na, and K) and anions (Cl and P). In 131 normal subjects, the 24 h urinary citrate was positively correlated with the net GI absorption of alkali (r = 0.49, p < 0.001). In 11 patients with distal renal tubular acidosis (RTA), urinary citrate excretion was subnormal relative to net GI alkali absorption, with data from most patients residing outside the 95% confidence ellipse described for normal subjects. However, the normal relationship between urinary citrate and net absorbed alkali was maintained in 11 patients with chronic diarrheal syndrome (CDS) and in 124 stone-forming patients devoid of RTA or CDS, half of whom had "idiopathic" hypocitraturia. The 18 stone-forming patients without RTA or CDS received potassium citrate (30-60 mEq/day). Both urinary citrate and net GI alkali absorption increased, yielding a significantly positive correlation (r = 0.62, p < 0.0001), with the slope indistinguishable from that of normal subjects. Thus, urinary citrate was normally dependent on the net GI absorption of alkali. This dependence was less marked in RTA, confirming the renal origin of hypocitraturia. However, the normal dependence was maintained in CDS and in idiopathic hypocitraturia, suggesting that reduced citrate excretion was largely dietary in origin as a result of low net alkali absorption (from a probable relative deficiency of vegetables and fruits or a relative excess of animal proteins).

  17. Effect of silica nanoparticles on polyurethane foaming process and foam properties (United States)

    Francés, A. B.; Navarro Bañón, M. V.


    Flexible polyurethane foams (FPUF) are commonly used as cushioning material in upholstered products made on several industrial sectors: furniture, automotive seating, bedding, etc. Polyurethane is a high molecular weight polymer based on the reaction between a hydroxyl group (polyol) and isocyanate. The density, flowability, compressive, tensile or shearing strength, the thermal and dimensional stability, combustibility, and other properties can be adjusted by the addition of several additives. Nanomaterials offer a wide range of possibilities to obtain nanocomposites with specific properties. The combination of FPUF with silica nanoparticles could develop nanocomposite materials with unique properties: improved mechanical and thermal properties, gas permeability, and fire retardancy. However, as silica particles are at least partially surface-terminated with Si-OH groups, it was suspected that the silica could interfere in the reaction of poyurethane formation.The objective of this study was to investigate the enhancement of thermal and mechanical properties of FPUF by the incorporation of different types of silica and determining the influence thereof during the foaming process. Flexible polyurethane foams with different loading mass fraction of silica nanoparticles (0-1% wt) and different types of silica (non treated and modified silica) were synthesized. PU/SiO2 nanocomposites were characterized by FTIR spectroscopy, TGA, and measurements of apparent density, resilience and determination of compression set. Addition of silica nanoparticles influences negatively in the density and compression set of the foams. However, resilience and thermal stability of the foams are improved. Silica nanoparticles do not affect to the chemical structure of the foams although they interfere in the blowing reaction.

  18. Famed Bulgarian physicists. I. St. Petroff's Goettingen research of the photostimulated interconversions of color centers in alkali halides: the discovery of the photostimulated aggregation

    CERN Document Server

    Georgiev, Mladen


    This essay tells briefly of the life and work of one of the most successful scientists originating from a Balkan settlement whose name and popularity have greatly exceeded its realm. The word is of a discovery during WWII of the photostimulated aggregation of the F centers (else alkali atoms) dissolved from the vapor into an alkali halide crystal. Using optical absorption techniques while a grantee of Humboldt's Foundation in Goettingen, Germany between 1943-1944, he found new absorption bands pertaining to small-size F center aggregates and followed their interconversions. A primary photochemical solid state reaction was evidenced for the first time leading to nanoscale products.

  19. Absorption spectra of alkali-C₆₀ nanoclusters. (United States)

    Rabilloud, Franck


    We investigate the absorption spectra of alkali-doped C60 nanoclusters, namely C60Nan, C60Kn, and C60Lin, with n = 1, 2, 6, 12, in the framework of the time-dependent density-functional theory (TDDFT). We study the dependence of the absorption spectra on the nature of the alkali. We show that in few cases the absorption spectra depend on the arrangement of the alkali atoms over the fullerene, though sometimes the absorption spectra do not allow us to distinguish between different configurations. When only one or two alkali atoms are adsorbed on the fullerene, the optical response of alkali-doped C60 is similar to that of the anion C60(-) with a strong response in the UV domain. In contrast, for higher concentration of alkali, a strong optical response is predicted in the visible range, particularly when metal-metal bonds are formed. The weak optical response of the I(h)-symmetry C60Li12 is proposed to be used as a signature of its structure.

  20. Alkali-metal azides interacting with metal-organic frameworks. (United States)

    Armata, Nerina; Cortese, Remedios; Duca, Dario; Triolo, Roberto


    Interactions between alkali-metal azides and metal-organic framework (MOF) derivatives, namely, the first and third members of the isoreticular MOF (IRMOF) family, IRMOF-1 and IRMOF-3, are studied within the density functional theory (DFT) paradigm. The investigations take into account different models of the selected IRMOFs. The mutual influence between the alkali-metal azides and the π rings or Zn centers of the involved MOF derivatives are studied by considering the interactions both of the alkali-metal cations with model aromatic centers and of the alkali-metal azides with distinct sites of differently sized models of IRMOF-1 and IRMOF-3. Several exchange and correlation functionals are employed to calculate the corresponding interaction energies. Remarkably, it is found that, with increasing alkali-metal atom size, the latter decrease for cations interacting with the π-ring systems and increase for the azides interacting with the MOF fragments. The opposite behavior is explained by stabilization effects on the azide moieties and determined by the Zn atoms, which constitute the inorganic vertices of the IRMOF species. Larger cations can, in fact, coordinate more efficiently to both the aromatic center and the azide anion, and thus stabilizing bridging arrangements of the azide between one alkali-metal and two Zn atoms in an η(2) coordination mode are more favored.

  1. Two-phase alkali-metal experiments in reduced gravity

    Energy Technology Data Exchange (ETDEWEB)

    Antoniak, Z.I.


    Future space missions envision the use of large nuclear reactors utilizing either a single or a two-phase alkali-metal working fluid. The design and analysis of such reactors require state-of-the-art computer codes that can properly treat alkali-metal flow and heat transfer in a reduced-gravity environment. A literature search of relevant experiments in reduced gravity is reported on here, and reveals a paucity of data for such correlations. The few ongoing experiments in reduced gravity are noted. General plans are put forth for the reduced-gravity experiments which will have to be performed, at NASA facilities, with benign fluids. A similar situation exists regarding two-phase alkali-metal flow and heat transfer, even in normal gravity. Existing data are conflicting and indequate for the task of modeling a space reactor using a two-phase alkali-metal coolant. The major features of past experiments are described here. Data from the reduced-gravity experiments with innocuous fluids are to be combined with normal gravity data from the two-phase alkali-metal experiments. Analyses undertaken here give every expectation that the correlations developed from this data base will provide a valid representation of alkali-metal heat transfer and pressure drop in reduced gravity.


    Directory of Open Access Journals (Sweden)

    Bwire S. Ndazi


    Full Text Available Chemical and thermal stability of rice husks against alkali treatment with 2 to 8% w/v NaOH are presented and discussed in this paper. The thermal stability of the rice husks was examined by using a thermal gravimetric analysis instrument. Chemical stability was evaluated by examining the organic components of rice husks using proximate analysis. The results indicated that the proportion of lignin and hemicellulose in rice husks treated with NaOH ranging from 4 to 8% decreased significantly by 96% and 74%, respectively. The thermal stability and final degradation temperatures of the alkali-treated rice husks were also lowered by 24-26°C due to degradation of hemicellulose and lignin during alkali treatment. Absence of the onset degradation zones in the alkali-treated rice husks was a further indication that hemicellulose and other volatile substances degraded during alkali treatment. This leads to a conclusion that alkali treatment of rice husks with more than 4% NaOH causes a substantial chemical degradation of rice husks, which subsequently decreases their thermal stability.

  3. Vibrations of alkali metal overlayers on metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Rusina, G G; Eremeev, S V; Borisova, S D [Institute of Strength Physics and Materials Science SB RAS, 634021, Tomsk (Russian Federation); Echenique, P M; Chulkov, E V [Donostia International Physics Center (DIPC), 20018 San Sebastian/Donostia, Basque Country (Spain); Benedek, G [Dipartimento di Scienza dei Materiali, Universita di Milano-Bicocca, Via Cozzi 53, 20125 Milano (Italy)], E-mail:


    We review the current progress in the understanding of vibrations of alkalis adsorbed on metal surfaces. The analysis of alkali vibrations was made on the basis of available theoretical and experimental results. We also include in this discussion our recent calculations of vibrations in K/Pt(111) and Li(Na)/Cu(001) systems. The dependence of alkali adlayer localized modes on atomic mass, adsorption position and coverage as well as the dependence of vertical vibration frequency on the substrate orientation is discussed. The square root of atomic mass dependence of the vertical vibration energy has been confirmed by using computational data for alkalis on the Al(111) and Cu(001) substrates. We have confirmed that in a wide range of submonolayer coverages the stretch mode energy remains nearly constant while the energy of in-plane polarized modes increases with the increase of alkali coverage. It was shown that the spectrum of both stretch and in-plane vibrations can be very sensitive to the adsorption position of alkali atoms and substrate orientation.

  4. Vibrations of alkali metal overlayers on metal surfaces (United States)

    Rusina, G. G.; Eremeev, S. V.; Echenique, P. M.; Benedek, G.; Borisova, S. D.; Chulkov, E. V.


    We review the current progress in the understanding of vibrations of alkalis adsorbed on metal surfaces. The analysis of alkali vibrations was made on the basis of available theoretical and experimental results. We also include in this discussion our recent calculations of vibrations in K/Pt(111) and Li(Na)/Cu(001) systems. The dependence of alkali adlayer localized modes on atomic mass, adsorption position and coverage as well as the dependence of vertical vibration frequency on the substrate orientation is discussed. The square root of atomic mass dependence of the vertical vibration energy has been confirmed by using computational data for alkalis on the Al(111) and Cu(001) substrates. We have confirmed that in a wide range of submonolayer coverages the stretch mode energy remains nearly constant while the energy of in-plane polarized modes increases with the increase of alkali coverage. It was shown that the spectrum of both stretch and in-plane vibrations can be very sensitive to the adsorption position of alkali atoms and substrate orientation.

  5. Silica research in Glasgow

    CERN Document Server

    Barr, B W; Casey, M M; Clubley, D; Crooks, D R M; Danzmann, K; Elliffe, E J; Gossler, S; Grant, A; Grote, H; Heptonstall, A; Hough, J; Jennrich, O; Lück, H B; McIntosh, S A; Newton, G P; Palmer, D A; Plissi, M V; Robertson, D I; Robertson, N A; Rowan, S; Skeldon, K D; Sneddon, P; Strain, K A; Torrie, C I; Ward, H; Willems, P A; Willke, B; Winkler, W


    The Glasgow group is involved in the construction of the GEO600 interferometer as well as in R and D activity on technology for advanced gravitational wave detectors. GEO600 will be the first GW detector using quasi-monolithic silica suspensions in order to decrease thermal noise significantly with respect to steel wire suspensions. The results concerning GEO600 suspension mounting and performance will be shown in the first section. Section 2 is devoted to the present results from the direct measurement of thermal noise in mirrors mounted in the 10 m interferometer in Glasgow which has a sensitivity limit of 4 x 10 sup - sup 1 sup 9 m Hz sup - sup 1 sup / sup 2 above 1 kHz. Section 3 presents results on the measurements of coating losses. R and D activity has been carried out to understand better how thermal noise in the suspensions affects the detector sensitivity, and in section 4 a discussion on the non-linear thermoelastic effect is presented.

  6. Alkali and heavy metal emissions of the PCFB-process; Alkali- ja raskasmetallipaeaestoet PCFB-prosessista

    Energy Technology Data Exchange (ETDEWEB)

    Kuivalainen, R.; Eriksson, T.; Lehtonen, P. [Foster Wheeler Energia Oy, Karhula (Finland)


    Pressurized Circulating Fluidized Bed (PCFB) combustion technology has been developed in Karhula R and D Center since 1986. As part of the development, 10 MW PCFB test facility was built in 1989. The test facility has been used for performance testing with different coal types through the years 1990-1995 in order to gain data for design and commercialization of the high-efficiency low-emission PCFB combustion technology. The main object of the project was to measure vapor phase Na and K concentrations in the PCFB flue gas after hot gas filter and investigate the effects of process conditions and sorbents on alkali release. The measurements were performed using plasma assisted method of TUT Laboratory of Plasma Technology and wet absorption method of VTT Energy. The measurements were carried out during three test campaigns at PCFB Test Facility in Karhula. In autumn 1995 both VTT and TUT methods were used. The measurements of the following test period in spring 1996 were performed by VTT, and during the last test segment in autumn 1996 TUT method was in use. During the last test period, the TUT instrument was used as semi-continuous (3 values/minute) alkali analyzer for part of the time. The measured Na concentrations were below 30 ppb(w) in all measured data points. The results of K were below 10 ppb(w). The accuracies of the both methods are about +50 % at this concentration range. The scatter of the data covers the effects of different process variables on the alkali emission. The measured emissions are at the same order of magnitude as the guideline emission limits estimated by gas turbine manufacturers

  7. Biomimetic mineral self-organization from silica-rich spring waters (United States)

    García-Ruiz, Juan Manuel; Nakouzi, Elias; Kotopoulou, Electra; Tamborrino, Leonardo; Steinbock, Oliver


    Purely inorganic reactions of silica, metal carbonates, and metal hydroxides can produce self-organized complex structures that mimic the texture of biominerals, the morphology of primitive organisms, and that catalyze prebiotic reactions. To date, these fascinating structures have only been synthesized using model solutions. We report that mineral self-assembly can be also obtained from natural alkaline silica-rich water deriving from serpentinization. Specifically, we demonstrate three main types of mineral self-assembly: (i) nanocrystalline biomorphs of barium carbonate and silica, (ii) mesocrystals and crystal aggregates of calcium carbonate with complex biomimetic textures, and (iii) osmosis-driven metal silicate hydrate membranes that form compartmentalized, hollow structures. Our results suggest that silica-induced mineral self-assembly could have been a common phenomenon in alkaline environments of early Earth and Earth-like planets. PMID:28345049

  8. Hydrothermal synthesis of meso porous silica MCM-41 using commercial sodium silicate

    Energy Technology Data Exchange (ETDEWEB)

    Melendez O, H. I.; Mercado S, A.; Garcia C, L. A.; Castruita, G.; Perera M, Y A., E-mail: [Centro de Investigacion en Quimica Aplicada, Bldv. Enrique Reyna Hermosillo No. 140, Saltillo 25294, Coahuila (Mexico)


    In this work, ordered meso porous silica MCM-41 was prepared by hydrothermal synthesis using industrial-grade sodium silicate (Na{sub 2}SiO{sub 3}) as silica source, hexadecyltrimethyl-ammonium bromide (CTAB) as template agent and ethyl acetate as ph regulator. The influence of CTAB/SiO{sub 2} molar ratio, reaction time, aging temperature, and co-surfactant type on the structural and morphological properties of the obtained silica was studied. The products were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and nitrogen adsorption-desorption isotherms. Ordered meso porous MCM-41 silica was obtained at 80 C by using a range of CTAB/SiO{sub 2} molar ratio from 0.35 to 0.71 and reaction times up to 72 h and isopropanol (i-Pr OH) as co-surfactant. (Author)

  9. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    Energy Technology Data Exchange (ETDEWEB)

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J., E-mail: [Molecular Materials and Nanosystems and Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (Netherlands); Gomes, Henrique L. [Instituto de Telecomunicações, Av. Rovisco, Pais 1, 1049-001 Lisboa, Portugal and Universidade do Algarve, Campus de Gambelas, 8005-139 Faro (Portugal); De Leeuw, Dago M. [Max-Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany and King Abdulaziz University, Jeddah (Saudi Arabia)


    Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10{sup 25}/m{sup 3}. The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics.

  10. The preparation of core-shell magnetic silica nanospheres for enhancing magnetism and fluorescence intensity. (United States)

    Yoo, Jeong Ha; Kim, Jong Sung


    Recently, magnetic and luminescent composite silica with structure of micro- and nanospheres containing both magnetic (Fe3O4) nanoparticles (MPs) and quantum dots (QDs) has attracted great interests. In this study, we have prepared core-shell structure of silica spheres in which magnets are incorporated into silica core and QDs into a mesoporous silica shell by using C18-TMS (octade-cyltrimethoxysilane). MPs were synthesized by a co-precipitation method from ferrous and ferric solutions with a molecular ratio of 2:3. Monodisperse magnetic silica cores have been prepared via sol-gel reaction of TEOS (tetraethoxysilane) and water using base catalyst. The size of magnetic silica nanospheres was confirmed by dynamic laser light scattering system (DLS) and scanning electoron microscope (SEM). The pore volume and surface area were calculated by using BET after calcination. The core-shell structure plays an important role in providing more domains for MPs in silica Core and QDs in silica shell. QDs were incorporated into the mesoporous shell by hydrophobic interactions. Magnetic characterization was performed using a superconducting quantum interference device (SQUID). The optical properties of the particles were characterized with UV/Vis spectrometer, PL spectrometer, and fluorescence microscope.

  11. Superconductivity in alkali-metal-doped picene. (United States)

    Mitsuhashi, Ryoji; Suzuki, Yuta; Yamanari, Yusuke; Mitamura, Hiroki; Kambe, Takashi; Ikeda, Naoshi; Okamoto, Hideki; Fujiwara, Akihiko; Yamaji, Minoru; Kawasaki, Naoko; Maniwa, Yutaka; Kubozono, Yoshihiro


    Efforts to identify and develop new superconducting materials continue apace, motivated by both fundamental science and the prospects for application. For example, several new superconducting material systems have been developed in the recent past, including calcium-intercalated graphite compounds, boron-doped diamond and-most prominently-iron arsenides such as LaO(1-x)F(x)FeAs (ref. 3). In the case of organic superconductors, however, no new material system with a high superconducting transition temperature (T(c)) has been discovered in the past decade. Here we report that intercalating an alkali metal into picene, a wide-bandgap semiconducting solid hydrocarbon, produces metallic behaviour and superconductivity. Solid potassium-intercalated picene (K(x)picene) shows T(c) values of 7 K and 18 K, depending on the metal content. The drop of magnetization in K(x)picene solids at the transition temperature is sharp (<2 K), similar to the behaviour of Ca-intercalated graphite. The T(c) of 18 K is comparable to that of K-intercalated C(60) (ref. 4). This discovery of superconductivity in K(x)picene shows that organic hydrocarbons are promising candidates for improved T(c) values.

  12. Bioinorganic Chemistry of the Alkali Metal Ions. (United States)

    Kim, Youngsam; Nguyen, Thuy-Tien T; Churchill, David G


    The common Group 1 alkali metals are indeed ubiquitous on earth, in the oceans and in biological systems. In this introductory chapter, concepts involving aqueous chemistry and aspects of general coordination chemistry and oxygen atom donor chemistry are introduced. Also, there are nuclear isotopes of importance. A general discussion of Group 1 begins from the prevalence of the ions, and from a comparison of their ionic radii and ionization energies. While oxygen and water molecule binding have the most relevance to biology and in forming a detailed understanding between the elements, there is a wide range of basic chemistry that is potentially important, especially with respect to biological chelation and synthetic multi-dentate ligand design. The elements are widely distributed in life forms, in the terrestrial environment and in the oceans. The details about the workings in animal, as well as plant life are presented in this volume. Important biometallic aspects of human health and medicine are introduced as well. Seeing as the elements are widely present in biology, various particular endogenous molecules and enzymatic systems can be studied. Sodium and potassium are by far the most important and central elements for consideration. Aspects of lithium, rubidium, cesium and francium chemistry are also included; they help in making important comparisons related to the coordination chemistry of Na(+) and K(+). Physical methods are also introduced.

  13. Superconductivity in alkali-doped fullerene nanowhiskers (United States)

    Takeya, Hiroyuki; Konno, Toshio; Hirata, Chika; Wakahara, Takatsugu; Miyazawa, Kun'ichi; Yamaguchi, Takahide; Tanaka, Masashi; Takano, Yoshihiko


    Superconductivity in alkali metal-doped fullerene nanowhiskers (C60NWs) was observed in K3.3C60NWs, Rb3.0C60NWs and Cs2.0Rb1.0C60NWs with transition temperatures at 17, 25 and 26 K, respectively. Almost full shielding volume fraction (~80%) was observed in K3.3C60NWs when subjected to thermal treatment at 200 °C for a duration of 24 h. In contrast, the shielding fraction of Rb3.0C60NWs and Cs2.0Rb1.0C60NWs were calculated to be 8% and 6%, respectively. Here we report on an extensive investigation of the superconducting properties of these AC60NWs (A  =  K3.3, Rb3.0 and Cs2.0Rb1.0). These properties are compared to the ones reported on the corresponding conventional (single-crystal or powder) K-doped fullerene. We also evaluated the critical current densities of these C60NWs using the Bean model under an applied magnetic field up to 50 kOe.

  14. Alternative alkali resistant deNOx catalysts

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Kristensen, Steffen Buus; Due-Hansen, Johannes;


    Alternative alkali resistant deNOx catalysts were prepared using three different supports ZrO2, TiO2 and Mordenite zeolite. The majority of the catalysts were prepared by incipient wetness impregnation of a commercial support, with vanadium, copper or iron precursor, one catalyst was prepared...... by onepot sol–gel method. All catalysts were characterized by BET, XRPD and NH3-TPD. Initial SCR activities of 8 out of 9 catalysts showed higher NO conversion at least at one temperature in the temperature range 300–500 ◦C compared to the conventional V2O5-WO3/TiO2 catalyst. After potassium poisoning (100......–130 µmol of K/g of catalyst) the relative drop in SCR activity and acidity was lower for all the alternative catalysts compared to the industrial V2O5-WO3/TiO2 catalyst. Furthermore, Cu/MOR and Nano-V2O5/Sul-TiO2 catalysts showed 8–16 times higher SCR activities than the conventional even after high...

  15. Influence of alkali metal doping on surface properties and catalytic activity/selectivity of CaO catalysts in oxidative coupling of methane

    Institute of Scientific and Technical Information of China (English)

    V.H.Rane; S.T.Chaudhari; V.R.Choudhary


    Surface properties (viz. surface area, basicity/base strength distribution, and crystal phases) of alkali metal doped CaO (alkali metal/Ca = 0.1 and 0.4) catalysts and their catalytic activity/selectivity in oxidative coupling of methane (OCM) to higher hydrocarbons at different reaction conditions (viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm3·g-1·h-1) have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties (viz. surface area, basicity/base strength distribution) and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity (strong basic sites) and the C2+ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO (Na/Ca = 0.1, before calcination) catalyst (calcined at 750 ℃), showed best performance (C2+selectivity of 68.8% with 24.7% methane conversion), whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.

  16. Selectivity between Oxygen and Chlorine Evolution in the Chlor-Alkali and Chlorate Processes. (United States)

    Karlsson, Rasmus K B; Cornell, Ann


    Chlorine gas and sodium chlorate are two base chemicals produced through electrolysis of sodium chloride brine which find uses in many areas of industrial chemistry. Although the industrial production of these chemicals started over 100 years ago, there are still factors that limit the energy efficiencies of the processes. This review focuses on the unwanted production of oxygen gas, which decreases the charge yield by up to 5%. Understanding the factors that control the rate of oxygen production requires understanding of both chemical reactions occurring in the electrolyte, as well as surface reactions occurring on the anodes. The dominant anode material used in chlorate and chlor-alkali production is the dimensionally stable anode (DSA), Ti coated by a mixed oxide of RuO2 and TiO2. Although the selectivity for chlorine evolution on DSA is high, the fundamental reasons for this high selectivity are just now becoming elucidated. This review summarizes the research, since the early 1900s until today, concerning the selectivity between chlorine and oxygen evolution in chlorate and chlor-alkali production. It covers experimental as well as theoretical studies and highlights the relationships between process conditions, electrolyte composition, the material properties of the anode, and the selectivity for oxygen formation.

  17. Preparation and Application Situation of Silica Gel%硅胶的制备及应用现状

    Institute of Scientific and Technical Information of China (English)



    硅胶不溶于水和任何溶剂,无毒无味,化学性质稳定,除强碱、氢氟酸外不与任何物质发生反应。根据其孔径的大小分为:大孔硅胶、粗孔硅胶、B型硅胶、细孔硅胶。由于孔隙结构的不同,因此它们的吸附性能各有特点。硅胶是一种高活性的吸附材料,通常以硅酸钠和硫酸为原料制备,文中介绍了各种硅胶的生产工艺,论述了硅胶的应用现状。%Silica gel was insoluble in water and any solvent,non-toxic and odorless,chemical stability,except strong alkali and hydrofluoric acid,and it can't react with any material.According to its aperture size's,it was divided into big pore silica gel,thick pore silica gel,the type B silica gel and the fine pore silica gel.Because the pore structure was different,so they had different features of adsorption performance.Silica gel was a highly active adsorption materials,usually prepared by the sodium silicate and sulfuric acid as raw material.Various silica gel production technology was introduced,and the present situation of the application of the silica gel was discussed.

  18. Inlfuence of the Alkali Treatment of HZSM-5 Zeolite on Catalytic Performance of PtSn-Based Catalyst for Propane Dehydrogenation

    Institute of Scientific and Technical Information of China (English)

    Huang Li; Zhou Shijian; Zhou Yuming; Zhang Yiwei; Xu Jun; Wang Li


    The porous material ATZ with micro-mesopore hierarchical porosity was prepared by alkali treatment of parent HZSM-5 zeolite and applied for propane dehydrogenation. The zeolite samples were characterized by XRD, N2-physisorption, and NH3-TPD analysis. The results showed that the alkali treatment can modify the physicochemical prop-erties of HZSM-5 zeolite. In this case, the porous material ATZ showed larger external surface area with less acid sites as compared to the HZSM-5 zeolite. It was found out that the alkali treatment of HZSM-5 zeolite could promote the catalytic performance of PtSn/ATZ catalyst. The possible reason was ascribed to the low acidity of ATZ. Furthermore, the presence of mesopores could reduce the carbon deposits on the metallic surface, which was also favorable for the dehydrogenation reaction.

  19. The Preparation of Magnetic Silica Nanospheres and Incorporation of CdSe/ZnS Quantum Dots-DNA Probe. (United States)

    Do, Youngjin; Kim, Jongsung


    Silica nanospheres containing magnetic particles were prepared, and CdSe/ZnS QDs functionalized with carboxyl group were incorporated into the silica nanospheres by EDC/NHS coupling reaction. The silica nanospheres were prepared by a co-precipitation of ferrous and ferric solutions followed by the sol-gel reaction of TEOS (tetraethoxysilane) and APTES (3-aminopropyltriethoxysilane) using base catalyst. The size of magnetic silica nanospheres was confirmed by Transmission electron microscope (TEM). Thiol group modified single stranded oligonucleotides were immobilized on the surface of QDs and fluorescence quenching by intercalation dye (TOTO-3) after hybridization with target oligonucleotide was observed. The fluorescence from QDs could be quenched by intercalating dye (TOTO-3) after hybridization of target DNA to probe DNA. This shows that the magnetic silica-QD-DNA probe can be used to detect specific DNA.

  20. Vulcanization characteristics and dynamic mechanical behavior of natural rubber reinforced with silane modified silica. (United States)

    Chonkaew, Wunpen; Minghvanish, Withawat; Kungliean, Ulchulee; Rochanawipart, Nutthaya; Brostow, Witold


    Two silane coupling agents were used for hydrolysis-condensation reaction modification of nanosilica surfaces. The surface characteristics were analyzed using Fourier transform infrared spectroscopy (FTIR). The vulcanization kinetics of natural rubber (NR) + silica composites was studied and compared to behavior of the neat NR using differential scanning calorimetry (DSC) in the dynamic scan mode. Dynamic mechanical analysis (DMA) was performed to evaluate the effects of the surface modification. Activation energy E(a) values for the reaction are obtained. The presence of silica, modified or otherwise, inhibits the vulcanization reaction of NR. The neat silica containing system has the lowest cure rate index and the highest activation energy for the vulcanization reaction. The coupling agent with longer chains causes more swelling and moves the glass transition temperature T(g) downwards. Below the glass transition region, silica causes a lowering of the dynamic storage modulus G', a result of hindering the cure reaction. Above the glass transition, silica-again modified or otherwise-provides the expected reinforcement effect.

  1. Polystyrene-block-poly(ethylene oxide) copolymers as templates for stacked, spherical large-mesopore silica coatings: dependence of silica pore size on the PS/PEO ratio. (United States)

    Nisticò, Roberto; Magnacca, Giuliana; Jadhav, Sushilkumar A; Scalarone, Dominique


    Large-mesopore silica films with a narrow pore size distribution and high porosity have been obtained by a sol-gel reaction of a silicon oxide precursor (TEOS) and using polystyrene-block-poly(ethylene oxide) (PS-b-PEO) copolymers as templates in an acidic environment. PS-b-PEO copolymers with different molecular weight and composition have been studied in order to assess the effects of the block length on the pore size of the templated silica films. The changes in the morphology of the porous systems have been investigated by transmission electron microscopy and a systematic analysis has been carried out, evidencing the dependence between the hydrophilic/hydrophobic ratio of the two polymer blocks and the size of the final silica pores. The obtained results prove that by tuning the PS/PEO ratio, the pore size of the templated silica films can be easily and finely predicted.

  2. Novel nanocomposites from spider silk–silica fusion (chimeric) proteins


    Wong Po Foo, Cheryl; Patwardhan, Siddharth V.; Belton, David J.; Kitchel, Brandon; Anastasiades, Daphne; Huang, Jia; Naik, Rajesh R.; Perry, Carole C.; Kaplan, David L.


    Silica skeletal architectures in diatoms are characterized by remarkable morphological and nanostructural details. Silk proteins from spiders and silkworms form strong and intricate self-assembling fibrous biomaterials in nature. We combined the features of silk with biosilica through the design, synthesis, and characterization of a novel family of chimeric proteins for subsequent use in model materials forming reactions. The domains from the major ampullate spidroin 1 (MaSp1) protein of Neph...

  3. Interactions and low energy collisions between an alkali ion and an alkali atom of different nucleus

    CERN Document Server

    Rakshit, Arpita; Berriche, Hamid; Deb, Bimalendu


    We study theoretically interaction potentials and low energy collisions between different alkali atoms and alkali ions. Specifically, we consider systems like X + Y$^{+}$, where X(Y$^{+})$ is either Li(Cs$^+$) or Cs((Li$^+$), Na(Cs$^+$) or Cs(Na$^+$) and Li(Rb$^+$) or Rb(Li$^+$). We calculate the molecular potentials of the ground and first two excited states of these three systems using pseudopotential method and compare our results with those obtained by others. We calculate ground-state scattering wave functions and cross sections of these systems for a wide range of energies. We find that, in order to get convergent results for the total scattering cross sections for energies of the order $1$ K, one needs to take into account at least 60 partial waves. In the low energy limit ($< 1 \\mu$K), elastic scattering cross sections exhibit Wigner law threshold behavior while in the high energy limit the cross sections go as $E^{-1/3}$. We discuss qualitatively the possibilities of forming cold molecular ion by ...

  4. Hydrogen storage over alkali metal hydride and alkali metal hydroxide composites

    Institute of Scientific and Technical Information of China (English)

    Pei Yu; Yong Shen Chua; Hujun Cao; Zhitao Xiong; Guotao Wu; Ping Chen


    Alkali metal hydroxide and hydride composite systems contain both protic (H bonded with O) and hydridic hydrogen. The interaction of these two types of hydrides produces hydrogen. The enthalpy of dehydrogenation increased with the increase of atomic number of alkali metals, i.e.,-23 kJ/molH2 for LiOH-LiH, 55.34 kJ/molH2 for NaOH-NaH and 222 kJ/molH2 for KOH-KH. These thermodynamic calculation results were consistent with our experimental results. H2 was released from LiOH-LiH system during ball milling. The dehydrogenation temperature of NaOH-NaH system was about 150◦C; whereas KOH and KH did not interact with each other during the heating process. Instead, KH decomposed by itself. In these three systems, NaOH-NaH was the only reversible hydrogen storage system, the enthalpy of dehydrogenation was about 55.65 kJ/molH2 , and the corresponding entropy was ca. 101.23 J/(molH2 ·K), so the temperature for releasing 1.0 bar H2 was as high as 518◦C, showing unfavorable thermodynamic properties. The activation energy for hydrogen desorption of NaOH-NaH was found to be 57.87 kJ/mol, showing good kinetic properties.

  5. Nanostructural Organization of Naturally Occurring Composites—Part II: Silica-Chitin-Based Biocomposites

    Directory of Open Access Journals (Sweden)

    Hermann Ehrlich


    Full Text Available Investigations of the micro- and nanostructures and chemical composition of the sponge skeletons as examples for natural structural biocomposites are of fundamental scientific relevance. Recently, we show that some demosponges (Verongula gigantea, Aplysina sp. and glass sponges (Farrea occa, Euplectella aspergillum possess chitin as a component of their skeletons. The main practical approach we used for chitin isolation was based on alkali treatment of corresponding external layers of spicules sponge material with the aim of obtaining alkali-resistant compounds for detailed analysis. Here, we present a detailed study of the structural and physicochemical properties of spicules of the glass sponge Rossella fibulata. The structural similarity of chitin derived from this sponge to invertebrate alpha chitin has been confirmed by us unambiguously using physicochemical and biochemical methods. This is the first report of a silica-chitin composite biomaterial found in Rossella species. Finally, the present work includes a discussion related to strategies for the practical application of silica-chitin-based composites as biomaterials.

  6. Simultaneous Synthesis of Dimethyl Carbonate and Poly(ethylene terephthalate) Using Alkali Metals as Catalysts%碱金属化合物催化同时合成碳酸二甲酯和聚对苯二甲酸乙二醇酯

    Institute of Scientific and Technical Information of China (English)

    张丹; 王庆印; 姚洁; 王越; 曾毅; 王公应


    Dimethyl carbonate (DMC) and poly(ethylene terephthalate) was simultaneously synthesized by the transesterification of ethylene carbonate (EC) with dimethyl terephthalate (DMT) in this paper. This reaction is an excellent green chemical process without poisonous substance. Various alkali metals were used as the catalysts. The results showed alkali metals had catalytic activity in a certain extent. The effect of reaction condition was also studied. When the reaction was carried out under the following conditions: the reaction temperature 250℃, molar ratio of EC to DMT 3: 1, reaction time 3h, and catalyst amount 0.004 (molar ratio to DMT), the yield of DMC was 68.9%.

  7. Infrared spectra of silica polymorphs (United States)

    Koike, C.; Noguchi, R.; Chihara, H.; Suto, H.; Ohtaka, O.; Imai, Y.; Matsumoto, T.; Tsuchiyama, A.

    The existence of silica within several debris disks has been suggested. We investigate the annealing conditions of α-cristobalite, and further prepare various types of silica, including α-cristobalite, α-quartz, coesite, stishovite, and fused quartz, which are natural, synthetic or commercial samples. We compare the results to previous studies and find that α-cristobalite synthesized at higher temperature than annealed silica. The interesting result of features similar to those of forsterite should be highlighted, where αcristobalite and coesite showed similar peaks at 16, 33, and 69 μm as forsterite. The 69 μm band for αcristobalite is especially very broad and strong, and shifts largely to a shorter wavelengths under cooling to low temperatures. The band for coesite, however, is very sharp, and shifts only a small amount to longer wavelengths under cooling to low temperatures. The peak positions of 16 and 69-μm band due to α-cristobalite can become index for temperature of silica dust. We discuss the possibility of silica detection around debris disks.

  8. Morphology of melt-rich channels formed during reaction infiltration experiments on partially molten mantle rocks (United States)

    Pec, Matej; Holtzman, Benjamin; Zimmerman, Mark; Kohlstedt, David


    Geochemical, geophysical and geological observations suggest that melt extraction from the partially molten mantle occurs by some sort of channelized flow. Melt-solid reactions can lead to melt channelization due to a positive feedback between melt flow and reaction. If a melt-solid reaction increases local permeability, subsequent flow is increased as well and promotes further reaction. This process can lead to the development of high-permeability channels which emerge from background flow. In nature, anastomozing tabular dunite bodies within peridotitic massifs are thought to represent fossilized channels that formed by reactive flow. The conditions under which such channels can emerge are treated by the reaction infiltration instability (RII) theory (e.g. Szymczak and Ladd 2014). In this contribution, we report the results of a series of Darcy type experiments designed to study the development of channels due to RII in mantle lithologies (Pec et al. 2015). We sandwiched a partially molten rock between a melt source and a porous sink and annealed it at high-pressures (P = 300 MPa) and high-temperatures (T = 1200° or 1250° C) under a controlled pressure gradient (∇P = 0-100 MPa/mm) for up to 5 hours. The partially molten rock is formed by 50:50 mixtures of San Carlos olivine (Ol, Fo ˜ 88) and clinopyroxene (Cpx) with either 4, 10 or 20 vol% of alkali basalt added. The source and sink are disks of alkali basalt and porous alumina, respectively. During the experiments, silica undersaturated melt from the melt source dissolves Cpx and precipitates an iron rich Ol (Fo ˜ 82) thereby forming a Cpx-free reaction layer at the melt source - partially molten rock interface. The melt fraction in the reaction layer increases significantly (40% melt) compared to the protolith, confirming that the reaction increases the permeability of the partially molten rock. In experiments annealed under a low pressure gradient (and hence slow melt flow velocity) the reaction layer is

  9. An alkali catalyzed trans-esterification of rice bran, cottonseed and waste cooking oil

    Directory of Open Access Journals (Sweden)

    Akhtar Faheem H.


    Full Text Available In this research work, biodiesel production by trans-esterification of three raw materials including virgin and used edible oil and non edible oil has been presented. A two step method following acidic and alkali catalyst was used for non edible oil due to the unsuitability of using the straight alkaline-catalyzed trans-esterification of high FFA present in rice bran oil. The acid value after processing for rice bran, cottonseed and waste cooking oil was found to be 0.95, 0.12 and 0.87 respectively. The influence of three variables on percentage yield i.e., methanol to oil molar ratio, reaction temperature and reaction time were studied at this stage. Cottonseed oil, waste cooking oil and rice bran oil showed a maximum yield of 91.7%, 84.1% and 87.1% under optimum conditions. Fuel properties of the three biodiesel satisfied standard biodiesel fuel results.

  10. Microporous silica gels from alkylsilicate-water two phase hydrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Chu, L.; Tejedor-Tejedor, M.I.; Anderson, M.A. [Univ. of Wisconsin, Madison, WI (United States). Water Chemistry Program


    Microporous silica gels have been synthesized through a nano-particulate sol-gel route. These gels have uniformly distributed and extremely small pores(< 15 {angstrom} in diameter). Hydrolysis and condensation reactions leading to these gels were carried out in an alkyl silicate-water (ammonia) two phase system. These reactions took place at the alkyl silicate droplet-water interfacial boundary. No alcohol was added. A clear, stable and uniformly distributed colloidal silica suspension having an average particle size less than 6 nm was prepared by this method. Fast hydrolysis, slow condensation and low solubility all contribute to a high supersaturation level and result in the formation of small particles. This process is consistent with classic nucleation theory. When the particles are produced under acidic rather than under basic reaction conditions, smaller particles are formed due to the slower condensation rate and lower solubility of these silica particles in acidic conditions. At the same pH, alkylsilicates having smaller alkyl groups react faster with water leading to smaller primary particles. Homogeneous nucleation conditions are achieved when the water/alkylsilicate ratio is high.

  11. Exposure to crystalline silica in abrasive blasting operations where silica and non-silica abrasives are used. (United States)

    Radnoff, Diane L; Kutz, Michelle K


    Exposure to respirable crystalline silica is a hazard common to many industries in Alberta but particularly so in abrasive blasting. Alberta occupational health and safety legislation requires the consideration of silica substitutes when conducting abrasive blasting, where reasonably practicable. In this study, exposure to crystalline silica during abrasive blasting was evaluated when both silica and non-silica products were used. The crystalline silica content of non-silica abrasives was also measured. The facilities evaluated were preparing metal products for the application of coatings, so the substrate should not have had a significant contribution to worker exposure to crystalline silica. The occupational sampling results indicate that two-thirds of the workers assessed were potentially over-exposed to respirable crystalline silica. About one-third of the measurements over the exposure limit were at the work sites using silica substitutes at the time of the assessment. The use of the silica substitute, by itself, did not appear to have a large effect on the mean airborne exposure levels. There are a number of factors that may contribute to over-exposures, including the isolation of the blasting area, housekeeping, and inappropriate use of respiratory protective equipment. However, the non-silica abrasives themselves also contain silica. Bulk analysis results for non-silica abrasives commercially available in Alberta indicate that many contain crystalline silica above the legislated disclosure limit of 0.1% weight of silica per weight of product (w/w) and this information may not be accurately disclosed on the material safety data sheet for the product. The employer may still have to evaluate the potential for exposure to crystalline silica at their work site, even when silica substitutes are used. Limited tests on recycled non-silica abrasive indicated that the silica content had increased. Further study is required to evaluate the impact of product recycling

  12. Molecular photons interfaced with alkali atoms. (United States)

    Siyushev, Petr; Stein, Guilherme; Wrachtrup, Jörg; Gerhardt, Ilja


    Future quantum communication will rely on the integration of single-photon sources, quantum memories and systems with strong single-photon nonlinearities. Two key parameters are crucial for the single-photon source: a high photon flux with a very small bandwidth, and a spectral match to other components of the system. Atoms or ions may act as single-photon sources--owing to their narrowband emission and their intrinsic spectral match to other atomic systems--and can serve as quantum nonlinear elements. Unfortunately, their emission rates are still limited, even for highly efficient cavity designs. Single solid-state emitters such as single organic dye molecules are significantly brighter and allow for narrowband photons; they have shown potential in a variety of quantum optical experiments but have yet to be interfaced with other components such as stationary memory qubits. Here we describe the optical interaction between Fourier-limited photons from a single organic molecule and atomic alkali vapours, which can constitute an efficient quantum memory. Single-photon emission rates reach up to several hundred thousand counts per second and show a high spectral brightness of 30,000 detectable photons per second per megahertz of bandwidth. The molecular emission is robust and we demonstrate perfect tuning to the spectral transitions of the sodium D line and efficient filtering, even for emitters at ambient conditions. In addition, we achieve storage of molecular photons originating from a single dibenzanthanthrene molecule in atomic sodium vapour. Given the large set of molecular emission lines matching to atomic transitions, our results enable the combination of almost ideal single-photon sources with various atomic vapours, such that experiments with giant single-photon nonlinearities, mediated, for example, by Rydberg atoms, become feasible.

  13. Influence of alkali, silicate, and sulfate content of carbonated concrete pore solution on mild steel corrosion behavior

    Energy Technology Data Exchange (ETDEWEB)

    L' Hostis, V. [CEA Saclay, DEN, DPC, SCCME, Lab Etud Comportement Betons and Argiles, F-91191 Gif Sur Yvette (France); Huet, B. [Schlumberger Riboud Prod Ctr, Schlumberger Carbon Serv, F-92142 Clamart (France); Tricheux, L. [CEBTP SOLEN, F-78990 Elancourt (France); Idrissi, H. [CNRS, Lab MATEIS UMR 5510, Equipe RI2S, Dept Sci and Genie Mat, F-69621 Villeurbanne (France)


    The increase in the rebar corrosion rate due to the concrete carbonation is the major cause of reinforced concrete degradation. The aim of this study was to investigate the corrosion behavior of mild steel rebars in simulated carbonated concrete solution. For this purpose, thermodynamic calculations, electrochemical techniques, gravimetric measurements, and surface analyses were used. Thermodynamic investigations of the nature of the interstitial solution provides an estimation of the influence of sulfate (SO{sub 4}{sup 2-}) and alkali (Na{sup +}, K{sup +}) content on carbonate alkalinity of the CO{sub 2}/H{sub 2}O open system (pCO{sub 2}=0. 3 mbar). in this system, calcium-silicate hydrates (C-S-H) remain thermodynamically unstable and amorphous silica controls silicate aqueous content at 100 ppm. Electrochemical results highlight a decrease in the corrosion rate with increasing carbonate alkalinity and the introduction of silicate. The introduction of sulfate at fixed carbonate alkalinity shows a dual effect: at high carbonate alkalinity, the corrosion rate is increased whereas at low carbonate alkalinity, corrosion rate is decreased. Those results are supported by surface analysis. Authors conclude that silicate and sulfate release from cement hydrates and fixation of alkali on carbonated hydrates are key parameters to estimate mild steel corrosion in carbonated concrete. (authors)

  14. Influence of alkali, silicate, and sulfate content of carbonated concrete pore solution on mild steel corrosion behavior

    Energy Technology Data Exchange (ETDEWEB)

    Huet, B. [Schlumberger Carbon Services, Schlumberger Riboud Product Center, Clamart (France); L' Hostis, V. [CEA, DEN, DPC, SCCME, Laboratoire d' Etude du Comportement des Betons et des Argiles, Gif-sur-Yvette, (France); Tricheux, L. [CEBTP-SOLEN, Elancourt, (France); Idrissi, H. [Laboratoire MATEIS UMR CNRS, Equipe RI2S, Department Science et Genie des Materiaux, Villeurbanne, (France)


    The increase in the rebar corrosion rate due to the concrete carbonation is the major cause of reinforced concrete degradation. The aim of this study was to investigate the corrosion behavior of mild steel rebars in simulated carbonated concrete solution. For this purpose, thermodynamic calculations, electrochemical techniques, gravimetric measurements, and surface analyses were used. Thermodynamic investigations of the nature of the interstitial solution provides an estimation of the influence of sulfate (SO{sub 4}{sup 2} {sup -}) and alkali (Na{sup +}, K{sup +}) content on carbonate alkalinity of the CO{sub 2}/H{sub 2}O open system (pCO{sub 2} = 0.3 mbar). In this system, calcium-silicate hydrates (C-S-H) remain thermodynamically unstable and amorphous silica controls silicate aqueous content at 100 ppm. Electrochemical results highlight a decrease in the corrosion rate with increasing carbonate alkalinity and the introduction of silicate. The introduction of sulfate at fixed carbonate alkalinity shows a dual effect: at high carbonate alkalinity, the corrosion rate is increased whereas at low carbonate alkalinity, corrosion rate is decreased. Those results are supported by surface analysis. Authors conclude that silicate and sulfate release from cement hydrates and fixation of alkali on carbonated hydrates are key parameters to estimate mild steel corrosion in carbonated concrete. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  15. Silica Aerogel: Synthesis and Applications

    Directory of Open Access Journals (Sweden)

    Jyoti L. Gurav


    Full Text Available Silica aerogels have drawn a lot of interest both in science and technology because of their low bulk density (up to 95% of their volume is air, hydrophobicity, low thermal conductivity, high surface area, and optical transparency. Aerogels are synthesized from molecular precursors by sol-gel processing. Special drying techniques must be applied to replace the pore liquid with air while maintaining the solid network. Supercritical drying is most common; however, recently developed methods allow removal of the liquid at atmospheric pressure after chemical modification of the inner surface of the gels, leaving only a porous silica network filled with air. Therefore, by considering the surprising properties of aerogels, the present review addresses synthesis of silica aerogels by the sol-gel method, as well as drying techniques and applications in current industrial development and scientific research.

  16. Nature of the Charge Localized Between Alkali Adatoms and Metal Substrates


    Wertheim, G. K.; Riffe, D. Mark; Citrin, P. H.


    Two previously unappreciated features in photoemission spectra from alkali atoms adsorbed on W(110), namely, the sign of the alkali-induced surface-atom core-level shift of the substrate at low coverage and the very large alkali shallow core-hole lifetime width at all coverages, show that the alkali-substrate interaction is not well described by a transfer of alkali charge. Instead, both features point to the formation of a charge cloud between the alkali adatom and substrate that is d...

  17. Effect of Steel Fiber on Alkali activated Fly Ash Concrete

    Directory of Open Access Journals (Sweden)



    Full Text Available Concrete is the world’s most important Construction material so the demand of cement is increases. The production of cement is highly energy intensive & the production on one ton of cement liberates about one ton of CO2 to atmosphere. The contribution of cement industry to the greenhouse gas emission is estimated to be about 70% of the total green gas emission. Also it consumes large amount of natural resources. Hence it is essential to find alternative to cement. Geopolymer concrete is an innovative material in which the binder is produced but the reaction of an alkaline liquid with a source material that is rich in silica alumina. The present work deals with the result of the experimental investigation carried out on geopolymer concrete using steel fiber. The study analyses the effect of steel on compressive strength. Geopolymer concrete mixes were prepared using low calcium fly ash & activated by alkaline solution. (NaOH & Na2SiO3 with alkaline liquid to fly ash ratio of 0.35 Alkaline solution. Used for present study combination of sodium hydroxide & sodium silicate with ratio 2.5. The mix was designed for molarity of 16M & grade chosen for investigation was M30. Hooked end steel fiber . All tests were conducted according to IS-code procedure. The result for each variation are tabulated & discussed in details & some important conclusions are made.

  18. Synthesis and Characterization of Bimodal Mesoporous Silica

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xiaofang; GUO Cuili; WANG Xiaoli; WU Yuanyuan


    Mesoporous silica with controllable bimodal pore size distribution was synthesized with cetyltrimethylammonium bromide (CTAB) as chemical template for small mesopores and silica gel as physical template for large mesopores.The structure of synthesized samples were characterized by Fourier transform infrared (FT-IR) spectroscopy,X-ray diffraction (XRD),scanning electron microscopy (SEM),transmission electron microscopy (TEM) and N2 adsorption-desorption measurements.The experimental results show that bimodal mesoporous silica consists of small mesopores of about 3 nm and large mesopores of about 45 nm.The small mesopores which were formed on the external surface and pore walls of the silica gel had similar characters with those of MCM-41,while large mesopores were inherited from parent silica gel material.The pore size distribution of the synthesized silica can be adjusted by changing the relative content of TEOS and silica gel or the feeding sequence of silica gel and NH4OH.

  19. Multi-photon processes in alkali metal vapors (United States)

    Gai, Baodong; Hu, Shu; Li, Hui; Shi, Zhe; Cai, Xianglong; Guo, Jingwei; Tan, Yannan; Liu, Wanfa; Jin, Yuqi; Sang, Fengting


    Achieving population inversion through multi-photon cascade pumping is almost always difficult, and most laser medium work under 1-photon excitation mechanism. But for alkali atoms such as cesium, relatively large absorption cross sections of several low, cascading energy levels enable them properties such as up conversion. Here we carried out research on two-photon excitation alkali fluorescence. Two photons of near infrared region are used to excite alkali atoms to n 2 D5/2, n 2 D3/2 or higher energy levels, then the blue fluorescence of (n+1) 2 P3/2,(n+1) 2 P1/2-->n 2 S1/2 are observed. Different pumping paths are tried and by the recorded spectra, transition routes of cesium are deducted and concluded. Finally the possibility of two-photon style DPALs (diode pumped alkali laser) are discussed, such alkali lasers can give output wavelengths in the shorter end of visual spectroscopy (400-460 nm) and are expected to get application in underwater communication and material laser processing.

  20. Utilization of Mineral Wools as Alkali-Activated Material Precursor

    Directory of Open Access Journals (Sweden)

    Juho Yliniemi


    Full Text Available Mineral wools are the most common insulation materials in buildings worldwide. However, mineral wool waste is often considered unrecyclable because of its fibrous nature and low density. In this paper, rock wool (RW and glass wool (GW were studied as alkali-activated material precursors without any additional co-binders. Both mineral wools were pulverized by a vibratory disc mill in order to remove the fibrous nature of the material. The pulverized mineral wools were then alkali-activated with a sodium aluminate solution. Compressive strengths of up to 30.0 MPa and 48.7 MPa were measured for RW and GW, respectively, with high flexural strengths measured for both (20.1 MPa for RW and 13.2 MPa for GW. The resulting alkali-activated matrix was a composite-type in which partly-dissolved fibers were dispersed. In addition to the amorphous material, sodium aluminate silicate hydroxide hydrate and magnesium aluminum hydroxide carbonate phases were identified in the alkali-activated RW samples. The only crystalline phase in the GW samples was sodium aluminum silicate. The results of this study show that mineral wool is a very promising raw material for alkali activation.

  1. Optothermal nonlinearity of silica aerogel

    CERN Document Server

    Braidotti, Maria Chiara; Fleming, Adam; Samuels, Michiel C; Di Falco, Andrea; Conti, Claudio


    We report on the characterization of silica aerogel thermal optical nonlinearity, obtained by z-scan technique. The results show that typical silica aerogels have nonlinear optical coefficient similar to that of glass $(\\simeq 10^{-12} $m$^2/$W), with negligible optical nonlinear absorption. The non\\-li\\-near coefficient can be increased to values in the range of $10^{-10} $m$^2/$W by embedding an absorbing dye in the aerogel. This value is one order of magnitude higher than that observed in the pure dye and in typical highly nonlinear materials like liquid crystals.

  2. Thermochemical ablation therapy of VX2 tumor using a permeable oil-packed liquid alkali metal.

    Directory of Open Access Journals (Sweden)

    Ziyi Guo

    Full Text Available Alkali metal appears to be a promising tool in thermochemical ablation, but, it requires additional data on safety is required. The objective of this study was to explore the effectiveness of permeable oil-packed liquid alkali metal in the thermochemical ablation of tumors.Permeable oil-packed sodium-potassium (NaK was prepared using ultrasonic mixing of different ratios of metal to oil. The thermal effect of the mixture during ablation of muscle tissue ex vivo was evaluated using the Fluke Ti400 Thermal Imager. The thermochemical effect of the NaK-oil mixture on VX2 tumors was evaluated by performing perfusion CT scans both before and after treatment in 10 VX2 rabbit model tumors. VX2 tumors were harvested from two rabbits immediately after treatment to assess their viability using trypan blue and hematoxylin and eosin (H.E. staining.The injection of the NaK-oil mixture resulted in significantly higher heat in the ablation areas. The permeable oil controlled the rate of heat released during the NaK reaction with water in the living tissue. Perfusion computed tomography and its parameter map confirmed that the NaK-oil mixture had curative effects on VX2 tumors. Both trypan blue and H.E. staining showed partial necrosis of the VX2 tumors.The NaK-oil mixture may be used successfully to ablate tumor tissue in vivo. With reference to the controlled thermal and chemical lethal injury to tumors, using a liquid alkali in ablation is potentially an effective and safe method to treat malignant tumors.

  3. Multifunctional clickable and protein-repellent magnetic silica nanoparticles. (United States)

    Estupiñán, Diego; Bannwarth, Markus B; Mylon, Steven E; Landfester, Katharina; Muñoz-Espí, Rafael; Crespy, Daniel


    Silica nanoparticles are versatile materials whose physicochemical surface properties can be precisely adjusted. Because it is possible to combine several functionalities in a single carrier, silica-based materials are excellent candidates for biomedical applications. However, the functionality of the nanoparticles can get lost upon exposure to biological media due to uncontrolled biomolecule adsorption. Therefore, it is important to develop strategies that reduce non-specific protein-particle interactions without losing the introduced surface functionality. Herein, organosilane chemistry is employed to produce magnetic silica nanoparticles bearing differing amounts of amino and alkene functional groups on their surface as orthogonally addressable chemical functionalities. Simultaneously, a short-chain zwitterion is added to decrease the non-specific adsorption of biomolecules on the nanoparticles surface. The multifunctional particles display reduced protein adsorption after incubation in undiluted fetal bovine serum as well as in single protein solutions (serum albumin and lysozyme). Besides, the particles retain their capacity to selectively react with biomolecules. Thus, they can be covalently bio-functionalized with an antibody by means of orthogonal click reactions. These features make the described multifunctional silica nanoparticles a promising system for the study of surface interactions with biomolecules, targeting, and bio-sensing.

  4. Microstructure and Thermomechanical Properties of Polyimide-Silica Nanocomposites

    Directory of Open Access Journals (Sweden)

    A. Al Arbash


    Full Text Available Novel polyimide-silica nanocomposites with interphase chemical bonding have been prepared using the sol-gel process. The morphology, thermal and mechanical properties were studied as a function of silica content and compared with the similar composites having no interphase interaction. The polyimide precursors, polyamic acids (PAAs with or without pendant hydroxyl groups were prepared from the reaction of pyromellitic dianhydride with a mixture of oxydianiline and 1,3 phenylenediamine or 2,4-diminophenol in dimethylacetamide. The PAA with pendant hydroxyl groups was reacted with isocyanatopropyltriethoxysilane to produce alkoxy groups on the chain. The reinforcement of PAA matrices with or without alkoxy groups on the chain was carried out by mixing appropriate amount of tetraethoxysilane (TEOS and carrying out its hydrolysis and condensation in a sol-gel process. Thin hybrid films were imidized by successive heating up to 300C∘. The presence of alkoxy groups on the polymer chain and their cocondensation with TEOS developed the silica network which was interconnected chemically with the polyimide matrix. SEM studies show a drastic decrease in the silica particle size in the chemically bonded system. Higher thermal stability and mechanical strength, improved transparency, and low values of thermal coefficient of expansion were observed in case of chemically bonded composites.

  5. Fluorescent quantification of amino groups on silica nanoparticle surfaces. (United States)

    Chen, Yang; Zhang, Yanqin


    Functionalization of the surfaces of silica particles is often the first step in their various applications. An improved heterogeneous Fmoc-Cl fluorescent assay using an aqueous solution was developed to detect the number of amino groups on solid-phase supports. The fluorescent Fmoc-Cl method is 50-fold more sensitive than the current UV assay using an organic solvent. This method, together with the homogeneous fluorescamine and OPA assays, is used to detect amino groups on the silica particle surface. The accuracy and effect factors of these methods were examined and the assays were optimized. The results showed that the amine groups on silica particles can produce stronger fluorescence than small amine molecules in solution, because the porous structure of the particle surface is a more hydrophobic environment. The number of active amino groups that can be conjugated with biomolecules is much less than the total number of amino groups on the silica particle. Compared with physical methods, chemical assays involving direct reaction with amino groups would furnish the closest result to the number of active amino groups on the particle surface.

  6. Niobia-silica and silica membranes for gas separation

    NARCIS (Netherlands)

    Boffa, Vittorio


    This thesis describes the development of ceramic membranes suitable for hydrogen separation and CO2 recovery from gaseous streams. The research work was focused on the three different parts of which gas selective ceramic membranes are composed, i.e., the microporous gas selective silica layer, the m

  7. Maternal exposure to alkali, alkali earth, transition and other metals: Concentrations and predictors of exposure. (United States)

    Hinwood, A L; Stasinska, A; Callan, A C; Heyworth, J; Ramalingam, M; Boyce, M; McCafferty, P; Odland, J Ø


    Most studies of metals exposure focus on the heavy metals. There are many other metals (the transition, alkali and alkaline earth metals in particular) in common use in electronics, defense industries, emitted via combustion and which are naturally present in the environment, that have received limited attention in terms of human exposure. We analysed samples of whole blood (172), urine (173) and drinking water (172) for antimony, beryllium, bismuth, cesium, gallium, rubidium, silver, strontium, thallium, thorium and vanadium using ICPMS. In general most metals concentrations were low and below the analytical limit of detection with some high concentrations observed. Few factors examined in regression models were shown to influence biological metals concentrations and explained little of the variation. Further study is required to establish the source of metals exposures at the high end of the ranges of concentrations measured and the potential for any adverse health impacts in children.

  8. Characterization of alkali-modified soy protein concentrate

    Directory of Open Access Journals (Sweden)

    Barać Miroljub B.


    Full Text Available To study the influence of the preparation mode, including mild alkali modification, of soy protein concentrate on soluble protein content and composition, some of its nutritive and functional properties were investigated. Soy protein concentrate prepared by aqueous alcohol leaching was modified in mild alkaline solutions (pH 8.0 at 40, 50 and 60° C for 60 minutes and compared with two principal types of commercial soy protein concentrate. Soluble protein content, composition and properties of soy protein concentrate, as well as their potential use are essentially determined by the preparation mode. Limited mild alkali hydrolysis increased protein solubility by 40-71%, while emulsion stability was increased by 18-56%. Major storage soybean proteins exhibited different stability to alcohol denaturation and mild alkali modification. The most susceptible were acidic -A3 - and -A5- subunits of glycinin.

  9. Orbital Feshbach Resonance in Alkali-Earth Atoms. (United States)

    Zhang, Ren; Cheng, Yanting; Zhai, Hui; Zhang, Peng


    For a mixture of alkali-earth atomic gas in the long-lived excited state ^{3}P_{0} and the ground state ^{1}S_{0}, in addition to nuclear spin, another "orbital" index is introduced to distinguish these two internal states. In this Letter we propose a mechanism to induce Feshbach resonance between two atoms with different orbital and nuclear spin quantum numbers. Two essential ingredients are the interorbital spin-exchange process and orbital dependence of the Landé g factors. Here the orbital degrees of freedom plays a similar role as the electron spin degree of freedom in magnetic Feshbach resonance in alkali-metal atoms. This resonance is particularly accessible for the ^{173}Yb system. The BCS-BEC crossover in this system requires two fermion pairing order parameters, and displays a significant difference compared to that in an alkali-metal system.

  10. Oscillation Frequencies for Simultaneous Trapping of Heteronuclear Alkali Atoms

    CERN Document Server

    Kaur, Kiranpreet; Arora, Bindiya


    We investigate oscillation frequencies for simultaneous trapping of more than one type of alkali atoms in a common optical lattice. For this purpose, we present numerical results for magic trapping conditions, where the oscillation frequencies for two different kind of alkali atoms using laser lights in the wavelength range 500-1200 nm are same. These wavelengths will be of immense interest for studying static and dynamic properties of boson-boson, boson-fermion, fermion-fermion, and boson-boson-boson mixtures involving different isotopes of Li, Na, K, Rb, Cs and Fr alkali atoms. In addition to this, we were also able to locate a magic wavelength around 808.1 nm where all the three Li, K, and Rb atoms are found to be suitable for oscillating at the same frequency in a common optical trap.

  11. Properties of Hooked Steel Fibers Reinforced Alkali Activated Material Concrete

    Directory of Open Access Journals (Sweden)

    Faris M. A.


    Full Text Available In this study, alkali activated material was produced by using Class F fly ash from Manjung power station, Lumut, Perak, Malaysia. Fly ash then was activated by alkaline activator which is consisting of sodium silicate (Na2SiO3 and sodium hydroxide (NaOH. Hooked end steel fibers were added into the alkali activated material system with percentage vary from 0 % – 5 %. Chemical compositions of fly ash were first analyzed by using x-ray fluorescence (XRF. All hardened alkali activated material samples were tested for density, workability, and compression after 28 days. Results show a slight increase of density with the addition of steel fibers. However, the workability was reduced with the addition of steel fibers content. Meanwhile, the addition of steel fibers shows the improvement of compressive strength which is about 19 % obtained at 3 % of steel fibers addition.

  12. Formation and Stability of High-Spin Alkali Clusters (United States)

    Schulz, C. P.; Claas, P.; Schumacher, D.; Stienkemeier, F.


    Helium nanodroplet isolation has been applied to agglomerate alkali clusters at temperatures of 380mK. The very weak binding to the surface of the droplets allows a selection of only weakly bound, high-spin states. Here we show that larger clusters of alkali atoms in high-spin states can be formed. The lack of strong bonds from pairing electrons makes these systems nonmetallic, vanderWaals like complexes of metal atoms. We find that sodium and potassium readily form such clusters containing up to 25atoms. In contrast, this process is suppressed for rubidium and cesium. Apparently, for these heavy alkalis, larger high-spin aggregates are not stable and depolarize spontaneously upon cluster formation.

  13. Neuropsychiatric manifestations of alkali metal deficiency and excess

    Energy Technology Data Exchange (ETDEWEB)

    Yung, C.Y.


    The alkali metals from the Group IA of the periodic table (lithium, sodium, potassium, rubidium, cesium and francium) are reviewed. The neuropsychiatric aspects of alkali metal deficiencies and excesses (intoxications) are described. Emphasis was placed on lithium due to its clinical uses. The signs and symptoms of these conditions are characterized by features of an organic brain syndrome with delirium and encephalopathy prevailing. There are no clinically distinctive features that could be reliably used for diagnoses. Sodium and potassium are two essential alkali metals in man. Lithium is used as therapeutic agent in bipolar affective disorders. Rubidium has been investigated for its antidepressant effect in a group of psychiatric disorders. Cesium is under laboratory investigation for its role in carcinogenesis and in depressive illness. Very little is known of francium due to its great instability for experimental study.

  14. Low-frequency Raman scattering in alkali tellurite glasses

    Indian Academy of Sciences (India)

    Angelos G Kalampounias


    Raman scattering has been employed to study the alkali-cation size dependence and the polarization characteristics of the low-frequency modes for the glass-forming tellurite mixtures, 0.1M2O–0.9TeO2 (M = Na, K, Rb and Cs). The analysis has shown that the Raman coupling coefficient alters by varying the type of the alkali cation. The addition of alkali modifier in the tellurite network leads to the conversion of the TeO4 units to TeO3 units with a varying number of non-bridging oxygen atoms. Emphasis has also been given to the lowfrequency modes and particular points related to the low-frequency Raman phenomenology are discussed in view of the experimental findings.

  15. Studying the effect of thermal and acid exposure on alkali activated slag Geopolymer

    Directory of Open Access Journals (Sweden)

    Khater H.M.


    Full Text Available This article reports a study about thermal stability as well as acid resistance of geopolymer materials prepared from Ground Granulated Blast Furnace Slag (GGBFS, Air Cooled Slag (ACS, Silica fume (SF and cement kiln dust (CKD using 6% (weight of equal mix from alkaline sodium hydroxide and sodium silicate activators. Study of addition of ACS, SF and CKD as partial replacement of GGBFS is investigated so as to improve the mechanical and microstructural properties of geopolymer mixes. Compressive strength and SEM were utilized in these studies. Materials were prepared using water/binder of 0.30 at 38°C and 100% RH. Results showed that geopolymer materials prepared using alkali activated slag exhibit large changes in compressive strength with increasing the firing temperature from 300 to 1000°C and exhibit an enhancement in thermal stability as compared to concrete specimens. Materials prepared by replacing GGBFS by 15% ACS resist thermal deterioration up to 1000°C. It was suggested to be suitable for refractory insulation applications as well as for production of nuclear concrete reactors. On the other hand, geopolymer mixes exhibit low stability upon subjecting to different concentration from the mix of nitric and hydrochloric acid in equal ratio (1:1. Current studies of geopolymer microstructure were focused on the morphology as well as the relationship between compositions and mechanical properties.

  16. Kinetics and Mechanism of Oxidation of t-Butylbenzylamine by Diperiodatoargentate(III in Aqueous Alkali

    Directory of Open Access Journals (Sweden)

    Mahantesh A. Angadi


    Full Text Available t-Butylbenzylamine (t-BA is used as a free base in the synthesis of salbutamol drug. Its mechanism of oxidation was proposed from kinetic studies. The kinetics of oxidation of t-butylbenzylamine by diperiodatoargentate(III (DPA was studied spectrophotometrically by monitoring decrease in absorbance of DPA. The reaction was found to be first order each in [DPA] and [t-BA]. The effect of alkali concentration in a wide range on rate of reaction was studied. The rate of reaction was found to be increased with increase in [OH–] in the lower range of [OH–], decreasing effect in the middle range and at higher range again increasing effect on rate of reaction was observed. The added periodate retarded the rate of reaction. The polymerization test revealed that oxidation was occurred with the intervention free radical. A suitable mechanism was proposed for a middle range of [OH–]. The active species of silver(III periodate for all the three different stages of [OH–] are assayed. Rate law was derived and verified. The oxidative product of t-BA was characterized by LC-ESI-MS spectra.

  17. Ringing phenomenon in silica microspheres

    Institute of Scientific and Technical Information of China (English)

    Chunhua Dong; Changling Zou; Jinming Cui; Yong Yang; Zhengfu Han; Guangcan Guo


    Whispering gallery modes in silica microspheres are excited by a tunable continuous-wave laser through the fiber taper. Ringing phenomenon can be observed with high frequency sweeping speed. The thermal nonlinearity in the microsphere can enhance this phenomenon. Our measurement results agree very well with the theoretical predictions by the dynamic equation.

  18. Water Contact Angle Dependence with Hydroxyl Functional Groups on Silica Surfaces under CO2 Sequestration Conditions. (United States)

    Chen, Cong; Zhang, Ning; Li, Weizhong; Song, Yongchen


    Functional groups on silica surfaces under CO2 sequestration conditions are complex due to reactions among supercritical CO2, brine and silica. Molecular dynamics simulations have been performed to investigate the effects of hydroxyl functional groups on wettability. It has been found that wettability shows a strong dependence on functional groups on silica surfaces: silanol number density, space distribution, and deprotonation/protonation degree. For neutral silica surfaces with crystalline structure (Q(3), Q(3)/Q(4), Q(4)), as silanol number density decreases, contact angle increases from 33.5° to 146.7° at 10.5 MPa and 318 K. When Q(3) surface changes to an amorphous structure, water contact angle increases 20°. Water contact angle decreases about 12° when 9% of silanol groups on Q(3) surface are deprotonated. When the deprotonation degree increases to 50%, water contact angle decreases to 0. The dependence of wettability on silica surface functional groups was used to analyze contact angle measurement ambiguity in literature. The composition of silica surfaces is complicated under CO2 sequestration conditions, the results found in this study may help to better understand wettability of CO2/brine/silica system.

  19. Nanoporous Silica-Based Protocells at Multiple Scales for Designs of Life and Nanomedicine

    Directory of Open Access Journals (Sweden)

    Jie Sun


    Full Text Available Various protocell models have been constructed de novo with the bottom-up approach. Here we describe a silica-based protocell composed of a nanoporous amorphous silica core encapsulated within a lipid bilayer built by self-assembly that provides for independent definition of cell interior and the surface membrane. In this review, we will first describe the essential features of this architecture and then summarize the current development of silica-based protocells at both micro- and nanoscale with diverse functionalities. As the structure of the silica is relatively static, silica-core protocells do not have the ability to change shape, but their interior structure provides a highly crowded and, in some cases, authentic scaffold upon which biomolecular components and systems could be reconstituted. In basic research, the larger protocells based on precise silica replicas of cells could be developed into geometrically realistic bioreactor platforms to enable cellular functions like coupled biochemical reactions, while in translational research smaller protocells based on mesoporous silica nanoparticles are being developed for targeted nanomedicine. Ultimately we see two different motivations for protocell research and development: (1 to emulate life in order to understand it; and (2 to use biomimicry to engineer desired cellular interactions.

  20. Organosilane grafted silica: Quantitative correlation of microscopic surface characters and macroscopic surface properties (United States)

    Ji, Tuo; Ma, Chi; Brisbin, Logan; Mu, Liwen; Robertson, Christopher G.; Dong, Yalin; Zhu, Jiahua


    In polymer composites, organosilanes are often used to modify the surface property of silica nanoparticles and improve the interfacial properties. Surface properties of the modified silica, such as grafting density and consequent surface energy, largely depend on the molecular structure of the silane. Achieving maximum interfacial bonding between the filler and polymer requires precise control of silica surface property. In this work, four silanes with similar molecular structure but different alkyl chain lengths, trimethoxy(propyl)silane, trimethoxy(octyl)silane, hexadecyltrimethoxysilane and trimethoxy(octadecyl)silane, are selected as model agents to study their roles in influencing silica surface property. The grafting density of silane on the silica is well controlled by regulating the reaction conditions. Three main surface characters, silane grafting density, surface energy and surface potential, are measured. More importantly, a linear relationship has been correlated when plotting grafting density vs. surface energy and grafting density vs. surface potential. Utilizing these relationships, a linear model has been developed to predict grafting density and surface energy by simply measuring surface potential. This model has been validated by both commercial silica and synthesized silica particles of different sizes.

  1. Precursor Mediated Synthesis of Nanostructured Silicas: From Precursor-Surfactant Ion Pairs to Structured Materials

    Directory of Open Access Journals (Sweden)

    Peter Hesemann


    Full Text Available The synthesis of nanostructured anionic-surfactant-templated mesoporous silica (AMS recently appeared as a new strategy for the formation of nanostructured silica based materials. This method is based on the use of anionic surfactants together with a co-structure-directing agent (CSDA, mostly a silylated ammonium precursor. The presence of this CSDA is necessary in order to create ionic interactions between template and silica forming phases and to ensure sufficient affinity between the two phases. This synthetic strategy was for the first time applied in view of the synthesis of surface functionalized silica bearing ammonium groups and was then extended on the formation of materials functionalized with anionic carboxylate and bifunctional amine-carboxylate groups. In the field of silica hybrid materials, the “anionic templating” strategy has recently been applied for the synthesis of silica hybrid materials from cationic precursors. Starting from di- or oligosilylated imidazolium and ammonium precursors, only template directed hydrolysis-polycondensation reactions involving complementary anionic surfactants allowed accessing structured ionosilica hybrid materials. The mechanistic particularity of this approach resides in the formation of precursor-surfactant ion pairs in the hydrolysis-polycondensation mixture. This review gives a systematic overview over the various types of materials accessed from this cooperative ionic templating approach and highlights the high potential of this original strategy for the formation of nanostructured silica based materials which appears as a complementary strategy to conventional soft templating approaches.

  2. Synthesis and Characterization of Polyvinylpyrrolidone Silica Core-Shell Nanocomposite Particles. (United States)

    Chen, Lian-Xi; Li, Jie; Li, Xi; Zhang, Zhong-Min; Jiao, Cai-Bin


    In this work, a novel and facile strategy for making a new type of polymer/silica nanocomposte particle was proposed. Colloidally stable polyvinypyrrolidone (PVP)/silica core-shell nanocomposite particles have been successfully synthesized using an azo initiator via seed polymerization of N-vinyl-2-pyrrolidone (NVP) and VFSs (VFSs) that were derived from vinyl triethoxysilane (VTES). It was suggested from the FTIR and TGA analysis that the copolymerization reaction of NVP with VFSs has been thoroughly carried out. In addition, SEM images showed that PVP/silica nanocomposite particles have relatively rough surface due to surface polymerization in comparison with VFSs. Furthermore, TEM results proved that the size of VFSs had considerable effects on the appearance of PVP/silica nanocomposite particles. Generally, it presented that several silica nanoparticle cores with an average size of 78 nm mainly pack together within each nanocomposite particle after seed polymerization. Interestingly, the average shell thickness was 59 nm for most PVP/silica nanocomposite particles with cores about 242 nm. However, when the core size was large enough to about 504 nm, a series of PVP/silica nanocomposite particles with a relative thin shell were observed.

  3. A hidden history of heartburn: The milk-alkali syndrome. (United States)

    Swaminathan, Krishnan


    Milk-alkali syndrome was once considered to be of historic interest and a rare cause of hypercalcemia. Currently, it should be an important consideration in the differential diagnosis of hypercalcemia, after malignancies and primary hyperparathyroidism. The resurgence is in part due to the easy availability of over the counter (OTC) calcium preparations. We describe a 50-year-old man who presented with severe hypercalcemia on two occasions associated with renal failure and metabolic alkalosis. Extensive investigations during the first admission failed to unravel a specific cause of hypercalcemia but a thorough history during his subsequent admission helped to confirm the diagnosis of milk-alkali syndrome.


    Institute of Scientific and Technical Information of China (English)

    LIU Xianfan; YANG Zhengxi; LIU Jiaduo; ZHANG Chengjiang; WU Dechao; LI Youguo


    Ultramafic hypoxenoliths found in the alkali-rich porphyry in the Liuhe Village, Heqing, Yunnan,China, are of great significance in understanding the origin and evolution of the porphyry. This paper discusses the mineralogical features of the hypoxenoliths. It shows that the xenoliths are characterized by the upper mantle rocks modified to certain extent by the enriched mantle fluid metasomatism in the mantle environment, with the enriched mantle property of Iow-degree partial melting. This constitutes the important mineralogical evidence for the petrogenesis and mineralization of alkali-rich porphyry.

  5. Upgrading of petroleum oil feedstocks using alkali metals and hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard


    A method of upgrading an oil feedstock by removing heteroatoms and/or one or more heavy metals from the oil feedstock composition. This method reacts the oil feedstock with an alkali metal and an upgradant hydrocarbon. The alkali metal reacts with a portion of the heteroatoms and/or one or more heavy metals to form an inorganic phase separable from the organic oil feedstock material. The upgradant hydrocarbon bonds to the oil feedstock material and increases the number of carbon atoms in the product. This increase in the number of carbon atoms of the product increases the energy value of the resulting oil feedstock.

  6. Rice Husk Ash as a Renewable Source for the Production of Value Added Silica Gel and its Application: An Overview

    Directory of Open Access Journals (Sweden)

    Ram Prasad


    properties assumes importance at this juncture. Copyright © 2012 by BCREC UNDIP. All rights reserved.Received: 23th November 2011, Revised: 09th January 2012, Accepted: 10th January 2012[How to Cite: R. Prasad, and M. Pandey. (2012. Rice Husk Ash as a Renewable Source for the Production of Value Added Silica Gel and its Application: An Overview. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (1: 1-25. doi:10.9767/bcrec.7.1.1216.1-25][How to Link / DOI: ] | View in 

  7. Accelerator, superplasticiter and silica gome by wet shotcrete; Hormigon Proyectado por Via Humeda

    Energy Technology Data Exchange (ETDEWEB)



    This project has been carried out by Geocontrol during the period September 1997-november 2000. The main target of this project was to establish a better knowledgement about the influence of the accelerator, silica fume, steel fibres and super plasticizer on the wet shotcrete properties. This project has been developed in three phases focused in three specifical targets: I. Effect of the accelerator, superplasticizer and silica fume dosages on shotcrete strength. II. Influence of steel fibres and silica fume on shotcrete characteristics. III. Steel fibres dosages and type effect of shotcrete absorbed energy. The main conclusions obtained from this research are the following. 1. Accelerators free of alkalis have a very little influence on the shotcrete strength reduction. 2. The best results are obtained when the accelerator dosage is the lowest, with a reference of the 4% of cement weigh. 3. The superplasticizer is very important in order to reach the lowest water/cement ratio. 4. Silica fume has a strong and positive influence on shotcrete characteristics but only if the dosages is higher than 30 kg/m''3. 5. The best results with silica fume are obtained when this product is added as a separate product, instead to be missed with other additive as superplasticizer. 6. Steel fibres addition improves dramatically the shotcrete post-failure characteristics. 7. A shotcrete without steel fibres and with a strength ranged between 25 and 40 MPa absorbers 130-180 Joules and another one with a steel mesh of 150x150x6 mm absorbers 1100 Joules. 8. Steel fibres shotcrete can reach the same energy absorption that another one reinforced with wire mesh. 9. During shotcreting the steel fibres dosages has a loss of 10 to 30 % due to shotcrete rebound. This research project allows to improve the knowledgement os shotcreting technique in order to use it with more efficiency than in the past. (Author)

  8. Alkali metal control over N-N cleavage in iron complexes. (United States)

    Grubel, Katarzyna; Brennessel, William W; Mercado, Brandon Q; Holland, Patrick L


    Though N2 cleavage on K-promoted Fe surfaces is important in the large-scale Haber-Bosch process, there is still ambiguity about the number of Fe atoms involved during the N-N cleaving step and the interactions responsible for the promoting ability of K. This work explores a molecular Fe system for N2 reduction, particularly focusing on the differences in the results obtained using different alkali metals as reductants (Na, K, Rb, Cs). The products of these reactions feature new types of Fe-N2 and Fe-nitride cores. Surprisingly, adding more equivalents of reductant to the system gives a product in which the N-N bond is not cleaved, indicating that the reducing power is not the most important factor that determines the extent of N2 activation. On the other hand, the results suggest that the size of the alkali metal cation can control the number of Fe atoms that can approach N2, which in turn controls the ability to achieve N2 cleavage. The accumulated results indicate that cleaving the triple N-N bond to nitrides is facilitated by simultaneous approach of least three low-valent Fe atoms to a single molecule of N2.

  9. Silica-Coated Liposomes for Insulin Delivery

    Directory of Open Access Journals (Sweden)

    Neelam Dwivedi


    Full Text Available Liposomes coated with silica were explored as protein delivery vehicles for their enhanced stability and improved encapsulation efficiency. Insulin was encapsulated within the fluidic phosphatidylcholine lipid vesicles by thin film hydration at pH 2.5, and layer of silica was formed above lipid bilayer by acid catalysis. The presence of silica coating and encapsulated insulin was identified using confocal and electron microscopy. The native state of insulin present in the formulation was evident from Confocal Micro-Raman spectroscopy. Silica coat enhances the stability of insulin-loaded delivery vehicles. In vivo study shows that these silica coated formulations were biologically active in reducing glucose levels.


    Institute of Scientific and Technical Information of China (English)

    LI Xiaohu; LU Yun; LIN Sicong


    This paper reports mainly the preparation of silica supported acetylacetone ligands and their cobalt complexes, the characterization of their chemical structure, and the evaluation of their catalytic activity in the reaction for the preparation of ethers directly from alkanols and benzyl chloride. The results indicate that those silica supported β-diketone cobalt complexes (SACO) not only can simplify the reaction procedure of the ether preparation but also show a much higher catalytic activity in comparison with other homogeneous catalysts. In addition, SACO can be recovered and reused although their catalytic activity descend gradually as a result of the decrease in their cobalt content.

  11. Time and frequency dependent rheology of reactive silica gels. (United States)

    Wang, Miao; Winter, H Henning; Auernhammer, Günter K


    In a mixture of sodium silicate and low concentrated sulfuric acid, nano-sized silica particles grow and may aggregate to a system spanning gel network. We studied the influence of the finite solubility of silica at high pH on the mechanical properties of the gel with classical and piezo-rheometers. Direct preparation of the gel sample in the rheometer cell avoided any pre-shear of the gel structure during the filling of the rheometer. The storage modulus of the gel grew logarithmically with time with two distinct growth laws. The system passes the gel point very quickly but still shows relaxation at low frequency, typically below 6 rad/s. We attribute this as a sign of structural rearrangements due to the finite solubility of silica at high pH. The reaction equilibrium between bond formation and dissolution maintains a relatively large bond dissolution rate, which leads to a finite life time of the bonds and behavior similar to physical gels. This interpretation is also compatible with the logarithmic time dependence of the storage modulus. The frequency dependence was more pronounced for lower water concentrations, higher temperatures and shorter reaction times. With two relaxation models (the modified Cole-Cole model and the empirical Baumgaertel-Schausberger-Winter model) we deduced characteristic times from the experimental data. Both models approximately described the data and resulted in similar relaxation times.

  12. Analysis of the Damping Behavior and Microstructure of Cement Matrix with Silane-treated Silica Fume

    Institute of Scientific and Technical Information of China (English)

    OU Jinping; LIU Tiejun; LI Jiahe


    The surface treatment of silica fume with silane coupling agent prior to incorporation in a cement mortar resulted in composites exhibiting increases in loss tangent by 5%-200% and storage modulus by 10%-20%, relative to the value obtained by using as-received silica fume. The scanning electron microscopy (SEM) images indicate that there is a morphological difference in the cement paste with treated and as-received silica fume. The X-ray diffraction (XRD), infrared (IR) spectrum analyses and mercury intrusion porosimetry (MIP) have provided evidence to understand the reaction mechanism between treated silica fume and the hydrate product of cement. This has led to the establishment of an initial microscopic model describing the damping behavior of cement matrix.

  13. High yield recombinant production of a self-assembling polycationic peptide for silica biomineralization. (United States)

    Zerfaß, Christian; Braukmann, Sandra; Nietzsche, Sandor; Hobe, Stephan; Paulsen, Harald


    We report the recombinant bacterial expression and purification at high yields of a polycationic oligopeptide, P5S3. The sequence of P5S3 was inspired by a diatom silaffin, a silica precipitating peptide. Like its native model, P5S3 exhibits silica biomineralizing activity, but furthermore has unusual self-assembling properties. P5S3 is efficiently expressed in Escherichia coli as fusion with ketosteroid isomerase (KSI), which causes deposition in inclusion bodies. After breaking the fusion by cyanogen bromide reaction, P5S3 was purified by cation exchange chromatography, taking advantage of the exceptionally high content of basic amino acids. The numerous cationic charges do not prevent, but may even promote counterion-independent self-assembly which in turn leads to silica precipitation. Enzymatic phosphorylation, a common modification in native silica biomineralizing peptides, can be used to modify the precipitation activity.

  14. IRMPD action spectroscopy of alkali metal cation-cytosine complexes: effects of alkali metal cation size on gas phase conformation. (United States)

    Yang, Bo; Wu, R R; Polfer, N C; Berden, G; Oomens, J; Rodgers, M T


    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both similar and distinctive spectral features over the range of ~1000-1900 cm(-1). The IRMPD spectra of the Li(+)(cytosine), Na(+)(cytosine), and K(+)(cytosine) complexes are relatively simple but exhibit changes in the shape and shifts in the positions of several bands that correlate with the size of the alkali metal cation. The IRMPD spectra of the Rb(+)(cytosine) and Cs(+)(cytosine) complexes are much richer as distinctive new IR bands are observed, and the positions of several bands continue to shift in relation to the size of the metal cation. The measured IRMPD spectra are compared to linear IR spectra of stable low-energy tautomeric conformations calculated at the B3LYP/def2-TZVPPD level of theory to identify the conformations accessed in the experiments. These comparisons suggest that the evolution in the features in the IRMPD action spectra with the size of the metal cation, and the appearance of new bands for the larger metal cations, are the result of the variations in the intensities at which these complexes can be generated and the strength of the alkali metal cation-cytosine binding interaction, not the presence of multiple tautomeric conformations. Only a single tautomeric conformation is accessed for all five alkali metal cation-cytosine complexes, where the alkali metal cation binds to the O2 and N3 atoms of the canonical amino-oxo tautomer of cytosine, M(+)(C1).

  15. Silica Pigments for Glossy Ink Jet Media

    Institute of Scientific and Technical Information of China (English)

    Sun Qi; Michael R. Sestrick; Yoshi Sugimoto; William A. Welsh


    Silica is a versatile pigment for ink jet media. Micronized silica gel is the worldwide standard for high performance matte ink jet media. For glossy ink jet media, several different forms of silica are widely used. Submicron silica gel dispersions, with either anionic or cationic surfaces, can be employed in either absorptive basecoat layers or in the glossy ink receptive top layer. Colloidal silica, with a variety of particle sizes and surface modifications, is utilized extensively in glossy top layers. It will show how various silica pigments can be utilized in glossy ink receptive coatings, both in cast based glossy media and RC based glossy media. Several novel silica pigments will be examined by relating the physical properties of the pigments and the formula variables to the print quality of the ink jet media.

  16. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fluorinated carboxylic acid alkali... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under...

  17. Formation of alkali-metal nanoparticles in alkali-silicate glasses under electron irradiation and thermal processing (United States)

    Bochkareva, E. S.; Sidorov, A. I.; Ignat'ev, A. I.; Nikonorov, N. V.; Podsvirov, O. A.


    Experiments and numerical simulation show that the irradiation of alkali-containing glasses using electrons at an energy of 35 keV and the subsequent thermal processing at a temperature above the vitrification point lead to the formation of spherical metal (lithium, sodium, and potassium) nanoparticles with oxide sheaths that exhibit plasmon resonances in the visible spectral range. Glasses containing two alkali metals exhibit mutual effect of metals on the formation of nanoparticles with two compositions due to the difference of ion radii and mobilities of metal ions.

  18. Biodiesel synthesis from cottonseed oil using homogeneous alkali catalyst and using heterogeneous multi walled carbon nanotubes: Characterization and blending studies

    Directory of Open Access Journals (Sweden)

    A. Arun Shankar


    Full Text Available The trans-esterification of cottonseed oil using strong alkali catalyst and using multi walled carbon nano tubes as catalyst to produce biodiesel was studied. The interaction effects of various factors such as temperature, amount of alkali used, alcohol to oil ratio and reaction time on yield of biodiesel were studied. The maximum yield of 95% biodiesel was obtained. The biodiesel produced was characterized using FT-IR spectral analysis and GC–MS analysis to ascertain the various functional groups and compounds available in it. The properties of biodiesel using homogeneous alkali catalyst and heterogeneous multi walled carbon nanotubes such as calorific value (36.18 MJ/kg, 33.78 MJ/kg, flash point (160 °C, 156 °C and other properties such as viscosity, cloud point, pour point and density were found to determine the quality of biodiesel produced. The studies were done by blending the biodiesel produced with diesel and properties of blended samples were estimated to ascertain the use of blended samples in internal combustion engines.

  19. Origin of organism-dependent biogenic silica quartz formation. (United States)

    Sato, Kiminori


    Organism-dependent biogenic quartz formation in the steady-state environment is a phenomenon that can address the global environmental issues such as diagenetic evolution, biogeochemical cycling, and reservoir formation, but detailed studies have not been performed so far. Here, steady-state quartz formation is studied for amorphous silica of different biogenic origin on the basis of the recently established mechanistic model [Sato et al., J. Phys. Chem. C 2011, 115, 18131]. Amorphous silica originated from rice husks possesses angstrom-scale pores larger by 1.3 Å than those originated from diatom algae. The slight difference of pore size dramatically reduces activation energies of water diffusion by 78% and reactions of water molecules at pore surfaces by 47%, resulting in the reduction of activation energy of biogenic quartz formation by 64%. The present findings evidence that angstrom-scale pores intrinsically residing in the amorphous matrix are the organism-dependent origin of steady-state biogenic quartz formation.

  20. Fluorescent Functionalized Mesoporous Silica for Radioactive Material Extraction

    Energy Technology Data Exchange (ETDEWEB)

    Li, Juan; Zhu, Kake; Shang, Jianying; Wang, Donghai; Nie, Zimin; Guo, Ruisong; Liu, Chongxuan; Wang, Zheming; Li, Xiaolin; Liu, Jun


    Mesoporous silica with covalently bound salicylic acid molecules incorporated in the structure was synthesized with a one-pot, co-condensation reaction at room temperature. The as-synthesized material has a large surface area, uniform particle size, and an ordered pore structure as determined by characterization with transmission electron microscopy, thermal gravimetric analysis, and infrared spectra, etc. Using the strong fluorescence and metal coordination capability of salicylic acid, functionalized mesoporous silica (FMS) was developed to track and extract radionuclide contaminants, such as uranyl [U(VI)] ions encountered in subsurface environments. Adsorption measurements showed a strong affinity of the FMS toward U(VI) with a Kd value of 105 mL/g, which is four orders of magnitude higher than the adsorption of U(VI) onto most of the sediments in natural environments. The new materials have a potential for synergistic environmental monitoring and remediation of the radionuclide U(VI) from contaminated subsurface environments.

  1. Purification and characterization of double-wall carbon nanotubes synthesized by catalytic chemical vapor deposition on mesoporous silica (United States)

    Ramesh, P.; Okazaki, T.; Sugai, T.; Kimura, J.; Kishi, N.; Sato, K.; Ozeki, Y.; Shinohara, H.


    Double-wall carbon nanotubes (DWNTs) have been selectively synthesized by catalytic chemical vapor deposition of alcohol over Fe/Co loaded mesoporous silica. The as-grown carbon nanotubes are purified using a multi-step process involving heat treatment in air followed by alkali and acid treatments. The nanotubes are characterized as-grown and after each step of the purification stage by thermo-gravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. It is observed that most of the mesoporous silica and metal particles have been removed from the as-grown nanotubes by these treatments. The carbon content of the nanotube material obtained after the purification is found to be more than 90 wt%.

  2. Alkali-Activated Geopolymers: A Literature Review (United States)


    stated that the main reaction product of hardened AAS paste is C-S-H, followed by hydrotalcite , hydrogarnet, tetracalium aluminate hydrate...hydration product. The hydrotalcite , hydrogarnet and ettringite are formed through the combination of the aluminum present in the slag and MgO, Fe2O3...AA-S specimen additional revealed hydrotalcite seen as six-coordinated aluminum. This was confirmed via x-ray diffraction. Regardless, the overall

  3. Water Penetration—Its Effect on the Strength and Toughness of Silica Glass (United States)

    Wiederhorn, Sheldon M.; Fett, Theo; Rizzi, Gabriele; Hoffmann, Michael J.; Guin, Jean-Pierre


    When a crack forms in silica glass, the surrounding environment flows into the crack opening, and water from the environment reacts with the glass to promote crack growth. A chemical reaction between water and the strained crack-tip bonds is commonly regarded as the cause of subcritical crack growth in glass. In silica glass, water can also have a secondary effect on crack growth. By penetrating into the glass, water generates a zone of swelling and, hence, creates a compression zone around the crack tip and on the newly formed fracture surfaces. This zone of compression acts as a fracture mechanics shield to the stresses at the crack tip, modifying both the strength and subcritical crack growth resistance of the glass. Water penetration is especially apparent in silica glass because of its low density and the fact that it contains no modifier ions. Using diffusion data from the literature, we show that the diffusion of water into silica glass can explain several significant experimental observations that have been reported on silica glass, including (1) the strengthening of silica glass by soaking the glass in water at elevated temperatures, (2) the observation of permanent crack face displacements near the crack tip of a silica specimen that had been soaked in water under load, and (3) the observation of high concentrations of water close to the fracture surfaces that had been formed in water. These effects are consistent with a model suggesting that crack growth in silica glass is modified by a physical swelling of the glass around the crack tip. An implication of water-induced swelling during fracture is that silica glass is more resistant to crack growth than it would be if swelling did not occur.

  4. Composite polymer electrolytes using fumed silica fillers: synthesis, rheology and electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Saad A.; Fedkiw, Peter S.; Baker, Gregory L.


    The goal of the synthesis research was to devise routes to PEG/fumed silica/lithium salt composites that can be processed and then photochemically cross-linked to form mechanically stable electrolytes. An essential feature of the system is that the ionic conductivity and the mechanical properties must be de-coupled from each other, i.e., cross-linking of the fumed silica matrix must not cause a significant deterioration of the conductivity of the composite. As shown in Figure 2, we prepared a range of surface-modified fumed silicas and investigated their ability to form mechanically stable composite electrolytes. The groups used to modify the surface properties of the silica ranged from simple linear alkyls that render the silica hydrophobia to polyethers that promote compatibility with the electrolyte. From these materials we developed a cross-linkable system that satisfies the criteria of processibility and high-conductivity. The key material needed for the cross-linking reaction are silicas that bear surface-attached monomers. As shown schematically in Figure 3a, we prepared fumed silicas with a combination of surface groups, for example, an octyl chain with different coverages of tethered methacrylates. The length of the tether was varied, and we found that both C{sub 3} and C{sub 8} tethers gave useful composites. The functionalized silicas were combined with PEG-DM, AIBN or benzophenone (free radical initiators), LiClO{sub 4} or Li imide, and either methyl, butyl, or octyl, methacrylate to form stable clear gels. Upon irradiation with UV light, polymerization of both the tethered methacrylate and the added methacrylate took place, yielding a cross-linked rubbery composite material. Ionic conductivity measurements before and after cross-linking showed only a slight decrease (see Figure 9 later), thereby offering strong experimental evidence that the mechanical properties conferred by the silica matrix are de-coupled from the ionic conductivity of the PEG

  5. Graft polymerization of styrene initiated by covalently bonded peroxide groups on silica. (United States)

    Bachmann, Stefan; Wang, Hongyu; Albert, Klaus; Partch, Richard


    The graft polymerization of styrene initiated by immobilized peroxide groups was investigated. Three different types of modification reactions were used to introduce peroxide groups which are directly attached onto the surface of two different silica supports. Silanol groups were chlorinated using thionyl chloride or tetrachlorosilane. In another reaction pathway 1,3,5-benzenetricarbonyl chloride enabled the introduction of free acid chloride residues bonded onto the surface of silica. tert-Butyl hydroperoxide (TBHP) was used to transform the chlorosilyl and the acid chloride groups into peroxide residues. In a further reaction step the covalently bonded peroxides initiated the polymerization of styrene to form grafted polystyrene directly attached onto the silica support. Solid-state 13C CP/MAS NMR spectroscopy, and thermogravimetric and scanning electron microscope measurements enabled a clear structure and property elucidation of the different bonded phases. The highest amount of grafted polystyrene was achieved employing the acid chloride synthesis pathway with silica-gel, whereas modification of spherical silica only led to minor amounts of grafted polymer. The results contribute to the evolving need to understand particle surface modifications and may have positive impact on development of new HPLC stationary phases for improved elutant resolution.

  6. Thermobarometry for spinel lherzolite xenoliths in alkali basalts (United States)

    Ozawa, Kazuhito; Youbi, Nasrrddine; Boumehdi, Moulay Ahmed; Nagahara, Hiroko


    geothermobarometry based on reactions with large and distinct volume changes, is necessary. Specification of mineral domains and their components representing the thermal state of the mantle just before xenolith extraction is one of the major tasks for the establishment of reliable geothermobarometry for spinel lherzolite xenoliths. Systematic variations of such mineralogical information among xenoliths transported by a single volcanic eruption guarantees proper estimation of a mantle geotherm. For the development of such geobarometry, it is important to choose appropriate xenolith locality, where previous studies provide enough information and where many xenolith samples are available for extending a range of derivation depth. Spinel lherzolite xenoliths in alkali basalts from Bou Ibalhatene maars in the Middle Atlas in Morocco are suitable study target. Geochemical, geochronological, petrological, and rheological aspects of the spinel lherzolite xenoliths have been studied (Raffone et al. 2009; El Messbahi et al., 2015; Witting et al., 2010; El Azzouzi et al., 2010), which show that they represent fragments of the lithospheric mantle formed and modified since 1.7Ga before their extraction from Miocene to recent. We have pinpointed portions of minerals in the xenolith samples and their components representing condition just before their entrapment in magmas, on which appropriate geothermobarometers are applied and detected ~0.5GPa pressure difference (1.5-2.0GPa) for ~100°C variation in temperatures (950-1050°C).

  7. A new mechanism for radiation damage processes in alkali halides

    NARCIS (Netherlands)

    Dubinko, V.I.; Turkin, A.A.; Vainshtein, D.I.; Hartog, H.W. den


    We present a theory of radiation damage formation in alkali halides based on a new mechanism of dislocation climb, which involves the production of VF centers (self-trapped hole neighboring a cation vacancy) as a result of the absorption of H centers of dislocation lines. We consider the evolution o

  8. Powder X-ray diffraction study af alkali alanates

    DEFF Research Database (Denmark)

    Cao, Thao; Mosegaard Arnbjerg, Lene; Jensen, Torben René

    for mobile applications, new materials with high gravimetric and volumetric storage capacity of hydrogen have to be developed. Alkali alanates are promising for hydrogen storage materials. Sodium alanate stores hydrogen reversibly at moderate conditions when catalysed with, e.g. titanium, whereas potassium...

  9. Alkali and Halogen Chemistry in Volcanic Gases on Io

    CERN Document Server

    Schaefer, L


    We use chemical equilibrium calculations to model the speciation of alkalis and halogens in volcanic gases emitted on Io. The calculations cover wide temperature (500-2000 K) and pressure (10^-6 to 10^+1 bars) ranges, which overlap the nominal conditions at Pele (T = 1760 K, P = 0.01 bars). About 230 compounds of 11 elements (O, S, Li, Na, K, Rb, Cs, F, Cl, Br, I) are considered. We predict the major alkali and halogen species in a Pele-like volcanic gas and the major alklai and halogen condensates. We also model disequilibrium chemistry of the alkalis and halogens in the volcanic plume. Based on this work and our prior modeling for Na, K, and Cl in a volcanic plume, we predict the major loss processes for the alkali halide gases are photolysis and/or condensation onto grains. On the basis of elemental abundances and photochemical lifetimes, we recommend searching for gaseous KCl, NaF, LiF, LiCl, RbF, RbCl, CsF, and CsCl around volcanic vents during eruptions. Based on abundance considerations and observation...

  10. Chlor-Alkali Industry: A Laboratory Scale Approach (United States)

    Sanchez-Sanchez, C. M.; Exposito, E.; Frias-Ferrer, A.; Gonzalez-Garaia, J.; Monthiel, V.; Aldaz, A.


    A laboratory experiment for students in the last year of degree program in chemical engineering, chemistry, or industrial chemistry is presented. It models the chlor-alkali process, one of the most important industrial applications of electrochemical technology and the second largest industrial consumer of electricity after aluminium industry.

  11. Influence of temperature on alkali stress adaptation in Listeria monocytogenes (United States)

    Listeria monocytogenes cells may induce alkali stress adaptation when exposed to sublethal concentrations of alkaline cleaners and sanitizers that may be frequently used in the food processing environment. In the present study, the effect of temperature on the induction and the stability of such alk...

  12. Red-luminescent europium (III) doped silica nanoshells: synthesis, characterization, and their interaction with HeLa cells. (United States)

    Yang, Jian; Sandoval, Sergio; Alfaro, Jesus G; Aschemeyer, Sharraya; Liberman, Alex; Martin, David T; Makale, Milan; Kummel, Andrew C; Trogler, William C


    A simple method to fabricate Eu(3+) doped silica nanoshells particles with 100 and 200 nm diameters is reported. Amino polystyrene beads were used as templates, and an 8 to 10 nm thick silica gel coating was formed by the sol-gel reaction. After removing the template by calcination, porous dehydrated silica gel nanoshells of uniform size were obtained. The Eu(3+) doped silica nanoshells exhibited a red emission at 615 nm on UV excitation. The porous structure of the silica shell wall was characterized by transmission electron microscopy measurements, while particle size and zeta potentials of the particles suspended in aqueous solution were characterized by dynamic light scattering. Two-photon microscopy was used to image the nanoshells after assimilation by HeLa cancer cells.

  13. A Better Understanding of the Formation of Silica Nanococoons%A Better Understanding of the Formation of Silica Nanococoons

    Institute of Scientific and Technical Information of China (English)

    许臻; 赵环宇; 闫卓君; 王思兵; 陈媛丽; 李宝宗; 李艺; 杨永刚


    Silica nanococoons with coiled or concentric circular pore channels in the walls attracted much attention, recently. However, the formation of them is not well illustrated. Herein, hollow silica shells with organized pore channels parallel to the shell surface were prepared through a single-templating method using the self-assemblies of a chiral low-molecular-weight amphiphile, L-18Phe6PyBr, as templates under a dilute concentration. These nano- cocoons were characterized using X-ray diffractometer and N2 sorption. The formation of them was clearly shown in the field-emission electron microscopy images which were taken at a low voltage. Moreover, transmission elec- tron microscopy images taken after different reaction times indicated a cooperative self-assemble mechanism. It was also found that the nanocoons were formed from coiled nanoribbons.

  14. Ordered mesoporous silica: microwave synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Fantini, M.C.A. [IF-USP, CP 66318, 05315-970, Sao Paulo, SP (Brazil)]. E-mail:; Matos, J.R. [IQ-USP, CP 26077, 05599-970, Sao Paulo, SP (Brazil); Silva, L.C. Cides da [IQ-USP, CP 26077, 05599-970, Sao Paulo, SP (Brazil); Mercuri, L.P. [IQSC-USP, CP 780, 13560-970, Sao Carlos, SP (Brazil); Chiereci, G.O. [IQSC-USP, CP 780, 13560-970, Sao Carlos, SP (Brazil); Celer, E.B. [Department of Chemistry, Kent State University, Kent, OH 44240 (United States); Jaroniec, M. [Department of Chemistry, Kent State University, Kent, OH 44240 (United States)


    Ordered mesoporous silicas, FDU-1, synthesized by using triblock copolymer, EO{sub 39}BO{sub 47}EO{sub 39}, as template were hydrothermally treated in a microwave oven at 373 K for different periods of time. The structural and morphological properties of these silicas were investigated by X-ray diffraction and nitrogen adsorption and compared with those for the FDU-1 samples prepared by conventional hydrothermal treatment at 373 K. All samples were calcined at 813 K in N{sub 2} and air. This procedure succeeded in producing ordered cage-like mesoporous structures even after 15 min of the microwave treatment. The best sample was obtained after 60 min of the microwave treatment, which is reflected by narrow pore size distribution, uniform pore size entrances and thick mesopore walls. Longer time of the microwave treatment increased nonuniformity of the pore entrance sizes as evidenced by changes in the hysteresis loops of nitrogen adsorption isotherms.

  15. Pore solution chemistry of alkali-activated ground granulated blast-furnace slag

    Energy Technology Data Exchange (ETDEWEB)

    Song, S.; Jennings, H.M. [Northwestern Univ., Evanston, IL (United States)


    The chemical composition and pH of the pore solution extracted from six different ground granulated blast-furnace slag (GGBFS) pastes were determined. The concentrations of Si, Ca, Al, and Mg are functions of the pH of the aqueous phase, with high pH associated with the higher concentrations of Si and Al and the lower concentrations of Ca and Mg. When GGBFS is mixed with an aqueous phase with pH higher than 11.5, the reaction is activated or accelerated. The main hydration product was identified as C-S-H, and hydrotalcite, at later stages of hydration, was observed in the pastes with an aqueous phase of a high pH. The effect of pore solution on the alkali activation of GGBFS is discussed with reference to the hydration products.

  16. Alkali treated Foumanat tea waste as an efficient adsorbent for methylene blue adsorption from aqueous solution

    Directory of Open Access Journals (Sweden)

    Azadeh Ebrahimian Pirbazari


    Full Text Available The adsorption of methylene blue (MB from aqueous solution by alkali treated Foumanat tea waste (ATFTW from agriculture biomass was investigated. The adsorbent was characterized by Scanning Electron Microscopy (SEM, Fourier Transform-Infrared Spectroscopy (FT-IR and nitrogen physisorption. FTIR results showed complexation and ion exchange appear to be the principle mechanism for MB adsorption. The adsorption isotherm data were fitted to Langmuir, Sips, Redlich-Peterson and Freundlich equations, and the Langmuir adsorption capacity, Qmax was found to be 461 mgg−1. It was found that the adsorption of MB increases by increasing temperature from 303 to 323 K and the process is endothermic in nature. The removal of MB by ATFTW followed pseudo-second order reaction kinetics based on Lagergren equations. Mechanism studies indicated that the adsorption of MB on the ATFTW was mainly governed by external mass transport where particle diffusion was the rate limiting step.

  17. Silica exposure and systemic vasculitis. (United States)

    Mulloy, Karen B


    Work in Department of Energy (DOE) facilities has exposed workers to multiple toxic agents leading to acute and chronic diseases. Many exposures were common to numerous work sites. Exposure to crystalline silica was primarily restricted to a few facilities. I present the case of a 63-year-old male who worked in DOE facilities for 30 years as a weapons testing technician. In addition to silica, other workplace exposures included beryllium, various solvents and heavy metals, depleted uranium, and ionizing radiation. In 1989 a painful macular skin lesion was biopsied and diagnosed as leukocytoclastic vasculitis. By 1992 he developed gross hematuria and dyspnea. Blood laboratory results revealed a serum creatinine concentration of 2.1 mg/dL, ethrythrocyte sedimentation rate of 61 mm/hr, negative cANCA (antineutrophil cytoplasmic antibody cytoplasmic pattern), positive pANCA (ANCA perinuclear pattern), and antiglomerular basement membrane negative. Renal biopsy showed proliferative (crescentric) and necrotizing glomerulonephritis. The patient's diagnoses included microscopic polyangiitis, systemic necrotizing vasculitis, leukocytoclastic vasculitis, and glomerulonephritis. Environmental triggers are thought to play a role in the development of an idiopathic expression of systemic autoimmune disease. Crystalline silica exposure has been linked to rheumatoid arthritis, scleroderma, systemic lupus erythematosus, rapidly progressive glomerulonephritis and some of the small vessel vasculitides. DOE workers are currently able to apply for compensation under the federal Energy Employees Occupational Illness Compensation Program (EEOICP). However, the only diseases covered by EEOICP are cancers related to radiation exposure, chronic beryllium disease, and chronic silicosis.

  18. Polystyrene-block-poly(ethylene oxide) copolymers as templates for stacked, spherical large-mesopore silica coatings: dependence of silica pore size on the PS/PEO ratio



    Large-mesopore silica films with a narrow pore size distribution and high porosity have been obtained by a sol–gel reaction of a silicon oxide precursor (TEOS) and using polystyrene-block-poly(ethylene oxide) (PS-b-PEO) copolymers as templates in an acidic environment. PS-b-PEO copolymers with different molecular weight and composition have been studied in order to assess the effects of the block length on the pore size of the templated silica films. The changes in the morphology of the porou...

  19. Comparative Study of Alkali-Activated Fly Ash Manufactured Under Pulsed Microwave Curing and Thermal Oven Curing


    Shi, Shi; Bai, Yun; Li, H.; Xu, D. L.; Basheer, P. A. Muhammed


    This paper compares the alkali-activated fly ash (AAFA) manufactured with thermal oven curing and pulsed microwave curing methods. Fly ash activated by 8M NaOH solution at a liquid to solid ratio of 0.3 was cured by thermal oven at 85°C and domestic microwave oven, respectively. Apart from compressive strength test, the temperature profiles of AAFA samples were captured by thermal camera. Reaction products of AAFA were characterised with XRD, FTIR and TG/DTG, while the microstructure of AAFA ...

  20. Syntheses and Structures of Alkali Metal Rare Earth Polyphosphates CsLn(PO3)4 (Ln = La, Ce)

    Institute of Scientific and Technical Information of China (English)

    ZHU Jing; CHENG Wen-Dan; ZHANG Hao; WU Dong-Sheng; ZHAO Dan


    Alkali metal-rare earth polyphosphates, CsLn(PO3)4 (Ln = La, Ce), were synthesized by the high temperature solution reaction and studied by single-crystal X-ray diffraction technique. They crystallize in the monoclinic space group P21 (Z = 2) and feature infinite PO4 spiral chains linked with neighboring CsO10 and LnO8 polyhedra. In addition, theoretically calculated energy band structure and density of states (DOS) by the density functional theory(DFT) predict that the solid-state compound CsLa(PO3)4 possesses insulative character.

  1. Mechanistic and kinetic analysis of the oxidative dehydrogenation of ethane via novel supported alkali chloride catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gaertner, C.; Veen, A.C. van; Lercher, J.A. [Technische Universitaet Muenchen (Germany). Catalysis Research Center


    The oxidative dehydrogenation of ethane over advanced catalysts is promising to selectively produce ethylene, an essential building block for the chemical industry. In this way, ethane from shale gas can be efficiently valorized. Supported alkali chloride catalysts are investigated in this work. Essential feature of those materials is the presence of a solid core (magnesium oxide in part doped with Dy{sub 2}O{sub 3}) covered under reaction conditions with a molten alkali chloride shell. It is shown that especially the lowered melting point of eutectic mixtures of LiCl with other alkali/alkaline earth metals is the key to taylor highly efficient materials. Elucidating the ODH reaction mechanism is essential to understand the reactivity of this novel catalyst class and provides the basis for improving performances. Information about elementary steps and the rate determining step were extracted from kinetic measurements, both in steady state and in transient configuration. Furthermore, isotopic labelling studies were performed, i.e. SSITKA studies and temperature programmed isotopic exchange experiments. Step experiments showed a significant oxygen uptake by the catalysts. Retained oxygen reacted quantitatively with ethane at nearly 100% selectivity to ethylene and conversion rates were comparable with rates observed during steady state operation. Thus, chemically bound oxygen in the melt is the active and selective intermediate in the ODH. Therefore, it is required to consider an intermediate and the activation is concluded to relate to the oxygen dissociation. The total concentration of stored oxygen can be correlated to the steady-state activity, while the viscosity of the melts mainly influences the selectivity towards ethene. Properties of the solid core impact on the catalyst efficiency suggesting that the oxygen species forms at the interface between support and overlayer. The quantity of retained oxygen additionally depends on the properties of the chloride

  2. Microstructural changes induced by CO2 exposure in alkali-activated slag/metakaolin pastes (United States)

    Bernal, Susan


    The structural changes induced by accelerated carbonation in alkali-activated slag/ metakaolin (MK) cements were determined. The specimens were carbonated for 540 h in an environmental chamber with a CO2 concentration of 1.0 ± 0.2%, a temperature of 20 ± 2ºC, and relative humidity of 65 ± 5 %. Accelerated carbonation led to decalcification of the main binding phase of these cements, which is an aluminium substituted calcium silicate hydrate (C-(N-)A-S-H) type gel, and the consequent formation of calcium carbonate. The sodium-rich carbonates trona (Na2CO3·NaHCO3·2H2O) and gaylussite (Na2Ca(CO3)2·5H2O) were identified in cements containing up to 10 wt.% MK as carbonation products. The formation of these carbonates is mainly associated with the chemical reaction between the CO2 and the free alkalis present in the pore solution. The structure of the carbonated cements is dominated by an aluminosilicate hydrate (N-A-S-H) type gel, independent of the MK content. The N-A-S-H type gels identified are likely to be derived both from the activation reaction of the MK, forming a low-calcium gel product which does not seem to undergo structural changes upon CO2 exposure, and the decalcification of C-(N-)A-S-H type gel. The carbonated pastes present a highly porous microstructure, more notable as the content of MK content in the cement increases, which might have a negative impact on the durability of these materials in service.

  3. Nanoengineering of methylene blue loaded silica encapsulated magnetite nanospheres and nanocapsules for photodynamic therapy

    Energy Technology Data Exchange (ETDEWEB)

    Andhariya, Nidhi [Bhavnagar University, Department of Physics (India); Chudasama, Bhupendra, E-mail: [Thapar University, School of Physics and Materials Science (India); Mehta, R. V. [Bhavnagar University, Department of Physics (India); Upadhyay, R. V. [Charotar University of Science and Technology, P.D. Patel Institute of Applied Sciences (India)


    Core-shell nanostructures have emerged as an important class of functional materials with potential applications in diverse fields, especially in health sciences. In this article, nanoengineering of novel magnetic colloidal dispersion containing surface modifiable silica with a core of single domain magnetite nanoparticles loaded with photosensitizer (PS) drug 'Methylene blue' (MB) has been described. Magnetite core is produced by the well-established chemical coprecipitation technique and silica shell is formed over it by the modified hydrolysis and condensation of TEOS (tetraethyl orthosilicate). Conditions for reaction kinetics have been established to tailor the core-shell structures in the form of nanospheres and nanocapsules. MB is loaded into the nanostructures by demethylation reaction. The major conclusion drawn from this study is that the synthesis route yields stable, non-aggregated MB loaded superparamagnetic magnetite-silica nanostructures with tailored morphology, tunable loading, and excellent magnetic properties.

  4. Direct esterification of olive-pomace oil using mesoporous silica supported sulfonic acids

    Directory of Open Access Journals (Sweden)

    F. Alrouh


    Full Text Available Mesoporous silica MCM-41 and SBA-15 containing propyl sulfonic acid groups were synthesized according to the literature and were characterized by X-ray diffraction, N2 adsorption and the H+ exchange capacities of the sulfonic acid groups were titrated. The esterification reaction of glycerol with olive-pomace oil has been carried out by using prepared functionalized mesoporous silica (MCM-41 and SBA-15 as catalysts. It has been monitored by GC two fatty acids (palmitic and oleic acids as reactants in olive-pomace oil and their related monoacylglycerols (Glycerol monopalmitate GMP and monooleate GMO as reaction product. The catalytic activities of the functionalized mesoporous silica were compared with commercial catalysts, these included homogeneous catalysts (p-toluenesulfonic acid and heterogeneous catalysts (Amberlyst-15. The total yield of monoacylglycerols (GMO + GMP was nearly 40%. Remarkably, we found that MCM-41-SO3H was recycled at least 3 times without any loss of activity.

  5. A facile route to prepare hierarchical magnetic cobalt-silica hollow nanospheres with tunable shell thickness

    Energy Technology Data Exchange (ETDEWEB)

    Wang Jun, E-mail:; Xu Chuanhui; Yao Min; Chen Jie [NingBo University, Faculty of Science (China); Xu Gaojie [Ningbo Institute of Material Technology and Engineering (China)


    Magnetic nanoshells composed of close-packed cobalt-silica nanoparticles have been successfully fabricated on silica spheres. The synthesis is facile and no high pressure, high temperature, or other severe reaction conditions were required. TEM images showed that two batches of the hollow-structured products have a good spherical morphology with an average diameter of 380 and 550 nm, respectively. The surface area and magnetic properties of cobalt-silica nanoshells are measured. By varying the times of the precipitation procedure, the shell thickness is successfully controlled within the 5-30 nm range and each time of procedure might increase the thickness about 5 nm. It is expected that the in situ reaction method can be extended to the synthesis of other hollow metal spheres. The prepared microcapsule with controllable shell thickness and interspaces has the potential to be used for controlled release applications.

  6. Cascade enzymatic catalysis in poly(acrylic acid) brushes-nanospherical silica for glucose detection. (United States)

    Zhao, Yan; Wang, Ying; Zhang, Xiaobin; Kong, Rongmei; Xia, Lian; Qu, Fengli


    The ultrasensitive monitoring of glucose with a fast and accurate method is significant in potential therapeutics and optimizes protein biosynthesis. Incorporation of enzyme into matrix is considered as promising candidates for constructing highly sensitive glucose-responsive systems. In this study, three-dimensional poly(acrylic acid) brushes-nanospherical silica (PAA-nano silica) with high amplification capability and stability were used to covalently immobilize bienzymes for cascade enzymatic catalysis. The major advantages of PAA-nano silica-bienzyme co-incorporation is that the enzymes are proximity distribution, and such close confinement both minimized the diffusion of intermediates among the enzymes in the consecutive reaction and improve the utilization efficiency of enzymes, thereby enhancing the overall reaction efficiency and specificity. Thus, this present bienzymatic biosensor shows robust signal amplification and ultrasensitivity of glucose-responsive properties with a detection limit of 0.04μM.

  7. Kinetics of alkali-based photocathode degradation (United States)

    Pavlenko, Vitaly; Liu, Fangze; Hoffbauer, Mark A.; Moody, Nathan A.; Batista, Enrique R.


    We report on a kinetic model that describes the degradation of the quantum efficiency (QE) of Cs3Sb and negative electron affinity (NEA) GaAs photocathodes under UHV conditions. In addition to the generally accepted irreversible chemical change of a photocathode's surface due to reactions with residual gases, such as O2, CO2, and H2O, the model incorporates an intermediate reversible physisorption step, similar to Langmuir adsorption. This intermediate step is needed to satisfactorily describe the strongly non-exponential QE degradation curves for two distinctly different classes of photocathodes -surface-activated and "bulk," indicating that in both systems the QE degradation results from surface damage. The recovery of the QE upon improvement of vacuum conditions is also accurately predicted by this model with three parameters (rates of gas adsorption, desorption, and irreversible chemical reaction with the surface) comprising metrics to better characterize the lifetime of the cathodes, instead of time-pressure exposure expressed in Langmuir units.

  8. Kinetics of alkali-based photocathode degradation

    Directory of Open Access Journals (Sweden)

    Vitaly Pavlenko


    Full Text Available We report on a kinetic model that describes the degradation of the quantum efficiency (QE of Cs3Sb and negative electron affinity (NEA GaAs photocathodes under UHV conditions. In addition to the generally accepted irreversible chemical change of a photocathode’s surface due to reactions with residual gases, such as O2, CO2, and H2O, the model incorporates an intermediate reversible physisorption step, similar to Langmuir adsorption. This intermediate step is needed to satisfactorily describe the strongly non-exponential QE degradation curves for two distinctly different classes of photocathodes –surface-activated and “bulk,” indicating that in both systems the QE degradation results from surface damage. The recovery of the QE upon improvement of vacuum conditions is also accurately predicted by this model with three parameters (rates of gas adsorption, desorption, and irreversible chemical reaction with the surface comprising metrics to better characterize the lifetime of the cathodes, instead of time-pressure exposure expressed in Langmuir units.

  9. Contribution a la caracterisation des betons endommages par des methodes de l'acoustique non lineaire. Application a la reaction alcalis-silice (United States)

    Kodjo, Apedovi

    The aim of this thesis is to contribute to the non-destructive characterization of concrete materials damaged by alkali-silica reaction (ASR). For this purpose, some nonlinear characterization techniques have been developed, as well as a nonlinear resonance test device. In order to optimize the sensitivity of the test device, the excitation module and signal processing have been improved. The nonlinear tests were conducted on seven samples of concrete damaged by ASR, three samples of concrete damaged by heat, three concrete samples damaged mechanically and three sound concrete samples. Since, nonlinear behaviour of the material is often attribute to its micro-defects hysteretic behaviour, it was shown at first that concrete damaged by ASR exhibits an hysteresis behaviour. To conduct this study, an acoustoelastic test was set, and then nonlinear resonance test device was used for characterizing sound concrete and concrete damaged by ASR. It was shown that the nonlinear technique can be used for characterizing the material without knowing its initial state, and also for detecting early damage in the reactive material. Studies were also carried out on the effect of moisture regarding the nonlinear parameters; they allowed understanding the low values of nonlinear parameters measured on concrete samples that were kept in high moisture conditions. In order to find a specific characteristic of damage caused by ASR, the viscosity of ASR gel was used. An approach, based on static creep analysis, performed on the material, while applying the nonlinear resonance technique. The spring-damping model of Maxwell was used for the interpretation of the results. Then, the creep time was analysed on samples damaged by ASR. It appears that the ASR gel increases the creep time. Finally, the limitations of the nonlinear resonance technique for in situ application have been explained and a new applicable nonlinear technique was initiated. This technique use an external source such as a

  10. Synthesis of highly fluorescent silica nanoparticles in a reverse microemulsion through double-layered doping of organic fluorophores

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Hyojong, E-mail:; Pak, Joonsung [Hallym University, Department of Chemistry (Korea, Republic of)


    Water-soluble, highly fluorescent double-layered silica nanoparticles (FL-DLSN) have been successfully synthesized through a reverse (water-in-oil) microemulsion method. The microemulsion was prepared by mixing a surfactant (Brij35), co-surfactant, organic solvent, water, and fluorescein as an organic fluorophore. The sizes of the silica nanoparticles were successfully controlled in the reverse microemulsion using Brij35 by changing the water-to-Brij35 ratio and by adding HCl. Initially, tetraethylorthosilicate was hydrolyzed by adding NH{sub 4}OH as a catalyst and then polymerized to generate core fluorescent silica nanoparticles with fluorescein. 3-(Aminopropyl)triethoxysilane (APTS) was sequentially added into the reaction mixture, and reacted on the surface of pre-generated core silica nanoparticles to form the second layer in the form of a shell. The second silica layer that was derived from the condensation of APTS effectively protected the fluorescein dye within the silica matrix. This is a novel and simple synthetic approach to generate highly fluorescent, monodispersed silica nanoparticles by doping organic molecules into a silica matrix.Graphical Abstract.

  11. Cloning of a Vacuolar H+-pyrophosphatase Gene from the Halophyte Suaeda corniculata whose Heterologous Overexpression Improves Salt,Saline-alkali and Drought Tolerance in Arabidopsis

    Institute of Scientific and Technical Information of China (English)

    Liang Liu; Ying Wang; Nan Wana; Yuan-Yuan Dong; Xiu-Duo Fan; Xiu-Ming Liu; Jing Yang


    Salt,saline-alkali conditions,and drought are major environmental factors limiting plant growth and productivity.The vacuolar H+-translocating inorganic pyrophosphatase (V-H+-PPase) is an electrogenic proton pump that translocates protons into vacuoles in plant cells.Expression of V-H+-PPase increases in plants under a number of abiotic stresses,and is thought to have an important role in adaptation to abiotic stress.In this work,we report the isolation and characterization of the gene,ScVP,encoding a vacuolar inorganic pyrophosphatase (V-H+-PPase) from the halophyte,Suaeda corniculata.Semiquantitative reverse transcription-polymerase chain reaction analysis showed that ScVP was induced in roots,stems and leaves under treatment with salt,saline-alkali and drought.Compared with wild-type (WT) Arabidopsis,transgenic plants overexpressing ScVP accumulated more Na+ in leaves and roots,and showed increased tolerance to high salinity,saline-alkali and drought stresses.The germination percentage of transgenic Arabidopsis seeds was higher than that of WT seeds under the abiotic stresses.The root length of transgenic plants under salt stress was longer than that of WT plants.Furthermore,the rate of water loss during drought stress was higher in WT than in transgenic plants.Collectively,these results indicate that ScVP plays an important role in plant tolerance to salt,saline-alkali and drought stress.

  12. Silica-supported ionic liquid as highly efficient catalyst for one-pot synthesis of acenaphtho[1,2-]furan compounds

    Indian Academy of Sciences (India)

    Reza Sandaroos; Mohammad Taghi Goldani; Saman Damavandi


    Some new derivatives of acenaphtho[1,2-]furan have been synthesized efficiently by one-pot reaction of (acenaphthylen-1-yloxy)trimethylsilane, various aldehydes and isocyanides at the presence of silica-supported ionic liquid.

  13. Mesoporous Silica: A Suitable Adsorbent for Amines

    Directory of Open Access Journals (Sweden)

    Abdollahzadeh-Ghom Sara


    Full Text Available Abstract Mesoporous silica with KIT-6 structure was investigated as a preconcentrating material in chromatographic systems for ammonia and trimethylamine. Its adsorption capacity was compared to that of existing commercial materials, showing its increased adsorption power. In addition, KIT-6 mesoporous silica efficiently adsorbs both gases, while none of the employed commercial adsorbents did. This means that KIT-6 Mesoporous silica may be a good choice for integrated chromatography/gas sensing micro-devices.

  14. Synthesis of naphthoxazinone derivatives using silica-bonded -sulfonic acid as catalyst under solvent-free conditions

    Indian Academy of Sciences (India)

    Khodabakhsh Niknam; Parisa Abolpour


    Silica-bonded -sulfonic acid is employed as a recyclable catalyst for the synthesis of naphthoxazinone derivatives from the reaction of -naphthol, aromatic aldehydes and urea at 150°C under solvent-free conditions. The heterogeneous catalyst was recycled for five runs after the reaction of -naphthol, benzaldehyde and urea without losing its catalytic activity.

  15. Alumina and Silica Oxides as Catalysts for the Oxidation of Benzoins to Benzils under Solvent-free Conditions

    Directory of Open Access Journals (Sweden)

    A. H. Dabbagh


    Full Text Available Alumina or silica gel are used as catalysts for a solvent-free oxidation of benzoins to the corresponding benzils. These catalysts are easily recovered after completion of the reactions, which are carried out either by heating in a sand bath or using microwave irradiation. Comparison of the results obtained with both catalysts indicates that all the reactants examined were oxidized faster on alumina than on silica under these conditions.

  16. Fabrication of Ultrafine Carbon Fibers Possessing a Nanoporous Structure from Electrospun Polyvinyl Alcohol Fibers Containing Silica Nanoparticles



    Ultrafine carbon fibers with a nanoporous structure were fabricated by the template method using silica nanoparticles (NPs) embedded in fibers of approximate diameter 500 nm, electrospun from an aqueous solution of polyvinyl alcohol, CoCl2, silica NPs, and N,N-dimethylformamide. Black, conductive fibers were obtained by heat treatment in air and a chemical vapor deposition reaction under methanol vapor for more than 5 h. Transmission electron microscopy (TEM) demonstrated that the fabricated ...

  17. Partial alkali-metal ion extraction from K0.8(Li0.27Ti1.73)O4 using PTFE as an extraction reagent. (United States)

    Ozawa, Tadashi C; Sasaki, Takayoshi


    The alkali-metal ion extraction ability of an inert material, polytetrafluoroethylene (PTFE; empirical formula CF2), was clarified by characterizing a partially alkali-metal ion-extracted layered compound, K0.8(Li0.27Ti1.73)O4. Washing K0.8(Li0.27Ti1.73)O4 in water extracts only 44% of the interlayer K(+) and no intralayer Li(+); on the other hand, 53% of the interlayer K(+) and approximately 10% of the intralayer Li(+) ions were extracted from K0.8(Li0.27Ti1.73)O4 by the reaction with PTFE at 350 °C under flowing Ar. A systematic decrease in the lattice parameters a and c along the intralayer directions and an increase in b along the interlayer direction were observed, consistent with the alkali-metal ion deintercalation amount as a function of the reaction temperatures and the reacted PTFE amounts. After the reaction with K0.8(Li0.27Ti1.73)O4 : CF2 = 1 : 0.6 in mol, the lattice parameter b increased to 1.5607(3) nm from 1.5522(2) of the pristine K0.8(Li0.27Ti1.73)O4, and this change in the lattice parameter was approximately one order of magnitude larger than those in a and c.

  18. Process for carbonaceous material conversion and recovery of alkali metal catalyst constituents held by ion exchange sites in conversion residue (United States)

    Sharp, David W.


    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered for the particles by contacting or washing them with an aqueous solution containing calcium or magnesium ions in an alkali metal recovery zone at a low temperature, preferably below about F. During the washing or leaching process, the calcium or magnesium ions displace alkali metal ions held by ion exchange sites in the particles thereby liberating the ions and producing an aqueous effluent containing alkali metal constituents. The aqueous effluent from the alkali metal recovery zone is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  19. Nanoporous silica membranes with high hydrothermal stability

    DEFF Research Database (Denmark)

    Boffa, Vittorio; Magnacca, Giualiana; Yue, Yuanzheng

    Despite the use of sol-gel derived nanoporous silica membranes in substitution of traditional separation processes is expected leading to vast energy savings, their intrinsic poor steam-stability hampers their application at an industrial level. Transition metal ions can be used as dopant...... to improve the stability of nanoporous silica structure. This work is a quantitative study on the impact of type and concentration of transition metal ions on the microporous structure and stability of amorphous silica-based membranes, which provides information on how to design chemical compositions...... and synthetic paths for the fabrication of silica-based membranes with a well accessible and highly stabile nanoporous structure...

  20. Practical Hydrogen Loading of Air Silica Fibres

    DEFF Research Database (Denmark)

    Sørensen, Henrik Rokkjær; Jensen, Jesper Bevensee; Jensen, Jesper Bo Damm;


    A method for hydrogen-loading air-silica optical fibres has been developed allowing out-diffusion times comparable to standard step-index fibres. Examples of the first grating written in Ge-doped air-silica fibres using a 266nm UV-laser are shown.......A method for hydrogen-loading air-silica optical fibres has been developed allowing out-diffusion times comparable to standard step-index fibres. Examples of the first grating written in Ge-doped air-silica fibres using a 266nm UV-laser are shown....

  1. Cellular membrane trafficking of mesoporous silica nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Fang, I-Ju [Iowa State Univ., Ames, IA (United States)


    This dissertation mainly focuses on the investigation of the cellular membrane trafficking of mesoporous silica nanoparticles. We are interested in the study of endocytosis and exocytosis behaviors of mesoporous silica nanoparticles with desired surface functionality. The relationship between mesoporous silica nanoparticles and membrane trafficking of cells, either cancerous cells or normal cells was examined. Since mesoporous silica nanoparticles were applied in many drug delivery cases, the endocytotic efficiency of mesoporous silica nanoparticles needs to be investigated in more details in order to design the cellular drug delivery system in the controlled way. It is well known that cells can engulf some molecules outside of the cells through a receptor-ligand associated endocytosis. We are interested to determine if those biomolecules binding to cell surface receptors can be utilized on mesoporous silica nanoparticle materials to improve the uptake efficiency or govern the mechanism of endocytosis of mesoporous silica nanoparticles. Arginine-glycine-aspartate (RGD) is a small peptide recognized by cell integrin receptors and it was reported that avidin internalization was highly promoted by tumor lectin. Both RGD and avidin were linked to the surface of mesoporous silica nanoparticle materials to investigate the effect of receptor-associated biomolecule on cellular endocytosis efficiency. The effect of ligand types, ligand conformation and ligand density were discussed in Chapter 2 and 3. Furthermore, the exocytosis of mesoporous silica nanoparticles is very attractive for biological applications. The cellular protein sequestration study of mesoporous silica nanoparticles was examined for further information of the intracellular pathway of endocytosed mesoporous silica nanoparticle materials. The surface functionality of mesoporous silica nanoparticle materials demonstrated selectivity among the materials and cancer and normal cell lines. We aimed to determine

  2. Silica deactivation of bead VOC catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Libanati, C.; Pereira, C.J. [Research Division, W. R. Grace and Co., Columbia, MD (United States); Ullenius, D.A. [Grace TEC Systems, De Pere, WI (United States)


    Catalytic oxidation is a key technology for controlling the emissions of Volatile Organic Compounds (VOCs) from industrial plants. The present paper examines the deactivation by silica of bead VOC catalysts in a flexographic printing application. Post mortem analyses of field-aged catalysts suggest that organosilicon compounds contained in the printing ink diffuse into the catalyst and deposit as silica particles in the micropores. Laboratory activity evaluation of aged catalysts suggests that silica deposition is non-selective and that silica masks the noble metal active site

  3. Effects of Al on mineralogy and kinetics of precipitation of silica minerals under crustal conditions (United States)

    Saishu, H.; Okamoto, A.; Tsuchiya, N.


    Silica is a dominant component in the Earth's crust. Dissolution and precipitation processes of silica minerals play significant roles on the spatial and temporal distributions of fluids and rock strength in the crusts. Quartz veins occur ubiquitously in the vicinity of seismogenic zones. However the rate equation of silica precipitation is important to consider the sealing of fractures by quartz on the earthquake cycle, it has not been determined except for precipitation rates on surface reactions (Rimstidt and Barnes, 1980) because of the following reasons: cristobalite and amorphous silica occur in the geothermal areas (Alekseyev et al., 2009) whereas quartz is stable in the crust, precipitation of silica minerals occurs not only on quartz surfaces but also via nucleation processes in fluids, and trace elements including Al, Na and K in solutions affect on the species and kinetics of silica precipitation (Okamoto et al., 2010). In the crust, feldspars are dominant constituents, thus the effects of these minor components are crucial for considering the silica precipitation. We conducted the hydrothermal flow-through experiments to investigate the overall precipitation rate of silica minerals and the effects of Al in the solutions under crustal conditions (430 °C and 31 MPa). The experimental apparatus is similar to that in Okamoto et al. (2010). A blank vessel without any rock/mineral substrates was used for precipitation of silica minerals. The Si-supersaturated solutions (C/Ceq = 3-3.5) were prepared by dissolution of quartz at 350 °C, and the concentration of Al in the input solution was controlled from 0 to 7 ppm by dissolution of albite with different temperatures. The experiments in pure Si solution revealed that the precipitation via nucleation in fluids was approximated as the third-order reaction whereas the precipitation on the pre-existing quartz surfaces was determined as the first-order reaction in Rimstidt and Barnes (1980). Activation energy of

  4. Characterization and Curing Kinetics of Epoxy/Silica Nano-Hybrids

    Directory of Open Access Journals (Sweden)

    Cheng-Fu Yang


    Full Text Available The sol-gel technique was used to prepare epoxy/silica nano-hybrids. The thermal characteristics, curing kinetics and structure of epoxy/silica nano-hybrids were studied using differential scanning calorimetry (DSC, 29Si nuclear magnetic resonance (NMR and transmission electron microscopy (TEM. To improve the compatibility between the organic and inorganic phases, a coupling agent was used to modify the diglycidyl ether of bisphenol A (DGEBA epoxy. The sol-gel technique enables the silica to be successfully incorporated into the network of the hybrids, increasing the thermal stability and improving the mechanical properties of the prepared epoxy/silica nano-hybrids. An autocatalytic mechanism of the epoxy/SiO2 nanocomposites was observed. The low reaction rate of epoxy in the nanocomposites is caused by the steric hindrance in the network of hybrids that arises from the consuming of epoxide group in the network of hybrids by the silica. In the nanocomposites, the nano-scale silica particles had an average size of approximately 35 nm, and the particles were well dispersed in the epoxy matrix, according to the TEM images.

  5. Facile and Controlled Synthesis of Silica Sol Nanospheres Through a Modified Sol-Gel Process

    Institute of Scientific and Technical Information of China (English)

    LI Jie; CHEN Lianxi; ZHANG Zhongming; JIAO Caibin


    An effective and reproducible preparation of silica sol nanospheres via a modified sol-gel process has been described. Monodisperse and stable silica sol nanospheres with uniformsize were successfully obtained through the optimized synthesis in which the mixture of tetraethyl orthosilicate (TEOS) and ethanol was followed by the addition of water and ammonium hydroxide (NH3) separately, and the size of silica sol spheres was strictly controlled in the range of 25-119 nm with a narrow size distribution by fine adjustment of several reaction parameters. Results showed that in the presence of low concentration of TEOS, spheres size rose first and reached maximum when H2O concentration was up to 66 g/L. However, the diameter of silica sol spheres decreased above 66 g/L of H2O concentration. Furthermore, it was also found that the size and size distribution of silica sol nanospheres were affected by NH3 concentration. As NH3 concentration increased from 15 to 35 g/L, the diameter declined from 83 to 64 nm. Nevertheless, higher NH3 concentration would result in relatively broad size distribution, and gelation occurred when NH3 concentration reached 44 g/L. In addition, the effect of the different feed rates of NH3 on the size growth of silica sol nanospheres was also discussed.

  6. Preparation of the methylene blue silica compound microcapsule; Mechirenburushirika fukugo maikuro kapuseru no chosei

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Koji [Yamagata University, Yamagata (Japan); Ono, Hideo


    By using methylene blue aqueous solution of the cationy for the dispersed phase of the W/0 emulsion, and using this for hydrolysis of TEOS and reaction field of the degeneracy conjunction, force - methylene blue compound microcapsule of 4.0 {mu}m mean particle sizes was prepared. When the water was supplied, though there was elution behavior of the methylene blue from this microcapsule in the condition that the methylene blue was fixed in the silica microcapsule without completely dissolving, the elution amount of methylene blue increased eluate isoelectric point silica, and the pH dependence was shown. Therefore, a part of methylene blue in dispersed phase combines with the silica in Coulomb force like during hydrolysis and degeneracy conjunction of TEOS, and it is fixed in the silica microcapsule resistant, and by the consistency of pH of the eluate, it is meanwhile regarded out for acidic as a dissolution of the methylene blue of the isoelectric point of the silica from the silica microcapsule. (translated by NEDO)

  7. Compositional Convection-Driven Differentiation in the Skaergaard Intrusion: A Reaction- Transport Model (United States)

    Sonnenthal, E.; McBirney, A.


    Considerable debate has focused on the role of thermal versus compositional convection and late-stage melt and volatile migration in the differentiation of layered intrusions, including the Skaergaard Intrusion. The result of these coupled processes is a hierarchy of structures from textural re-equilibration, to mm-scale rhythmic layering, to large-scale mobilization and recrystallization involving melt and volatiles. In the Skaergaard Intrusion, there is evidence that the base of the intrusion crystallized from melts strongly enriched in iron, presumably derived from the walls and/or roof. To investigate the scenario that iron-rich melts migrated from or through the crystallizing walls and ponded on the floor, we developed a two-dimensional reaction-transport model having the projected cross-section of the intrusion. Simulations of coupled flow and reaction of melt, heat, and minerals were performed using the RCTMAG code developed by the authors. Processes include conservation of fluid mass, energy, advective and diffusive multicomponent transport, and crystallization/melting. Crystal-melt equilibria and compositions are treated using distribution coefficients based on literature values or derived from lab and/or field data. Permeability and porosity changes are coupled to crystallization and melting, with the resulting volume changes affecting flow. Simulations show that iron-rich melt develops within the sidewall mush and tends to migrate through the mush toward the base. Compositional convection dominates over thermal convection because heat loss through the walls and roof lead to crystallization and melt compositional changes, affecting density more than temperature. Chemical and thermal diffusion within the mush has subtle effects on mineral compositions and modes, primarily because water and alkalis diffuse faster than other components. The propensity for melt to migrate through the mush is clearly aided by the increase in iron and volatiles, counteracting

  8. A Highly Active and Selective Manganese Oxide Promoted Cobalt-on-Silica Fischer-Tropsch Catalyst

    NARCIS (Netherlands)

    den Breejen, Johan P.; Frey, Anne M.; Yang, Jia; Holmen, Anders; van Schooneveld, Matti M.; de Groot, Frank M. F.; Stephan, Odile; Bitter, Johannes H.; de Jong, Krijn P.


    A highly active and selective manganese oxide-promoted silica-supported cobalt catalyst for the Fischer-Tropsch reaction is reported. Co/MnO/SiO2 catalysts were prepared via impregnation of a cobalt nitrate and manganese nitrate precursor, followed by drying and calcination in an NO/He flow. The cat

  9. Porous structure and particle size of silica and hydrotalcite catalyst precursors

    NARCIS (Netherlands)

    Titulaer, M.K.


    The subject of this thesis is the control of the porous structure of catalyst bodies. The first part deals with silica, that can be utilized as catalyst support with many industrially important catalytic reactions. The second part of the thesis deals with the preparation and characterization of soli

  10. Rapid pathogen detection with bacterial-assembled magnetic mesoporous silica. (United States)

    Lee, Soo Youn; Lee, Jiho; Lee, Hye Sun; Chang, Jeong Ho


    We report rapid and accurate pathogen detection by coupling with high efficiency magnetic separation of pathogen by Ni(2+)-heterogeneous magnetic mesoporous silica (Ni-HMMS) and real time-polymerase chain reaction (RT-PCR) technique. Ni-HMMS was developed with a significant incorporation of Fe particles within the silica mesopores by programmed thermal hydrogen reaction and functionalized with Ni(2+) ion on the surface by the wet impregnation process. High abundant Ni(2+) ions on the Ni-HMMS surface were able to assemble with cell wall component protein NikA (nickel-binding membrane protein), which contains several pathogenic bacteria including Escherichia coli O157:H7. NikA protein expression experiment showed the outstanding separation rate of the nikA gene-overexpressed E. coli (pSY-Nik) when comparing with wild-type E. coli (44.5 ± 13%) or not over-expressed E. coli (pSY-Nik) (53.2 ± 2.7%). Moreover, Ni-HMMS showed lower obstacle effect by large reaction volume (10 mL) than spherical core/shell-type silica magnetic nanoparticles functionalized with Ni(2+) (ca. 40 nm-diameters). Finally, the Ni-HMMS was successfully assessed to separate pathogenic E. coli O157:H7 and applied to direct and rapid RT-PCR to quantitative detection at ultralow concentration (1 Log10 cfu mL(-1)) in the real samples (milk and Staphylococcus aureus culture broth) without bacterial amplification and DNA extraction step.

  11. Morphological Control of Multifunctional Mesoporous Silica Nanomaterials for Catalysis Applications

    Energy Technology Data Exchange (ETDEWEB)

    Huh, Seong [Iowa State Univ., Ames, IA (United States)


    I found an efficient method to control the morphology of the organically monofunctionalized mesoporous silica materials by introducing different types of organoalkoxysilanes in a base-catalyzed co-condensation reaction. The monofunctionalized materials exhibit different particle morphologies relative to the pure MCM-41 material. The concentration dependence of the morphology is a critical factor to determine the final particle shape. A proposed mechanism of the shape evolution is also offered. After understanding the role of organoalkoxysilanes in producing various well-shaped nanomaterials, I also obtained a series of bifunctional mesoporous silica materials with certain particle morphology. A series of bifunctional mesoporous silica nanospheres (MSNs) whose physicochemical properties was investigated via solid state NMR techniques and Cu2+ adsorption capacity tests, The ratio of two different organic groups inside of mesopores of these MSNs could be fine-tuned. These MSNs serve as a useful model system to study substrate selectivity in catalytic reactions and sorption phenomena. For example, the Cu2+ adsorption capacity of these materials was dictated by the chemical nature of the mesopores generated by the different organic functional groups. An investigation of the substrate selectivity of the bifunctionalized MSNs in a competitive nitroaldol reaction using an equimolar amount of two competing 4-nitrobenzaldehyde derivatives was performed. Shape-controlled bifunctional MSNs were employed as the catalysts. The properties of the MSNs were investigated using various spectroscopic methods and electron microscopy. The more hydrophobic the surface organic groups are, the higher the ratio of hydrophobic final product. This is the first example to demonstrate the selection of substrate using physicochemical nature of the mesopore surface other than the conventional shape selection in zeolite systems. I also created a cooperative dual catalyst

  12. Synthesis of silicon carbide by carbothermal reduction of silica

    Energy Technology Data Exchange (ETDEWEB)

    Abel, J.L.; Ambrozio, F.; Beneduce, F. [Centro Universitario FEI, Itajuba, MG (Brazil); Instituto de Pesquisas Tecnologicas (IPT), Sao Paulo, SP (Brazil)


    Full text: The production of silicon carbide (SiC) in an industrial scale still by carbothermal reduction of silica for its synthesis. This study aims to identify, in a comparative way, among the common reducers like petroleum coke, carbon black, charcoal and graphite the carbothermal reduction of silica from peat or organic soil. It is shown that peat, also occurs in nature together with high purity silica sand deposits, where the proximity of raw materials and their quality are key elements that determine the type, purity and cost of production of SiC. Tests were running from samples produced in the electric resistance furnace with controlled atmosphere at temperatures of 1550 deg C, 1600°C and 1650°C, both the precursors and products of reaction of carbothermal reduction were characterized by applying techniques of X-ray diffraction, scanning electron microscopy (SEM) and Energy- Dispersive X-ray analysis Spectroscopy (EDS). The results showed the formation of SiC for all common reducers, as well as for peat, but it was not possible to realize clearly the difference between them, being necessary, specific tests. (author)

  13. Acetylcholinesterase immobilized onto PEI-coated silica nanoparticles. (United States)

    Tumturk, Hayrettin; Yüksekdag, Hazer


    Polyethyleneimine (PEI) coated-silica nanoparticles were prepared by the Stöber method. The formation and the structure of the nanoparticles were characterized by ATR-FT-IR spectroscopy and transmission electron microscopy (TEM). TEM images of the silica and PEI-coated nanoparticles revealed that they were well dispersed and that there was no agglomeration. The acetylcholineesterase enzyme was immobilized onto these nanoparticles. The effects of pH and temperature on the storage stability of the free and immobilized enzyme were investigated. The optimum pHs for free and immobilized enzymes were determined as 7.0 and 8.0, respectively. The optimum temperatures for free and immobilized enzymes were found to be 30.0 and 35.0°C, respectively. The maximum reaction rate (Vmax) and the Michaelis-Menten constant (Km) were investigated for the free and immobilized enzyme. The storage stability of acetylcholinesterase was increased when immobilized onto the novel PEI-coated silica nanoparticles. The reuse numbers of immobilized enzyme were also studied. These hybrid nanoparticles are desirable as carriers for biomedical applications.

  14. Generation and characterization of alkali metal clusters in Y-FAU zeolites. An ESR and MAS NMR spectroscopic study (United States)

    Hannus, István; Béres, Attila; Nagy, János B.; Halász, János; Kiricsi, Imre


    Charged and neutral metal clusters of various compositions and sizes can be prepared by controlling the alkali metal content by the decomposition of alkali azides and the composition of the host zeolite by ion-exchange. ESR signals show that electron transfer from alkali metal atoms to alkali metal cations does occur, but in a direction opposite to that predicted by the gas-phase thermochemistry. Alkali metal clusters proved to be very active basic catalytic centers.

  15. Coagulated silica - a-SiO2 admixture in cement paste (United States)

    Pokorný, Jaroslav; Pavlíková, Milena; Záleská, Martina; Rovnaníková, Pavla; Pavlík, Zbyšek


    Amorphous silica (a-SiO2) in fine-grained form possesses a high pozzolanic activity which makes it a valuable component of blended binders in concrete production. The origin of a-SiO2 applied in cement-based composites is very diverse. SiO2 in amorphous form is present in various amounts in quite a few supplementary cementing materials (SCMs) being used as partial replacement of Portland cement. In this work, the applicability of a commercially produced coagulated silica powder as a partial replacement of Portland cement in cement paste mix design is investigated. Portland cement CEM I 42.5R produced according to the EU standard EN 197-1 is used as a reference binder. Coagulated silica is applied in dosages of 5 and 10 % by mass of cement. The water/binder ratio is kept constant in all the studied pastes. For the applied silica, specific surface area, density, loss on ignition, pozzolanic activity, chemical composition, and SiO2 amorphous phase content are determined. For the developed pastes on the basis of cement-silica blended binder, basic physical properties as bulk density, matrix density, and total open porosity are accessed. Pore size distribution is determined using MIP analysis. Initial and final setting times of fresh mixtures are measured by automatic Vicat apparatus. Effect of silica admixture on mechanical resistivity is evaluated using compressive strength, bending strength, and dynamic Young's modulus measurement. The obtained data gives evidence of a decreased workability of paste mixtures with silica, whereas the setting process is accelerated. On the other hand, reaction activity of silica with Portland cement minerals results in a slight decrease of porosity and improvement of mechanical resistivity of cement pastes containing a-SiO2.

  16. Electrochemical promotion of catalytic reactions (United States)

    Imbihl, R.


    The electrochemical promotion of heterogeneously catalyzed reactions (EPOC) became feasible through the use of porous metal electrodes interfaced to a solid electrolyte. With the O 2- conducting yttrium stabilized zirconia (YSZ), the Na + conducting β″-Al 2O 3 (β-alumina), and several other types of solid electrolytes the EPOC effect has been demonstrated for about 100 reaction systems in studies conducted mainly in the mbar range. Surface science investigations showed that the physical basis for the EPOC effect lies in the electrochemically induced spillover of oxygen and alkali metal, respectively, onto the surface of the metal electrodes. For the catalytic promotion effect general concepts and mechanistic schemes were proposed but these concepts and schemes are largely speculative. Applying surface analytical tools to EPOC systems the proposed mechanistic schemes can be verified or invalidated. This report summarizes the progress which has been achieved in the mechanistic understanding of the EPOC effect.

  17. Coherent coupling of alkali atoms by random collisions

    CERN Document Server

    Katz, Or; Firstenberg, Ofer


    Random spin-exchange collisions in warm alkali vapor cause rapid decoherence and act to equilibriate the spin state of the atoms. In contrast, here we demonstrate experimentally and theoretically a coherent coupling of one alkali specie to another specie, mediated by these random collisions. We show that, the minor specie (potassium) inherits the magnetic properties of the dominant specie (rubidium), including its lifetime (T1), coherence time (T2), gyromagnetic ratio, and SERF magnetic-field threshold. We further show that this coupling can be completely controlled by varying the strength of the magnetic field. Finally, we explain these phenomena analytically by modes-mixing of the two species via spin-exchange collisions.

  18. Alkali-helium snowball complexes formed on helium nanodroplets. (United States)

    Müller, S; Mudrich, M; Stienkemeier, F


    We systematically investigate the formation and stability of snowballs formed by femtosecond photoionization of small alkali clusters bound to helium nanodroplets. For all studied alkali species Ak = (Na,K,Rb,Cs) we observe the formation of snowballs Ak(+)He(N) when multiply doping the droplets. Fragmentation of clusters Ak(N) upon ionization appears to enhance snowball formation. In the case of Na and Cs we also detect snowballs Ak(2) (+)He(N) formed around Ak dimer ions. While the snowball progression for Na and K is limited to less than 11 helium atoms, the heavier atoms Rb and Cs feature wide distributions at least up to Ak(+)He(41). Characteristic steps in the mass spectra of Cs-doped helium droplets are found at positions consistent with predictions on the closure of the first shell of helium atoms around the Ak(+) ion based on variational Monte Carlo simulations.

  19. Coherent coupling of alkali atoms by random collisions. (United States)

    Katz, Or; Peleg, Or; Firstenberg, Ofer


    Random spin-exchange collisions in warm alkali vapor cause rapid decoherence and act to equilibrate the spin state of the atoms in the vapor. In contrast, here we demonstrate experimentally and theoretically a coherent coupling of one alkali species to another species, mediated by these random collisions. We show that the minor species (potassium) inherits the magnetic properties of the dominant species (rubidium), including its lifetime (T_{1}), coherence time (T_{2}), gyromagnetic ratio, and spin-exchange relaxation-free magnetic-field threshold. We further show that this coupling can be completely controlled by varying the strength of the magnetic field. Finally, we explain these phenomena analytically by mode mixing of the two species via spin-exchange collisions.

  20. Penetration of alkali atoms throughout a graphene membrane: theoretical modeling. (United States)

    Boukhvalov, D W; Virojanadara, C


    Theoretical studies of penetration of various alkali atoms (Li, Na, Rb, Cs) throughout a graphene membrane grown on a silicon carbide substrate are reported and compared with recent experimental results. Results of first principles modeling demonstrate a rather low (about 0.8 eV) energy barrier for the formation of temporary defects in the carbon layer required for the penetration of Li at a high concentration of adatoms, a higher (about 2 eV) barrier for Na, and barriers above 4 eV for Rb and Cs. Experiments prove migration of lithium adatoms from the graphene surface to the buffer layer and SiC substrate at room temperature, sodium at 100 °C and impenetrability of the graphene membrane for Rb and Cs. Differences between epitaxial and free-standing graphene for the penetration of alkali ions are also discussed.