WorldWideScience

Sample records for alkali carbonate reactions

  1. Lithological influence of aggregate in the alkali-carbonate reaction

    International Nuclear Information System (INIS)

    Lopez-Buendia, A.M.; Climent, V.; Verdu, P.

    2006-01-01

    The reactivity of carbonate rock with the alkali content of cement, commonly called alkali-carbonate reaction (ACR), has been investigated. Alkali-silica reaction (ASR) can also contribute in the alkali-aggregate reaction (AAR) in carbonate rock, mainly due to micro- and crypto-crystalline quartz or clay content in carbonate aggregate. Both ACR and ASR can occur in the same system, as has been also evidenced on this paper. Carbonate aggregate samples were selected using lithological reactivity criteria, taking into account the presence of dedolomitization, partial dolomitization, micro- and crypto-crystalline quartz. Selected rocks include calcitic dolostone with chert (CDX), calcitic dolostone with dedolomitization (CDD), limestone with chert (LX), marly calcitic dolostone with partial dolomitization (CD), high-porosity ferric dolostone with clays (FD). To evaluate the reactivity, aggregates were studied using expansion tests following RILEM AAR-2, AAR-5, a modification using LiOH AAR-5Li was also tested. A complementary study was done using petrographic monitoring with polarised light microscopy on aggregates immersed in NaOH and LiOH solutions after different ages. SEM-EDAX has been used to identify the presence of brucite as a product of dedolomitization. An ACR reaction showed shrinkage of the mortar bars in alkaline solutions explained by induced dedolomitization, while an ASR process typically displayed expansion. Neither shrinkage nor expansion was observed when mortar bars were immersed in solutions of lithium hydroxide. Carbonate aggregate classification with AAR pathology risk has been elaborated based on mechanical behaviours by expansion and shrinkage. It is proposed to be used as a petrographic method for AAR diagnosis to complement the RILEM AAR1 specifically for carbonate aggregate. Aggregate materials can be classified as I (non-reactive), II (potentially reactive), and III (probably reactive), considering induced dedolomitization ACR

  2. Alkali aggregate reactions in concrete: a review of the Ethiopian ...

    African Journals Online (AJOL)

    The reaction of aggregates with alkalis in the cement to produce alkali silica reaction and alkali carbonate reaction is reviewed. The effects of the two reactions on the durability of concrete structures are highlighted. By taking samples of aggregates and cement test results, the potential of alkali silica reaction in Ethiopia is ...

  3. Alteration of alkali reactive aggregates autoclaved in different alkali solutions and application to alkali-aggregate reaction in concrete

    International Nuclear Information System (INIS)

    Lu Duyou; Mei Laibao; Xu Zhongzi; Tang Mingshu; Fournier, Benoit

    2006-01-01

    Surface alteration of typical aggregates with alkali-silica reactivity and alkali-carbonate reactivity, i.e. Spratt limestone (SL) and Pittsburg dolomitic limestone (PL), were studied by XRD and SEM/EDS after autoclaving in KOH, NaOH and LiOH solutions at 150 deg. C for 150 h. The results indicate that: (1) NaOH shows the strongest attack on both ASR and ACR aggregates, the weakest attack is with LiOH. For both aggregates autoclaved in different alkali media, the crystalline degree, morphology and distribution of products are quite different. More crystalline products are formed on rock surfaces in KOH than that in NaOH solution, while almost no amorphous product is formed in LiOH solution; (2) in addition to dedolomitization of PL in KOH, NaOH and LiOH solutions, cryptocrystalline quartz in PL involves in reaction with alkaline solution and forms typical alkali-silica product in NaOH and KOH solutions, but forms lithium silicate (Li 2 SiO 3 ) in LiOH solution; (3) in addition to massive alkali-silica product formed in SL autoclaved in different alkaline solutions, a small amount of dolomite existing in SL may simultaneously dedolomitize and possibly contribute to expansion; (4) it is promising to use the duplex effect of LiOH on ASR and ACR to distinguish the alkali-silica reactivity and alkali-carbonate reactivity of aggregate when both ASR and ACR might coexist

  4. Alkali silica reaction (ASR) in cement free alkali activated sustainable concrete.

    Science.gov (United States)

    2016-12-19

    This report summarizes the findings of an experimental evaluation into alkali silica : reaction (ASR) in cement free alkali-activated slag and fly ash binder concrete. The : susceptibility of alkali-activated fly ash and slag concrete binders to dele...

  5. THE COURSE OF THE ALKALI-AGGREGATE REACTION IN THE PRESENCE OF LITHIUM NITRATE

    Directory of Open Access Journals (Sweden)

    Owsiak Z.

    2013-06-01

    Full Text Available Lithium nitrate is recognized as a chemical compound capable of inhibiting the alkali-silica aggregate reaction. The extent to which the reaction is inhibited or limited is affected by the amount of the applied lithium compound and by the kind of reactive aggregate that has been used. In the case of the polymineral aggregate this process is particularly complex, as the alkali-silicate reaction may be accompanied by other alkali-aggregate reactions, i.a. the alkali-carbonate reaction. The paper presents the results of the investigation on the effect of lithium nitrate on the course of the alkali - reactive gravel aggregate reaction. The investigation was conducted in accordance with ASTM 1260 standard. The investigation results showed that lithium nitrate, when applied in appropriate amount, inhibits the process of mortar samples expansion. The appearance of spalls in the samples modified with a lithium compound indicates the occurrence of two reaction types: alkalisilica and alkali-carbonate.

  6. Adsorption and reaction of carbon dioxide on pure and alkali-metal promoted cold-deposited copper films

    Science.gov (United States)

    Pohl, M.; Otto, A.

    1998-05-01

    The adsorption and reaction of carbon dioxide on pure and potassium-doped cold-deposited copper films has been investigated at low temperatures and under UHV conditions using surface enhanced Raman spectroscopy (SERS) and X-ray photoemission spectroscopy (XPS). On pure copper films, an activated anionic CO δ- 2 species has been observed in addition to a weakly physisorbed CO 2 species. On potassium-doped copper films, monodentate carbonate as well as carbon monoxide has been observed in addition to the two carbon dioxide species. After adsorbing CO 2 on preadsorbed hydrogen, weak features at 2841 and 2949 cm -1 indicate the formation of formate. This result is compared to formate on pure copper films, synthesised by adsorbing formic acid on preoxidised copper films and subsequent annealing to 200 K.

  7. Historical and Experimental Studies of Alkali and Trinitrotoluene Reaction

    Science.gov (United States)

    1975-04-01

    aqueous-alcoholic alkali. 11hen a component is added whose carbon is bonded to active hydrogen atoms., an irt-ýsive pigmentation takes place irmiediately...The reactions giving pigmented products in the ŕxylol musk" was S attributed to the hydrogen atoms of the methyl group attached to the ring...readily reacts with TNT. The solution goes from orange to coffee -black as increasing amounts of TNT are added, with stirring, to the alkaline

  8. Studies on the alkali-silica reaction rim in a simplified calcium-alkali-silicate system

    NARCIS (Netherlands)

    Zheng, Kunpeng; Adriaensens, Peter; De Schutter, Geert; Ye, G.; Taerwe, Luc

    2016-01-01

    This work is intended to provide a better understanding about the properties and roles of the reaction rim in an alkali-silica reaction. A simplified calcium-alkali-silicate system was created to simulate the multiple interactions among reactive silica, alkaline solution and portlandite near the

  9. Dedolomitization and Alkali Reactions in Ohio-sourced Dolstone Aggregates

    Science.gov (United States)

    2017-11-01

    Concrete samples produced using NW-Ohio sourced aggregates were evaluated for susceptibility to degradation and premature failure due to cracks formed by the volume expansion during hydration of silica gels produced by alkali-silica reactions between...

  10. Influence of Exposure Conditions on the Efficacy of Lithium Nitrate in Mitigating Alkali Silica Reaction

    Science.gov (United States)

    Zapała-Sławeta, Justyna; Owsiak, Zdzisława

    2017-10-01

    Lithium nitrate is known to have the highest potential to inhibit alkali silica reaction in concrete. It is well soluble in water and does not increase the pH of concrete pore solution. The extent to which the alkali silica reaction is mitigated is affected by the amount of the applied lithium ions, exposure conditions and by the kind of reactive aggregate. It is known that some lithium compounds such as lithium carbonate or lithium fluoride, when used in insufficient amount, may increase expansion due to alkali silica reaction. This effect was not detected in the presence of lithium nitrate. The aim of this study was to determine the effect of lithium nitrate on alkali silica reaction in mortars exposed to different conditions. Expansion studies were conducted in accordance with the accelerated mortar bar test (ASTM C1260) and the standard mortar bar test (ASTM C227). It was observed that the long-term expansion results are different from the values obtained in the accelerated mortar bar test. Lithium nitrate does not reduce ASR-induced expansion when mortars are stored under conditions specified in ASTM C 227. The microstructure of the mortar samples exposed to different conditions was examined and X-ray microanalysis was performed. The microstructure and compositions of the alkali-silica reaction products varied. The amount of alkali silica gel in mortars with lithium nitrate in which the expansion was high was greater than that in the mortar bars tested by accelerated method.

  11. Concrete alkali-silica reaction and nuclear radiation damage

    International Nuclear Information System (INIS)

    Ichikawa, Tsuneki

    2008-01-01

    The deterioration of concrete by alkali-silica reaction of aggregates (ASR) and the effect of nuclear radiations on the ASR have been reviewed based on our studies on the mechanism of ASR and the effect of nuclear radiations on the resistivity of minerals to alkaline solution. It has been found that the ASR is initiated by the attack of alkaline solution in concrete to silicious aggregates to convert them into hydrated alkali silicate. The consumption of alkali hydroxide by the aggregates induces the dissolution of Ca 2+ ions into the solution. The alkali silicate surrounding the aggregates then reacts with Ca 2+ ions to convert to insoluble tight and rigid reaction rims. The reaction rim allows the penetration of alkaline solution but prevents the leakage of viscous alkali silicate, so that alkali silicate generated afterward is accumulated in the aggregate to give an expansive pressure enough for cracking the aggregate and the surrounding concrete. The effect of nuclear radiation on the reactivity of quartz and plagioclase, a part of major minerals composing volcanic rocks as popular aggregates, to alkaline solution has been examined for clarifying whether nuclear radiations accelerates the ASR. It has been found that the irradiation of these minerals converts them into alkali-reactive amorphous ones. The radiation dose for plagioclase is as low as 10 8 Gy, which suggests that the ASR of concrete surrounding nuclear reactors is possible to be accelerated by nuclear radiation. (author)

  12. Method for intercalating alkali metal ions into carbon electrodes

    Science.gov (United States)

    Doeff, Marca M.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard

    1995-01-01

    A low cost, relatively flexible, carbon electrode for use in a secondary battery is described. A method is provided for producing same, including intercalating alkali metal salts such as sodium and lithium into carbon.

  13. Thermodynamic and kinetic analysis of solid-phase interaction of alkali metal carbonates with arsenic pentoxide

    International Nuclear Information System (INIS)

    Pashinkin, A.S.; Buketov, E.A.; Isabaeva, S.M.; Kasenov, B.K.

    1985-01-01

    The thermodynamic analysis of solid-phase reactions of alkali metal carbonates with arsenic pentoxide showing the possibility of formation of all arsenates at a higher than the room temperature is performed. Energetically most advantageous is formation of meta-arsenates. It is shown that temperature increase favours the reaction process. By Gibbs standard energy decrease the reactions form the Li>Na>K>Rb>Cs series. On the base of calculation data linear dependence of Gibbs standard energy in reactions on the atomic number of alkali metalis established. By the continuous weighing method the kinetics of interaction of alkali metal carbonates with arsenic pentoxide under isothermal conditions in the 450-500 deg C range is studied. Studies is the dependence of apparent energy of interaction of carbonates wih As 2 0 5 an atomic parameters of al

  14. Continuing studies of alkali-aggregate reactions in concrete

    International Nuclear Information System (INIS)

    Gilliot, J.E.; Beddoes, R.J.

    1981-01-01

    Studies are continuing into the nature of the different forms of the alkali-aggregate reaction. No general agreement exists as to the detailed nature of the expansive mechanisms. Alkali is known to react internally with opaline silica because of its microporous nature whereas reaction at the external surface is thought to be relatively more important in the case of quartz. A combination of Fourier shape and surface texture analysis, microscopy and osmotic studies is being used to obtain information on the relative importance of these two forms of alkaline attack on silica. Analytical methods are much more rapid than dimensional change tests and it is hoped that a better understanding of the expansion mechanism will lead to more certain recognition of potentially alkali expansive aggregates

  15. The alkali-aggregate reaction - concrete microstructure evolution

    International Nuclear Information System (INIS)

    Regourd, M.; Hornain, H.; Poitevin, P.

    1981-01-01

    The alkali-aggregate reaction has been studied by scanning electron microscopy and energy dispersive X-ray analysis, electron probe microanalysis, and X-ray diffraction in concretes containing glass aggregates or hornfels and greywacke aggregates. The surface reaction of the natural aggregates in alkaline solutions has been analysed by X-ray photo-electron spectrometry. The study of concretes with glass aggregates stored at 20 degrees Celcius and 100 percent relative humidity has revealed, irrespective of alkali content and type of cement, the formation of a gel containing SiO 2 , Na 2 O, CaO, MgO and Al 2 O 3 . Under heat and pressure (210 degrees Celcius at MPa for 48 hours), the gel crystallizes and yields silicates not very different from tobermorite found in autoclaved normal concretes but cotaining Na and K in solid solutions. The alkali reaction in two natural aggregate concretes, is also shown by the formation of gels and silicate crystals. The progressive structuring of the gels in silicate crystals is promoted by an increase in temperature. Ettringite and Ca(OH) 2 reinforce the alkali-aggregate reaction which may be looked upon as a hydration reaction, partially of the pozzolanic type

  16. Coprecipitation of alkali metal ions with calcium carbonate

    International Nuclear Information System (INIS)

    Okumura, Minoru; Kitano, Yasushi

    1986-01-01

    The coprecipitation of alkali metal ions Li + , Na + , K + and Rb + with calcium carbonate has been studied experimentally and the following results have been obtained: (1) Alkali metal ions are more easily coprecipitated with aragonite than with calcite. (2) The relationship between the amounts of alkali metal ions coprecipitated with aragonite and their ionic radii shows a parabolic curve with a peak located at Na + which has approximately the same ionic radius as Ca 2+ . (3) However, the amounts of alkali metal ions coprecipitated with calcite decrease with increasing ionic radius of alkali metals. (4) Our results support the hypothesis that (a) alkali metals are in interstitial positions in the crystal structure of calcite and do not substitute for Ca 2+ in the lattice, but (b) in aragonite, alkali metals substitute for Ca 2+ in the crystal structure. (5) Magnesium ions in the parent solution increase the amounts of alkali metal ions (Li + , Na + , K + and Rb + ) coprecipitated with calcite but decrease those with aragonite. (6) Sodium-bearing aragonite decreases the incorporation of other alkali metal ions (Li + , K + and Rb + ) into the aragonite. (author)

  17. Alkali-aggregate reactions, strengthening or total collaps?

    DEFF Research Database (Denmark)

    Nielsen, Anders

    2000-01-01

    Alkali-aggregate reactions (AAR) can have many different effects, ranging from nothing happening to total cracking of the structure. The reason for this is related to the fact that chemistry and mechanics interfere with each other in the reactions. So, factors such as the concrete composition......, the production procedure, the design, and the climatic conditions, and in repair situations, the repair conditions, influence the development of the reactions.An overview of the many consequences and the influencing factors is necessary, when a certain structure suspected of being influenced by AAR is going...

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

    Directory of Open Access Journals (Sweden)

    Olague, C.

    2003-12-01

    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

  19. Influence of lithium hydroxide on alkali-silica reaction

    International Nuclear Information System (INIS)

    Bulteel, D.; Garcia-Diaz, E.; Degrugilliers, P.

    2010-01-01

    Several papers show that the use of lithium limits the development of alkali-silica reaction (ASR) in concrete. The aim of this study is to improve the understanding of lithium's role on the alteration mechanism of ASR. The approach used is a chemical method which allowed a quantitative measurement of the specific degree of reaction of ASR. The chemical concrete sub-system used, called model reactor, is composed of the main ASR reagents: reactive aggregate, portlandite and alkaline solution. Different reaction degrees are measured and compared for different alkaline solutions: NaOH, KOH and LiOH. Alteration by ASR is observed with the same reaction degrees in the presence of NaOH and KOH, accompanied by the consumption of hydroxyl concentration. On the other hand with LiOH, ASR is very limited. Reaction degree values evolve little and the hydroxyl concentration remains about stable. These observations demonstrate that lithium ions have an inhibitor role on ASR.

  20. Alteration of alkali reactive aggregates autoclaved in different alkali solutions and application to alkali-aggregate reaction in concrete (II) expansion and microstructure of concrete microbar

    International Nuclear Information System (INIS)

    Lu Duyou; Mei Laibao; Xu Zhongzi; Tang Mingshu; Mo Xiangyin; Fournier, Benoit

    2006-01-01

    The effect of the type of alkalis on the expansion behavior of concrete microbars containing typical aggregate with alkali-silica reactivity and alkali-carbonate reactivity was studied. The results verified that: (1) at the same molar concentration, sodium has the strongest contribution to expansion due to both ASR and ACR, followed by potassium and lithium; (2) sufficient LiOH can completely suppress expansion due to ASR whereas it can induce expansion due to ACR. It is possible to use the duplex effect of LiOH on ASR and ACR to clarify the ACR contribution when ASR and ACR may coexist. It has been shown that a small amount of dolomite in the fine-grained siliceous Spratt limestone, which has always been used as a reference aggregate for high alkali-silica reactivity, might dedolomitize in alkaline environment and contribute to the expansion. That is to say, Spratt limestone may exhibit both alkali-silica and alkali-carbonate reactivity, although alkali-silica reactivity is predominant. Microstructural study suggested that the mechanism in which lithium controls ASR expansion is mainly due to the favorable formation of lithium-containing less-expansive product around aggregate particles and the protection of the reactive aggregate from further attack by alkalis by the lithium-containing product layer

  1. Elastic modulus of the alkali-silica reaction rim in a simplified calcium-alkali-silicate system determined by nano-indentation

    NARCIS (Netherlands)

    Zheng, Kunpeng; Lukovic, M.; De Schutter, Geert; Ye, G.; Taerwe, Luc

    2016-01-01

    This work aims at providing a better understanding of the mechanical properties of the reaction rim in the alkali-silica reaction. The elastic modulus of the calcium alkali silicate constituting the reaction rim, which is formed at the interface between alkali silicate and Ca(OH)2 in a

  2. Ion conducting fluoropolymer carbonates for alkali metal ion batteries

    Science.gov (United States)

    DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Balsara, Nitash P.; Thelen, Jacob; Devaux, Didier

    2017-09-05

    Liquid or solid electrolyte compositions are described that comprise a homogeneous solvent system and an alkali metal salt dissolved in said solvent system. The solvent system may comprise a fluoropolymer, having one or two terminal carbonate groups covalently coupled thereto. Batteries containing such electrolyte compositions are also described.

  3. Alkali-silica reaction resistant concrete using pumice blended cement

    Science.gov (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

  4. The Deteriorating Impact of Alkali-Silica Reaction on Concrete : Expansion and Mechanical Properties

    NARCIS (Netherlands)

    Esposito, R.

    2016-01-01

    The assessment of concrete structures affected by alkali-silica reaction (ASR) is a complex problem due to the multiscale nature of this long-term phenomenon. The reaction starts within the concrete constituents with the formation of an expansive alkali-silica gel at reaction products level. Being

  5. 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)

    1997-04-01

    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.

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

    International Nuclear Information System (INIS)

    Kurtis, K.E.; Monteiro, P.J.M.; Brown, J.T.; Meyer-Ilse, W.

    1997-01-01

    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. Electrochemical lithium migration to mitigate alkali-silica reaction in existing concrete structures

    NARCIS (Netherlands)

    Silva De Souza, L.M.

    2016-01-01

    Alkali-silica reaction (ASR) is a deterioration process that affects the durability of concrete structures worldwide. During the reaction, hydroxyl and alkali ions present in the pore solution react with reactive silica from the aggregate, forming a hygroscopic ASR gel. Alternatively, the silica

  8. A light water excess heat reaction suggests that cold fusion may be alkali-hydrogen fusion

    International Nuclear Information System (INIS)

    Bush, R.T.

    1992-01-01

    This paper reports that Mills and Kneizys presented data in support of a light water excess heat reaction obtained with an electrolytic cell highly reminiscent of the Fleischmann-Pons cold fusion cell. The claim of Mills and Kneizys that their excess heat reaction can be explained on the basis of a novel chemistry, which supposedly also explains cold fusion, is rejected in favor of their reaction being, instead, a light water cold fusion reaction. It is the first known light water cold fusion reaction to exhibit excess heat, it may serve as a prototype to expand our understanding of cold fusion. From this new reactions are deduced, including those common to past cold fusion studies. This broader pattern of nuclear reactions is typically seen to involve a fusion of the nuclides of the alkali atoms with the simplest of the alkali-type nuclides, namely, protons, deuterons, and tritons. Thus, the term alkali-hydrogen fusion seems appropriate for this new type of reaction with three subclasses: alkali-hydrogen fusion, alkali-deuterium fusion, and alkali-tritium fusion. A new three-dimensional transmission resonance model (TRM) is sketched. Finally, preliminary experimental evidence in support of the hypothesis of a light water nuclear reaction and alkali-hydrogen fusion is reported. Evidence is presented that appears to strongly implicate the transmission resonance phenomenon of the new TRM

  9. Effect of silicate modulus and metakaolin incorporation on the carbonation of alkali silicate-activated slags

    International Nuclear Information System (INIS)

    Bernal, Susan A.; Mejia de Gutierrez, Ruby; Provis, John L.; Rose, Volker

    2010-01-01

    Accelerated carbonation is induced in pastes and mortars produced from alkali silicate-activated granulated blast furnace slag (GBFS)-metakaolin (MK) blends, by exposure to CO 2 -rich gas atmospheres. Uncarbonated specimens show compressive strengths of up to 63 MPa after 28 days of curing when GBFS is used as the sole binder, and this decreases by 40-50% upon complete carbonation. The final strength of carbonated samples is largely independent of the extent of metakaolin incorporation up to 20%. Increasing the metakaolin content of the binder leads to a reduction in mechanical strength, more rapid carbonation, and an increase in capillary sorptivity. A higher susceptibility to carbonation is identified when activation is carried out with a lower solution modulus (SiO 2 /Na 2 O ratio) in metakaolin-free samples, but this trend is reversed when metakaolin is added due to the formation of secondary aluminosilicate phases. High-energy synchrotron X-ray diffractometry of uncarbonated paste samples shows that the main reaction products in alkali-activated GBFS/MK blends are C-S-H gels, and aluminosilicates with a zeolitic (gismondine) structure. The main crystalline carbonation products are calcite in all samples and trona only in samples containing no metakaolin, with carbonation taking place in the C-S-H gels of all samples, and involving the free Na + present in the pore solution of the metakaolin-free samples. Samples containing metakaolin do not appear to have the same availability of Na + for carbonation, indicating that this is more effectively bound in the presence of a secondary aluminosilicate gel phase. It is clear that claims of exceptional carbonation resistance in alkali-activated binders are not universally true, but by developing a fuller mechanistic understanding of this process, it will certainly be possible to improve performance in this area.

  10. The Deteriorating Impact of Alkali-Silica Reaction on Concrete: Expansion and Mechanical Properties

    OpenAIRE

    Esposito, R.

    2016-01-01

    The assessment of concrete structures affected by alkali-silica reaction (ASR) is a complex problem due to the multiscale nature of this long-term phenomenon. The reaction starts within the concrete constituents with the formation of an expansive alkali-silica gel at reaction products level. Being the expansive gel confined within the concrete micro-structure, an internal pressure is built up that induces damage at aggregate level. This micro-cracking affects the mechanical characteristics of...

  11. Investigation on the expansion value of turbine generator foundation affected by Alkali-Silica reaction

    International Nuclear Information System (INIS)

    Takakura, T.; Ishikawa, T.; Mitsuki, S.; Matsumoto, N.; Takiguchi, K.; Masuda, Y.; Nishiguchi, I.

    2005-01-01

    It is well known that expansion of concrete is occurred in the concrete structure affected by Alkali-silica reaction in addition to crack propagation. However it is difficult to measure expansion value after the alkali silica reaction occurrence in a structure. The turbine generator foundation which is the core discussion item of this paper has been monitored for expansion values and reinforcement bar strains, upon which the expansion of the structure due to affect of the alkali silica reaction is found out. The total expansion values of the turbine generator foundation due to the affect of Alkali-silica reaction were estimated according to those measurement results in order to be utilized for a turbine generator foundation analysis. (authors)

  12. The effects of supplementary cementitious materials on alkali-silica reaction : [technical summary].

    Science.gov (United States)

    2015-07-01

    The Kansas Department of Transportation (KDOT) has controlled alkali-silica : reaction (ASR) for more than 70 years through the use of selected aggregates. : Sand and gravel sources had to be tested using Kansas Test Method KTMR- : 23 (1999), Wetting...

  13. Forecasting approach of electrochemical valorisation of CO2 in alkali molten carbonates

    International Nuclear Information System (INIS)

    Chery, Deborah

    2015-01-01

    Carbon Dioxide is a greenhouse which can be valorised by means of electrochemical valorisation into carbon monoxide. The main goals of the thesis consist in the theoretical determination of the conductive conditions leading to this electrochemical valorisation in alkali molten carbonates along with the study of the feasibility of this electrochemical reduction in binary and ternary eutectics under experimental condition. CO 2 solubility has been determined by manometric measure and increase along with the temperature. CO 2 electrochemical experimental feasibility into CO in eutectics on gold plate electrode and graphite carbon has been proved by cyclic volt-amperometry for temperatures exceeding 550 C, without gold plate electrode pretreatment and with gold plate pretreatment by an pre-electrolysis at potential slightly negative as the CO 2 reduction potential. A global approach of reactional mechanisms implied in CO 2 reduction is proposed. (author)

  14. Alkali-Silica Reaction in Concrete from Fontana Dam, North Carolina, Tennessee Valley Authority.

    Science.gov (United States)

    1986-09-01

    picture is complicated by the instances of reaction in phyllite3 and other micaceous rocks. g. These include Dolar -Mantuani5 who found reacted...expansion of cylinders. SanJ made from graywacke d-ill cores showed some expansivity in mortar bars. Dolar -Mantuani described the argillites as...Mechanics of Alkali-Silica Reaction," ASTM Bull. No. 205, p 40, 1955. 5. L. Dolar -Mantuani, "Alkali-Silica-Reactive Rocks in the Canadian Sield

  15. Assessment of concrete bridge decks with alkali silica reactions

    DEFF Research Database (Denmark)

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

    2008-01-01

    , 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...

  16. Recovery of alkali and alumina from Bayer red mud by the calcification-carbonation method

    Science.gov (United States)

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

    2016-03-01

    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.

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

    OpenAIRE

    Etxeberria, M.; Vázquez, E.

    2010-01-01

    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 accumulat...

  18. Relation of expansion due to alkali silica reaction to the degree of reaction measured by SEM image analysis

    International Nuclear Information System (INIS)

    Haha, M. Ben; Gallucci, E.; Guidoum, A.; Scrivener, K.L.

    2007-01-01

    Scanning Electron Microscopy Image Analysis (SEM-IA) was used to quantify the degree of alkali silica reaction in affected microbars, mortar and concrete prisms. It was found that the degree of reaction gave a unique correlation with the macroscopic expansion for three different aggregates, stored at three temperatures and with two levels of alkali. The relationships found for the concretes and the mortars overlap when normalised by the aggregate content. This relationship seems to be linear up to a critical reaction degree which coincides with crack initiation within the reactive aggregates

  19. Cement Type Influence on Alkali-Silica Reaction in Concrete with Crushed Gravel Aggregate

    Science.gov (United States)

    Rutkauskas, A.; Nagrockienė, D.; Skripkiūnas, G.

    2017-10-01

    Alkali-silica reaction is one of the chemical reactions which have a significant influence for durability of concrete. During alkali and silica reaction, silicon located in aggregates of the concrete, reacts with high alkali content. This way in the micropores of concrete is forming hygroscopic gel, which at wet environment, expanding and slowly but strongly destroying concrete structures. The goal of this paper- to determine the influence of cement type on alkali-silica reaction of mortars with crushed gravel. In the study crushed gravel with fraction 4/16 mm was used and four types of cements tested: CEM I 42.5 R; CEM I 42.5 SR; CEM II/A-S 42.5; CEM II/A-V 52.5. This study showed that crushed gravel is low contaminated on reactive particles containing of amorphous silica dioxide. The expansion after 14 days exceed 0.054 %, by RILEM AAR-2 research methodology (testing specimen dimension 40×40×160 mm). Continuing the investigation to 56 days for all specimens occurred alkaline corrosion features: microcracking and the surface plaque of gel. The results showed that the best resistance to alkaline corrosion after 14 days was obtained with cement CEM I 42.5 SR containing ash additive, and after 56 days with cement CEM II/A-V 52.5 containing low alkali content. The highest expansion after 14 and 56 days was obtained with cement CEM I 42.5 R without active mineral additives.

  20. Automated Detection of Alkali-silica Reaction in Concrete using Linear Array Ultrasound Data

    Energy Technology Data Exchange (ETDEWEB)

    Santos-Villalobos, Hector J [ORNL; Clayton, Dwight A [ORNL; Ezell, N Dianne Bull [ORNL; Clayton, Joseph A [ORNL; Baba, Justin S [ORNL

    2017-01-01

    Alkali-silica reaction (ASR) is a chemical reaction in either concrete or mortar between hydroxyl ions of the alkalis (sodium and potassium) from hydraulic cement (or other sources), and certain siliceous minerals present in some aggregates. The reaction product, an alkali-silica gel, is hygroscopic having a tendency to absorb water and swell, which under certain circumstances, leads to abnormal expansion and cracking of the concrete. This phenomenon affects the durability and performance of concrete structures severely since it can cause significant loss of mechanical properties. Developing reliable methods and tools that can evaluate the degree of the ASR damage in existing structures, so that informed decisions can be made toward mitigating ASR progression and damage, is important to the long term operation of nuclear power plants especially if licenses are extended beyond 60 years. This paper examines an automated method of determining the extent of ASR damage in fabricated concrete specimens.

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

    International Nuclear Information System (INIS)

    Poyet, S.; Sellier, A.; Capra, B.; Foray, G.; Torrenti, J.M.; Cognon, H.; Bourdarot, E.

    2007-01-01

    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)

  2. The effects of potassium and rubidium hydroxide on the alkali-silica reaction

    International Nuclear Information System (INIS)

    Shomglin, K.; Turanli, L.; Wenk, H.-R.; Monteiro, P.J.M.; Sposito, G.

    2003-01-01

    Expansion of mortar specimens prepared with an aggregate of mylonite from the Santa Rosa mylonite zone in southern California was studied to investigate the effect of different alkali ions on the alkali-silica reaction in concrete. The expansion tests indicate that mortar has a greater expansion when subjected to a sodium hydroxide bath than in a sodium-potassium-rubidium hydroxide bath. Electron probe microanalysis (EPMA) of mortar bars at early ages show that rubidium ions, used as tracer, were present throughout the sample by the third day of exposure. The analysis also shows a high concentration of rubidium in silica gel from mortar bars exposed to bath solutions containing rubidium. The results suggest that expansion of mortar bars using ASTM C 1260 does not depend on the diffusion of alkali ions. The results indicate that the expansion of alkali-silica gel depends on the type of alkali ions present. Alkali-silica gel containing rubidium shows a lower concentration of calcium, suggesting competition for the same sites

  3. Alkalies and cement clinker reactions on basic refractories

    Energy Technology Data Exchange (ETDEWEB)

    Cherif, K. [INR Analyse Physico-Chemical, Manzah (Tunisia); Palco, S.; Guo, Z.; Rigaud, M. [CIREP-Ecole Polytechnique, Montreal, PQ (Canada)

    2002-07-01

    In an effort to characterize the mechanisms, by which cement clinkers do react with doloma, magnesia, or spinel (magnesia-alumina spinel) to form stable coatings, new testing procedures are presented. In order to quantify the extend of the interactions between the brick and the cement raw-meal at the initial coating formation a test method was designed to measure the MOR on sandwiches prepared under specified procedures. The effects of the microstructure of refractory bricks, as well as of the properties of tested raw meal, are evaluated in terms of their effects on the mechanism of coating - formation by means of microscopy. Induction heating was used for fast heat-up in the specially designed experimental setup with the aim to simulate the thermal shock with the simultaneous attack of cement-raw meal enhanced by the presence of alkalies. The effects on structural changes of bricks are evaluated by using different methods of chemical and structural analyzes. (orig.)

  4. Carbonation Resistance of Alkali-Activated Slag Under Natural and Accelerated Conditions

    NARCIS (Netherlands)

    Nedeljkovic, M.; Zuo, Y.; Arbi, Kamel; Ye, G.

    2018-01-01

    In this paper, carbonation resistance of alkali-activated slag (AAS) pastes exposed to natural and accelerated conditions up to 1 year was investigated. Two aspects of carbonation mechanism were evaluated. The first was the potential carbonation of the main binding phases in finely powdered AAS

  5. Alkali-silica reaction of aggregates in real concrete and mortar specimen

    Czech Academy of Sciences Publication Activity Database

    Lukschová, Šárka

    -, č. 18 (2009), s. 75-78 ISSN 1214-9691 Institutional research plan: CEZ:AV0Z30460519 Keywords : alkali-silica reaction * concrete * mocroscopy Subject RIV: DB - Geology ; Mineralogy www.irsm.cas.cz/?Lang=CZE&Menu=25,29,0,0

  6. Low tensile strength in older concrete structures with alkali-silica reaction

    NARCIS (Netherlands)

    Siemes, A.J.M.; Visser, J.H.M.

    2000-01-01

    During an extensive investigation of some 25 concrete bridges and other structures suffer-ing from alkali-silica reaction it has been found that the uniaxial tensile strength of the concrete was extremely low in relation to both the compressive strength and the splitting tensile strength. It is

  7. The alkali-silica reaction: mineralogical and geochemical aspects of some Dutch concretes and Norwegian mylonites

    NARCIS (Netherlands)

    Broekmans, M.A.T.M.

    2002-01-01

    Maarten Broekmans has studied the alkali-silica reaction in two Dutch concretes by means of optical microscopy, geochemical analyses on bulk material and after selective digestion in acid, and with element mapping in polished thin sections. He furthermore characterized the nature of the

  8. The effects of supplementary cementitious materials on alkali-silica reaction.

    Science.gov (United States)

    2015-07-01

    The Kansas Department of Transportation (KDOT) has controlled alkali-silica reaction (ASR) for more than : 70 years through the use of selected aggregates. Sand and gravel sources had to be tested using Kansas Test Method : KTMR-23 (1999), Wetting an...

  9. Regioselective hydrogen isotope exchange reaction in benzoic acid and its alkali metal salts

    International Nuclear Information System (INIS)

    Nakagawa, Akiko; Hasegawa, Hideaki; Oohashi, Kunio; Seki, Hiroko.

    1997-01-01

    The hydrogen isotope exchange reaction of benzoic and acid its alkali metal salts with deuterium oxide was studied in the presence of RhCl 3 ·3H 2 O. The products were analyzed by 1 H- and 13 C-NMR spectroscopies. High regioselectivity of the exchange at the ortho positions was established, and the extent of deuterium labeling and the distribution of d 0 , d 1 , and d 2 were determined. The reaction mechanism was briefly discussed. (author)

  10. Alkali-silica reaction products: Comparison between samples from concrete structures and laboratory test specimens

    International Nuclear Information System (INIS)

    Sachlova, Sarka; Prikryl, Richard; Pertold, Zdenek

    2010-01-01

    Alkali-silica gels (ASG) were investigated in concrete from bridge structures (constructed from the 1920s to 2000), as well as in experimental specimens; employing optical microscopy, petrographic image analysis, and scanning electron microscopy combined with energy dispersive spectroscopy (SEM/EDS). The main differences were found in the chemical composition and morphology of the ASGs. ASGs which had formed in older concrete samples (50-80 years old) show a partly crystalline structure and higher Ca 2+ content, indicating their aging and maturation. Younger concrete samples and experimental test specimens exhibit the presence of amorphous ASG. The chemistry of ASG from experimental specimens reflects the chemical composition of accelerating solutions. - Research Highlights: → Quantitative analysis of alkali-silica gels → Comparison of ASR in experimental conditions with ASR in bridge structures → Investigation of factors affecting alkali-silica reaction → Investigation of ASR of different types of aggregates

  11. Influence of stress restraint on the expansive behaviour of concrete affected by alkali-silica reaction

    International Nuclear Information System (INIS)

    Berra, M.; Faggiani, G.; Mangialardi, T.; Paolini, A.E.

    2010-01-01

    The primary objective of this study was to ascertain whether the Threshold Alkali Level (TAL) of the concrete aggregates may be taken as a suitable reactivity parameter for the selection of aggregates susceptible of alkali-silica reaction (ASR), even when ASR expansion in concrete develops under restrained conditions. Concrete mixes made with different alkali contents and two natural siliceous aggregates with very different TALs were tested for their expansivity at 38 o C and 100% RH under unrestrained and restrained conditions. Four compressive stress levels over the range from 0.17 to 3.50 N/mm 2 were applied by using a new appositely designed experimental equipment. The lowest stress (0.17 N/mm 2 ) was selected in order to estimate the expansive pressure developed by the ASR gel under 'free' expansion conditions. It was found that, even under restrained conditions, the threshold alkali level proves to be a suitable reactivity parameter for designing concrete mixes that are not susceptible of deleterious ASR expansion. An empirical relationship between expansive pressure, concrete alkali content and aggregate TAL was developed in view of its possible use for ASR diagnosis and/or safety evaluation of concrete structures.

  12. Characterization and Modeling of Alkali-Silica Reaction of Reactive Siliceous Materials in Conducting Model and Mortar Experiments

    OpenAIRE

    Baingam, Lalita

    2016-01-01

    The use of certain aggregate in harden concrete may cause in a particular chemical process in whichvarious silica forms of aggregate react with alkali hydroxides dissolved in the pore solution of concrete,attributing to the alkali silica reaction (ASR). The ASR can produce hydrous calcium-alkali silicate andalkali-silicate gels. This so-called ASR gel adsorbs water and the resulting in swelling expansion, causescracks in the aggregate grains and in the surrounding cement paste matrix leading ...

  13. 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: pvgomes@uol.com.br [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

    2014-08-15

    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)

  14. Laser scanning confocal microscopy for in situ monitoring of alkali-silica reaction.

    Science.gov (United States)

    Collins, C L; Ideker, J H; Kurtis, K E

    2004-02-01

    Alkali-silica reaction (ASR) occurs in concrete between reactive siliceous components in the aggregate and the strongly alkaline pore solution, resulting in the formation of a potentially expansive gel product. Lithium additives have been shown to reduce expansion associated with ASR, but the mechanism(s) by which lithium reduces expansion have not been understood. Therefore, development of an in situ method to observe reactions associated with ASR is highly desirable, as it will allow for non-destructive observation of the reaction product formation and damage evolution over time, as the reaction progresses. A technique to image into mortar through glass aggregate by laser scanning confocal microscopy (LSCM), producing three-dimensional representations of the sample was developed. This LSCM technique was utilized to monitor the progress of alkali-silica reaction in mortar samples prepared with alkali-reactive glass aggregate both in the presence and in the absence of lithium additives: LiNO3, LiCl or LiOH. The method proved to be effective in qualitatively monitoring crack formation and growth and product formation, within cracks and at the paste/aggregate interface. In particular, dendritic products were observed at the paste/aggregate interface only in those samples containing lithium, suggesting that these products may play a role in ASR mitigation.

  15. Alkali Silica Reaction In The Presence Of Metakaolin - The Significant Role of Calcium Hydroxide

    Science.gov (United States)

    Zapała-Sławeta, Justyna

    2017-10-01

    Reducing the internal corrosion, which is the result of reactions between alkalis and reactive aggregates is especially important in ensuring durability properties of concrete. One of the methods of inhibiting the reaction is using some mineral additives which have pozzolanic properties. This paper presents the efficacy of high-reactivity metakaolin in reducing expansion due to alkali-silica reaction. It was demonstrated that metakaolin in the amount from 5% to 20% by mass of Portland cement reduce linear expansion of mortar bars with opal aggregate. Nevertheless, the safe expansion level in the specimens, classified as non-destructive to concrete, was recorded for the mortars prepared with 20% addition of metakaolin. Depletion of free calcium hydroxide content was considered as one of the most beneficial effects of metakaolin in controlling alkali silica reaction. Based on thermogravimetric analysis (TGA) performed on mortar bars with and without metakaolin the differences in portlandite content were determined. Microstructural observation of the specimens containing metakaolin indicated the presence of a reaction products but fewer in number than those forming in the mortars without mineral additives.

  16. Effect of Rice Straw Extract and Alkali Lignin on the Corrosion Inhibition of Carbon Steel

    International Nuclear Information System (INIS)

    Rabiahtul Zulkafli; Norinsan Kamil Othman; Irman Abdul Rahman; Azman Jalar

    2014-01-01

    A paddy residue based corrosion inhibitor was prepared by treating finely powdered rice straw with aqueous ethanol under acid catalyst (0.01 M H 2 SO 4 ). Commercial alkali lignin was obtained from Sigma-Aldrich. Prior to the corrosion test, the extraction yield and alkali lignin was characterized via FTIR to determine the functional group. The effect of paddy residue extract and commercial alkali lignin on the corrosion inhibition of carbon steel in 1 M HCl was investigated through the weight loss method, potentiodynamic polarization technique and scanning electron microscopy (SEM). The corrosion inhibition efficiency of the extract and alkali lignin at different immersion times (3 h, 24 h and 42 h) was evaluated. The results show that the paddy waste extract exhibited lesser weight loss of carbon steel in the acidic medium in comparison to the commercial alkali lignin, suggesting that the paddy residue extract is more effective than the commercial alkali lignin in terms of its corrosion inhibition properties. The results obtained proves that the extract from paddy residue could serve as an effective inhibitor for carbon steel in acidic mediums. (author)

  17. Reaction dynamics of electronically excited alkali atoms with simpler molecules

    International Nuclear Information System (INIS)

    Weiss, P.S.; Mestdagh, J.M.; Schmidt, H.; Vernon, M.F.; Covinsky, M.H.; Balko, B.A.; Lee, Y.T.

    1985-05-01

    The reactions of electronically excited sodium atoms with simple molecules have been studied in crossed molecular beams experiments. Electronically excited Na(3 2 P/sub 3/2/, 4 2 D/sub 5/2/, and 5 2 S/sub 1/2/) were produced by optical pumping using single frequency dye lasers. The effects of the symmetry, and the orientation and alignment of the excited orbital on the chemical reactivity, and detailed information on the reaction dynamics were derived from measurements of the product angular and velocity distributions. 12 refs., 9 figs

  18. Investigation of structural properties associated with alkali-silica reaction by means of macro- and micro-structural analysis

    International Nuclear Information System (INIS)

    Mo Xiangyin; Fournier, Benoit

    2007-01-01

    Structural properties associated with alkali-silica reaction were systematically investigated by means of macro-structural accelerated mortar prism expansion levels testing, combined with micro-structural analysis. One part of this study is to determine the reactivity of the aggregate by means of accelerated mortar bar tests, and also to evaluate perlite aggregate constituents, especially the presence of deleterious components and find main causes of the alkali-silica reaction, which was based on the petrographic studies by optical microscope and the implication of X-ray diffraction on the aggregate. Results implied that the aggregate was highly alkali-silica reactive and the main micro-crystalline quartz-intermediate character and matrix that is mainly composed of chalcedony are potentially suitable for alkali-silica reaction. The other part is to study the long-term effect of lithium salts against alkali-silica reaction by testing accelerated mortar prism expansion levels. The macro-structural results were also consistent with the micro-structural mechanisms of alkali-silica reaction of mortar prisms containing this aggregate and the effect of chemical admixtures by means of the methods of scanning electron microscope-X-ray energy-dispersive spectroscopy and X-ray diffraction. It was indicated by these techniques that lithium salts, which were introduced into concrete containing reactive aggregate at the mixing stage, suppressed the alkali-silica reaction by producing non-expansive crystalline materials

  19. 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

    2017-03-01

    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.

  20. A comparative evaluation of metakaolin and silica fume to control alkali-silica reaction in concrete

    Energy Technology Data Exchange (ETDEWEB)

    Nkinamubanzi, P.C.; Fournier, B.; Chevrier, R. [Natural Resources Canada, Ottawa, ON (Canada). CANMET Materials Technology Laboratory

    2007-07-15

    This study evaluated the efficacy of different types of cementing materials. An accelerated modified mortar bar test was used to evaluate the efficacy of supplementary cementing materials (SCMs) including silica fume, metakaolin, fly ash, and slag in binary and ternary cementitious systems. Spratt and Sudbury aggregates were used as reference reactive aggregates. Thermal analyses of past specimens incorporating silica fume and metakaolin were conducted. The role of alkalis in pozzolanic reaction products through pore solution analysis on paste specimens was also investigated. The study showed that additions of metakaolin was needed to achieve expansion reductions similar to reductions obtained using silica fume. The cause was attributed to the lower alkali binding capacity and portlandite consumption of the metakaolin material. The study also showed that the efficacy of the SCMs in counteracting alkali-silica reactions (ASR) in concrete varied widely depending on the nature and the composition of the materials used, as well as on the reactivity level of the aggregates and the proportion of the SCMs in the concrete mixtures. 17 refs., 10 tabs., 19 figs, 2 appendices.

  1. Electrical conductivity and thermal behavior of solid electrolytes based on alkali carbonates and sulfates

    NARCIS (Netherlands)

    Brosda, S.; Bouwmeester, Henricus J.M.; Guth, U.

    1997-01-01

    Both thermal stability and electrical conductivity of alkali ion conducting Na2CO3 and Na2SO4, were improved by adding alkaline earth carbonates and sulfates, respectively, as well as insulating materials like ¿-Al2O3. The admixing of divalent compounds causes two effects. First a more or less

  2. Volcanic Aggregates from Azores and Madeira Archipelagos (Portugal): An Overview Regarding the Alkali Silica Reactions

    Science.gov (United States)

    Medeiros, Sara; Ramos, Violeta; Fernandes, Isabel; Nunes, João Carlos; Fournier, Benoit; Santos Silva, António; Soares, Dora

    2017-12-01

    Alkali-silica reaction (ASR) is a type of deterioration that has been causing serious expansion, cracking and durability/operational issues in concrete structures worldwide. The presence of sufficient moisture, high alkali content in the cement paste and reactive forms of silica in the aggregates are the required conditions for this reaction to occur. Reactive aggregates of volcanic nature have been reported in different countries such as Japan, Iceland and Turkey, among others. The presence of silica minerals and SiO2-rich volcanic glass is regarded as the main cause for the reactivity of volcanic rocks. In Portugal, volcanic aggregates are mainly present in Azores and Madeira Archipelagos and, for several years, there was no information regarding the potential alkali-reactivity of these rocks. Since the beginning of this decade some data was obtained by the work of Medeiros (2011) and Ramos (2013) and by the national research projects ReAVA, (Characterization of potential reactivity of the volcanic aggregates from the Azores Archipelago: implications on the durability of concrete structures) and IMPROVE (Improvement of performance of aggregates in the inhibition of alkali-aggregate reactions in concrete), respectively. In order to investigate the potential alkali-reactivity of aggregates from both archipelagos, a total of sixteen aggregates were examined under the optical microscope and, some of them, also under the Scanning Electron Microscope with Energy Dispersive X-ray Spectroscopy. A set of geochemical analyses and laboratory expansion tests were also performed on those volcanic aggregates. The main results showed that the presence of volcanic glass is rare in both archipelagos and that the samples of Madeira Archipelago contain clay minerals (mainly from scoria/tuff formations inter-layered with the lava flows), which can play a role in concrete expansion. The results of the laboratory tests showed that one of the samples performed as potentially reactive

  3. Alkali-aggregate reaction under the influence of deicing salts in the Hokuriku district, Japan

    International Nuclear Information System (INIS)

    Katayama, Tetsuya; Tagami, Masahiko; Sarai, Yoshinori; Izumi, Satoshi; Hira, Toshikatsu

    2004-01-01

    Concrete cores taken from highway bridges and culverts undergoing alkali-silica reaction (ASR) were investigated petrographically by means of core scanning, point counting, polarizing microscopy, scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), electron-probe microanalysis with energy-dispersive spectrometry, in conjunction with wet chemical analyses and expansion tests. Field damage was roughly proportional to the content of andesite in the gravel aggregates due to the presence of highly reactive cristobalite and tridymite. Electron-probe microanalyzer analysis of unhydrated cement phases in the concrete revealed that the cement used had contained at least 0.5% to 1.0% alkali (Na 2 Oeq) and that both the aggregates and the deicing salts had supplied part of the water-soluble alkali to concrete toward the threshold of producing ASR (Na 2 O eq 3.0 kg/m 3 ). An accelerated concrete core expansion test (1 M NaOH, 80 deg. C) of the damaged structures mostly gave core expansions of >0.10% at 21 days (or >0.05% at 14 days), nearly comparable to those of a slow expansion test with saturated NaCl solution (50 deg. C, 91 days) which produced Cl-containing ASR gel

  4. Role of PFA quality and conditioning in minimising alkali-silica reaction in concrete

    Energy Technology Data Exchange (ETDEWEB)

    McCarthy, M.J.; Dhir, R.K.; Halliday, J.E.; Wibowo, A. [University of Dundee, Dundee (United Kingdom). Division of Civil Engineering

    2006-02-15

    This paper describes the work of a study carried out to assess the effect of pulverised fuel ash (PFA) quality (including conditioned (moistened) PFA) on its ability to minimise the risk of alkali-silica reaction (ASR) in concrete and thereby, whether the wider range of materials covered in BS 3892-1, BS 3892-2 and BS EN 450 can be used in this role. A total of 11 PFAs (within and between sources) and three types of aggregate combination, covering materials used in the UK, were examined. Two series of tests were carried out, which used concrete mixes proportioned to (a) the BS 812-123 standard method (alkali content 7.0 kg/m{sup 3}) and (b) the BRE method (alkali content from 3.6 to 6.0 kg/m{sup 3}), using the BS 812-123 test procedure (38{sup o}C, above water). The results obtained over three years, established that the physical and chemical properties of PFA (fineness and alkali content (Na{sub 2}Oeq)) had only a minor influence on its ability to minimise ASR risk. Conditioning of PFA and its loss on ignition appeared to have no effect. Overall, the results suggest that PFA to BS 3892-2 and to BS EN 450, may be considered to be equally as effective as BS 3892-1 PFA in minimising ASR in concrete, containing potentially reactive aggregates available in the UK. The outcomes of this and other work have been considered by the ASI concrete committee and this has led to a change in BS 8500, which now permits the use of BS EN 450 PFA.

  5. Investigation of structural integrity for turbine generator foundation affected by alkali-silica reaction

    International Nuclear Information System (INIS)

    Ryo Fujimoto; Hiroshi Shimizu; Hisashi Sekimoto; Yuichi Watanabe; Tatsuya Ishikawa

    2005-01-01

    Turbine Generator Foundation is a reinforced concrete structure having a table deck to support equipments and columns to support the table deck. After operation of the plant, the expansion of the table deck in turbine longitudinal axis in the structure has been observed. By investigation of concrete material property, it is found that the expansion has been caused by alkali-silica reaction (ASR). In this study, we evaluate the material properties of the structure affected by ASR and safety margin of capacity of the structure by nonlinear analysis using beam element model with those material properties. (authors)

  6. Investigations on the carbon contaminations on the alkali cells of DPAL with hydrocarbon buffer gas

    Science.gov (United States)

    Li, Zhiyong; Tan, Rongqing; Wang, Yujie; Ye, Qing; Bian, Jintian; Huang, Wei; Li, Hui; Han, Gaoce

    2017-10-01

    Diode pumped alkali laser (DPAL) with hydrocarbon buffer gases has the features of low threshold and high efficiency. The chemical reaction between alkali and hydrocarbon gases affects the life time of DPAL. In this paper, a method based on Fourier transform infrared spectroscopy and Lambert-Beer law is adopted to find a safe temperature at which DPAL runs for a long term. A theoretical model is established to figure out ways to reduce the peak temperature in the cell window. The results indicates that 170 °C is a safe temperature. Although the absorbance of the cell window to the pump light and alkali laser is lower, there is temperature increase. Small light-transmitting area and air blowing on the windows can reduce the peak temperature effectively. Cooling the cell window is essential and critical in a long-term running DPAL.

  7. Experimental collaboration for thick concrete structures with alkali-silica reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ezell, N Dianne Bull [ORNL; Hayes, Nolan W. [ORNL; Lenarduzzi, Roberto [ORNL; Clayton, Dwight A. [ORNL; Ma, John [The University of Tennessee, Knoxville; Le Pape, Sihem [ORNL; Le Pape, Yann [ORNL

    2018-04-01

    Alkali-Silica Reaction (ASR) is a reaction that occurs over time in concrete between alkaline cement paste and reactive, non-crystalline silica in aggregates. An expansive gel is formed within the aggregates which results in micro-cracks in aggregates and adjacent cement paste. The reaction requires the presence of water and has been predominantly detected in groundwater-impacted portions of below grade structures, with limited impact to exterior surfaces in above grade structures. ASR can potentially affect concrete properties and performance characteristics such as compressive strength, modulus of elasticity, shear strength, and tensile strength. Since ASR degradation often takes significant amounts of time, developing ASR detection techniques is important to the sustainability and extended operation lifetimes of nuclear power plants (NPPs). The University of Tennessee, Knoxville (UTK) in collaboration with Oak Ridge National Laboratory (ORNL) designed and built an experiment representative of typical NPP structures to study ASR in thick concrete structures.

  8. 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.

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

    Directory of Open Access Journals (Sweden)

    Etxeberria, M.

    2010-02-01

    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.

  10. Characterization of Alkali-Silica Reaction in Concrete Specimens Using a Nonlinear Vibration Technique

    Science.gov (United States)

    Lesnicki, Krzysztof J.; Kim, Jin-Yeon; Kurtis, Kimberly; Jacobs, Laurence J.

    2011-06-01

    A nonlinear vibration technique has been developed for the nondestructive characterization of damage introduced by alkali-silica reactions (ASR) in concrete. The response of a concrete specimen to increasing impact load is analyzed to obtain a relationship between the amplitude of the response and the resonance frequency, and thus the nonlinearity of the specimen. As commonly observed in nonlinear hysteretic materials, the resonance frequency of a specimen decreases with an increasing level of excitation strain. Concrete is a nonlinear hysteretic material to begin with, but the progress of the alkali-silica reaction causes an increase in nonlinearity through the formation of expansive ASR gel and the resulting microcracks. This increase in material nonlinearity is measured with the aforementioned procedure. The specimens used in the research are of varying reactivity with respect to ASR, which is induced in accordance with ASTM C 1293. The results show a substantial difference in nonlinearity between samples with highly reactive aggregate, and those with a non-reactive one. Complementary expansion measurements are also performed to independently verify the reactivity of the aggregate used. These results show that the developed nonlinear vibration technique has the potential to characterize the amount of ASR-induced damage in concrete.

  11. Significance of Alkali-Silica reaction in nuclear safety-related concrete structures

    International Nuclear Information System (INIS)

    Le Pape, Y.; Field, K.G.; Mattus, C.H.; Naus, D.J.; Busby, J.T.; Saouma, V.; Ma, Z.J.; Cabage, J.V.; Guimaraes, M.

    2015-01-01

    Nuclear Power Plant license renewal up to 60 years and possible life extension beyond has established a renewed focus on long-term aging of nuclear generating stations materials, and particularly, on concrete. Large irreplaceable sections of most nuclear generating stations include concrete components. The Expanded Materials Degradation Analysis, jointly performed by the Department of Energy, the U.S. Nuclear Regulatory Commission, the Academia and the Power Generation Industry, identified the need to develop a consistent knowledge base of alkali-silica reaction (ASR) within concrete as an urgent priority (Graves et al., 2014). ASR results in an expansion of Concrete produced by the reaction between alkali (generally from cement), reactive aggregate (like amorphous silica) and water absorption. ASR causes expansion, cracking and loss of mechanical properties. Considering that US commercial reactors in operation enter the age when ASR distress can be potentially observed and that numerous non-nuclear infrastructures (transportation, energy production) in a majority of the States have already experienced ASR-related concrete degradation, the susceptibility and significance of ASR for nuclear concrete structures must be addressed. This paper outlines an on-going research program including the investigation of the possibility of ASR in nuclear power plants, and the assessment of the residual shear bearing capacity of ASR-subjected nuclear structures. (authors)

  12. 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

    2000-01-01

    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...

  13. Effect of Alkali-Silica Reaction on Shear Strength of Reinforced Concrete Structural Members

    Energy Technology Data Exchange (ETDEWEB)

    Hariri-Ardebili, Mohammad [Univ. of Colorado, Boulder, CO (United States); Saouma, Victor [Univ. of Colorado, Boulder, CO (United States); Le Pape, Yann [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-10-01

    Alkali-silica reaction (ASR) was discovered in the early 40s by Stanton (1940) of the California Division of Highways. Since, it has been recognized as a major degradation mechanism for concrete dams and transportation infrastructures. Sometimes described as the ’cancer of concrete’, this internal swelling mechanism causes expansion, cracking and loss of mechanical properties. There are no known economically viable solutions applicable to massive concrete to prevent the reaction once initiated. The e ciency of the mitigation strategies for ASR subjected structures is limited. Several cases of ASR in nuclear generating stations have been disclosed in Japan (Takatura et al. 2005), Canada at Gentilly 2 NPP (Tcherner and Aziz 2009) 1, and more recently, in the United States for which the U.S. Nuclear Regulatory Commission issued Information Notice (IN) 2011-20, ’Concrete Degradation by Alkali Silica Reaction,’ on November 18, 2011, to provide the industry with information related to the ASR identified at Seabrook. Considering that US commercial reactors in operation enter the age when ASR degradation can be visually detected and that numerous non nuclear infrastructures (transportation, energy production) have already experienced ASR in a large majority of the States (e.g., Department of Transportation survey reported by Touma (Touma 2000)), the susceptibility and significance of ASR for nuclear concrete structures must be addressed in the perspective of license renewal and long-term operation beyond 60 years. The aim of this report is to perform an extensive parametric series of 3D nonlinear finite element analyses of three di erent “beam-like” geometries, including two di erent depths, three di erent types of boundary conditions, and four other parameters: namely, the ASR volumetric expansion, the reinforcement ratio, the loss of elastic modulus induced by ASR and the loss of tensile strength caused by ASR.

  14. Study on the influence of Alkali-Silica reaction on structural behavior of reinforced concrete members

    International Nuclear Information System (INIS)

    Murazumi, Y.; Watanabe, Y.; Matsumoto, N.; Mitsugi, S.; Takiguchi, K.; Masuda, Y.

    2005-01-01

    Expansion produced by alkali-silica reaction (ASR) has been observed in the turbine generator foundation of the unit 1, Ikata nuclear power station, Japan. The foundation is a reinforced concrete frame structure. This paper, as a part of the series of investigation and experiments, discusses tests on structural behavior of concrete members affected by ASR. The purpose of the study is to obtain experimental results on the effects of ASR on bending and shear behavior of reinforced concrete beams and shear walls, and compare with the calculated results by present evaluation methods for normal concrete structures For the experiments on bending/shear behavior of beam, bending test models with a small amount of rebar and shear test models with larger amount were made of concrete in which ASR was induced by adding alkali or concrete without ASR. It was found from the results that bending strength of the bending test models and shear strength of the shear test models did not fall, nor was it lower than the calculated strength for concrete members without ASR. In the shear wall test, the two test models were made of either concrete with ASR or one without it. Horizontal load was applied with actuators on the test model fixed on the test floor, while vertical load was applied with oil jacks. The results did not indicate that ASR lowered the stiffness or strength of the wall test models, showing the strength was able to be calculated with the same formula for reinforced concrete wall without ASR. (authors)

  15. Nondestructive analysis of alkali-silica reaction damage in concrete slabs using shear waves

    Science.gov (United States)

    Khazanovich, Lev; Freeseman, Katelyn; Salles, Lucio; Clayton, Dwight

    2018-04-01

    Alkali-silica reaction (ASR) is the chemical reaction that occurs in concrete. It is caused by the interaction of alkalis in Portland cement and silica in aggregates and results in microcracks within the material. This type of damage has been the focus of nondestructive evaluation efforts in recent history, but no work was done on in-situ structures or large-scale samples. To address these limitations, an ultrasonic linear array device, MIRA, was utilized for this research. An experimental investigation was performed on four slabs with various levels of alkali-silica reaction at the Electric Power Research Institute (EPRI) [1]. One-period impulses with a target of 50kHz center frequency were selected in this study. We propose the use of the Hilbert Transform Indicator (HTI) for quantification of ASR damage [2]. A higher HTI value would be indicative of damaged concrete, while a low value represents sound concrete. In general, values below 90 are regarded as an indicator of sound concrete while values above 100 indicate the presence of damage [3]. The ability of the HTI values to distinguish between areas of damaged concrete was evident via the production of color intensity maps. The maps show that the control specimen, was in good condition, while other slabs exhibited higher levels of damage as indicated by the HTI values. It should be noted that extreme damage conditions were not present in any of the slabs. Evaluation of migration-based reconstructions can give a qualitative characterization of large scale or excessive subsurface damage. However, for detection of stochastic damage mechanisms such as freeze-thaw damage, evaluation of the individual time-history data can provide additional information. A comparison of the spatially diverse measurements on several concrete slabs with varying freeze-thaw damage levels is given in this study. Signal characterization scans of different levels of freeze-thaw damage at various transducer spacing is investigated. The

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

    Directory of Open Access Journals (Sweden)

    Keum-Il Song

    2014-01-01

    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.

  17. Carbon fibre-reinforced, alkali-activated slag mortars

    Directory of Open Access Journals (Sweden)

    Garcés, P.

    2007-12-01

    Full Text Available The paper describes the effect of carbon fibre on alkaliactivated slag mortar (AAS mechanical strength, volume stability and reinforcing steel corrosion, compared to its effect on the same properties in Portland cement (PC properties. Mechanical strength and volume stability tests were performed as set out in the respective Spanish UNE standards. The corrosion rate of steel embedded in the specimens studied was determined from polarization resistance analysis. One of the findings of the study performed was that carbon fibre failed to improve AAS or CP mortar strength. As far as volume stability is concerned, the inclusion of carbon fibres in AAS with a liquid/solid ratio of 0.5 reduced drying shrinkage by about 50%. The effect of carbon fibre on PC mortars differed from its effect on AAS mortars. Studies showed that in the presence of carbonation, steel corrosion reached higher levels in carbon-fibre reinforced AAS mortars; the inclusion of 1% carbon fibre improved corrosion resistance perceptibly in these same mortars, however, when exposed to chloride attack.Se ha estudiado el efecto de la incorporación de fibras de carbón en el comportamiento mecánico, estabilidad de volumen y nivel de corrosión de la armadura en morteros de escorias activadas alcalinamente (AAS. Se evalúa la influencia de las fibras de carbón en el comportamiento de morteros alcalinos en comparación con el efecto que producen en morteros de Portland (CP. Los ensayos mecánicos y de estabilidad de volumen se han realizado según lo establecido en la norma UNE que los regula. Se ha utilizado la técnica de la Resistencia a la Polarización para determinar la velocidad de corrosión del acero embebido en las muestras estudiadas. Como consecuencia del estudio realizado, se ha podido concluir que la adición de fibras de carbón a morteros de AAS y CP no mejora las características resistentes de los mismos. En relación con la estabilidad de volumen, la incorporación de

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

    KAUST Repository

    Tiecher, Francieli

    2012-11-01

    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.

  19. Influence of alkali-silica reaction on the physical, mechanical, and structural behaviour of reinforced concrete

    DEFF Research Database (Denmark)

    Barbosa, Ricardo Antonio

    Alkali-silica reaction (ASR) is one of the major concrete deterioration mechanisms in the world. Cracking in concrete structures due to ASR has been observed worldwide. In Denmark numerous concrete structures have been built with a critical amount of ASR-reactive aggregate, mostly as porous opaline...... load-carrying capacity. The decisions to demolish and reconstruct these bridges have been based on visual appearance of drilled concrete cores and rough estimates of their residual loadcarrying capacity. Research into the mechanical properties of drilled cores and the residual load-carrying capacity...... the strength in the direction parallel to ASR cracks. Consequently, evaluation of compressive strength based on vertically drilled cores (ASR cracks oriented perpendicular to the load direction) can be rather conservative. It is argued that the difference in compressive strength for the two crack orientations...

  20. Effect of moisture conditions and transfers on alkali silica reaction damaged structures

    International Nuclear Information System (INIS)

    Multon, Stephane; Toutlemonde, Francois

    2010-01-01

    The aim of this paper is to point out the water driving effect on the alkali silica reaction (ASR) expansion and particularly when modifications of moisture conditions occur. After being submitted to a unidirectional moisture gradient during 14 months, the upper faces of ASR reactive beams were covered by water for 9 months. This late water supply on the upper face rapidly produced large expansions, which mainly occurred along the transverse and the vertical directions resulting in large longitudinal cracks. Companion nonreactive specimens were kept in the same environmental conditions in order to quantify the basic characteristics of moisture-dependent expansive behaviour of the material. The paper focuses on the effects of late water supply or late drying on already ASR-damaged concrete, which is a significant concern for real-life structures. Both structural effects of late water supply on ASR progress in already damaged structures and interpretation of such phenomena are described.

  1. Alkali resistant Ni-loaded yolk-shell catalysts for direct internal reforming in molten carbonate fuel cells

    Science.gov (United States)

    Jang, Won-Jun; Hong, Young Jun; Kim, Hak-Min; Shim, Jae-Oh; Roh, Hyun-Seog; Kang, Yun Chan

    2017-06-01

    A facile and scalable spray pyrolysis process is applied to synthesize multi-shelled Ni-loaded yolk-shell catalysts on various supports (Al2O3, CeO2, ZrO2, and La(OH)3). The prepared catalysts are applied to direct internal reforming (DIR) in a molten carbonate fuel cell (MCFC). Even on exposure to alkali hydroxide vapors, the Ni-loaded yolk-shell catalysts remain highly active for DIR-MCFCs. The Ni@Al2O3 microspheres show the highest conversion (92%) of CH4 and the best stability among the prepared Ni-loaded yolk-shell catalysts. Although the initial CH4 conversion of the Ni@ZrO2 microspheres is higher than that of the Ni@CeO2 microspheres, the Ni@CeO2 microspheres are more stable. The catalytic performance is strongly dependent on the surface area and acidity and also partly dependent on the reducibility. The acidic nature of Al2O3 combined with its high surface area and yolk-shell structure enhances the adsorption of CH4 and resistance against alkali poisoning, resulting in efficient DIR-MCFC reactions.

  2. Structural and electronic properties of alkali-doped single-walled carbon nanotubes

    Science.gov (United States)

    Nemes, Norbert Marcel

    In this thesis, we study the properties of alkali doped single walled carbon nanotubes (SWNT). SWNT are crystallized into ropes, which display the one-dimensional electronic properties of the constituent nanotubes. Using x-ray diffraction, we show that the alkali atoms invade the channels in the triangular rope lattice and determine the structure of the doped ropes. We show that the diffraction profile of the doped SWNT is best described by a model where the alkali ions surround each tube in an ordered fashion by dilating the channels. Alkali doped SWNT exhibit colors similar to alkali doped graphite (GIC). We study their electronic structure with IR reflectivity; the alkali dopants donate their valence electron to the SWNT host, so the free carrier concentration increases, shifting the Drude-edge into the visible spectral range. This is accompanied by a large shift of the Fermi-level, so the characteristic transitions between the 1D van Hove singularities of the undoped SWNT diminish. The presence of the alkali ions around the SWNT breaks the translational symmetry and increases coupling between parallel tubes within ropes. We find that the momentum relaxation time shortens as the ropes become more three dimensional. We also find that alkali disorder contributes to the scattering. In p-type, HNO3 doped SWNT, the charge transfer is smaller; only the first subband of the semiconducting tubes gets depleted, shown by the disappearance of the first van Hove transition. This indicates a Fermi-level shift of ˜0.3 eV. The reflectivity has structure at low energy, which moves the Drude-peak to a sharp, intense peak at 0.1 eV in the optical conductivity, reminiscent of quasi-1D TTF-TCNQ. The DC conductivity also increases ˜80-fold during doping. The low temperature divergence of undoped SWNT disappears in alkali doped SWNT. However, we find that oxygen can modulate the low-T divergence. After outgassing, the divergence becomes ˜10 times stronger. We interpret the low

  3. The influence of alkali metal impurities on the uranium dioxide hydrofluorination reaction

    International Nuclear Information System (INIS)

    Ponelis, A.A.

    1989-01-01

    The effect alkali metal impurities (sodium and potassium) in the uranium dioxide (UO 2 ) feed material have on the conversion to uraniumtetrafluoride (UF 4 ) was examined. A direct correlation exists between impurity level and sintering with concomitant reduced conversion. The sintering mechanism is attributable to decreased specific surface area. The typical 'die-off' of reaction or conversion can be explained in terms of increased particle growth rather than an arbitray zero porosity function. Hydrofluorination temperatures varied from 250 to 650 degrees C using pellets varying in size from 0.42 mm to 10 mm. Scanning electron microscope photographs show clearly the particle or grain growth in the pellet as well as the increased size with impurity level. A new dimensionless constant, N KP , is defined to facilitate explanation of the reaction as a function of pellet radius. N KP is defined as the ratio of pellet diffusion resistance to particle diffusion resistance of the reacting HF gas. At high values of this number (N KP >40) the conversion is limited to the outer periphery of the pellet while at low values (N KP KP at higher reaction temperatures which means that the particle diffusion resistance increases with increasing impurity level and results in easier sintering of these materials. 53 refs., 206 figs., 94 tabs

  4. Interactions of alkali metals and electrolyte with cathode carbons

    Energy Technology Data Exchange (ETDEWEB)

    Naas, Tyke

    1997-12-31

    The Hall-Heroult process for electrolytic reduction of alumina has been the only commercial process for production of primary aluminium. The process runs at high temperature and it is important to minimize the energy consumption. To save energy it is desirable to reduce the operating temperature. This can be achieved by adding suitable additives such as LiF or KF to the cryolitic electrolyte. This may conflict with the objective of extending the lifetime of the cathode linings of the cell as much as possible. The thesis investigates this possibility and the nature of the interactions involved. It supports the hypothesis that LiF-additions to the Hall-Heroult cell electrolyte is beneficial to the carbon cathode performance because the diminished sodium activity reduces the sodium induced stresses during the initial period of electrolysis. The use of KF as an additive is more dangerous, but the results indicate that additions up to 5% KF may be tolerated in acidic melts with semigraphitic or graphitic cathodes with little risk of cathode problems. 153 refs., 94 figs., 30 tabs.

  5. The chemistry of the liquid alkali metals

    International Nuclear Information System (INIS)

    Addison, C.C.

    1984-01-01

    A study of liquid alkali metals. It encourages comparison with molecular solvents in chapter covering the nature and reactivity of dissolved species, solvation, solubility and electrical conductivity of solutions. It demonstrates lab techniques unique to liquid alkali metals. It discusses large-scale applications from storage batteries to sodium-cooled reactors and future fusion reactors, and associated technological problems. Contents: Some Basic Physical and Chemical Properties; Manipulation of the Liquids; The Chemistry of Purification Methods; Species Formed by Dissolved Elements; Solubilities and Analytical Methods; Alkali Metal Mixtures; Solvation in Liquid Metal; Reactions Between Liquid Alkali Metals and Water; Reactions of Nitrogen with Lithium and the Group II Metals in Liquid Sodium; The Formation, Dissociation and Stability of Heteronuclear Polyatomic Anions; Reactions of the Liquid Alkali Metals and Their Alloys with Simple Alipatic Hydrocarbons; Reactions of the Liquid Alkali Metals with Some Halogen Compounds; Hydrogen, Oxygen and Carbon Meters; Surface Chemistry and Wetting; Corrosion of Transition Metals by the Liquid Alkali Metals; Modern Applications of the Liquid Alkali Metals

  6. Influence of the carbonate-free clay calcination temperature and curing conditions on the properties of alkali-activated mortar

    OpenAIRE

    Bumanis, Girts; Bajare, Diana; Korjakins, Aleksandrs

    2014-01-01

    Alkali-activated materials (AAMs) are one of the most perspective alternatives to the traditional Portland cement based materials. AAMs could reduce the environmental pollution and greenhouse gas emission due to the lower heat consumption in production (up to 80% compared to the ordinary Portland cement). In the current research alkali-activated mortar was developed from the locally available low-carbonate Illite clay. Experimental work consisted of Illite clay calcination at different temper...

  7. Cascade enzymatic reactions for efficient carbon sequestration.

    Science.gov (United States)

    Xia, Shunxiang; Zhao, Xueyan; Frigo-Vaz, Benjamin; Zheng, Wenyun; Kim, Jungbae; Wang, Ping

    2015-04-01

    Thermochemical processes developed for carbon capture and storage (CCS) offer high carbon capture capacities, but are generally hampered by low energy efficiency. Reversible cascade enzyme reactions are examined in this work for energy-efficient carbon sequestration. By integrating the reactions of two key enzymes of RTCA cycle, isocitrate dehydrogenase and aconitase, we demonstrate that intensified carbon capture can be realized through such cascade enzymatic reactions. Experiments show that enhanced thermodynamic driving force for carbon conversion can be attained via pH control under ambient conditions, and that the cascade reactions have the potential to capture 0.5 mol carbon at pH 6 for each mole of substrate applied. Overall it manifests that the carbon capture capacity of biocatalytic reactions, in addition to be energy efficient, can also be ultimately intensified to approach those realized with chemical absorbents such as MEA. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Experimental simulation of the alkali-carbonate metasomatism

    Science.gov (United States)

    Gorbachev, Nikolay; Kostyuk, Anastasia

    2010-05-01

    Close association of alkaline and ultrabasic rocks, carbonatites, apatitic and sulfidic mineralization, features of structure testify about mantle a source and the important role alcalic-carbonaceous fluids in genesis of these rocks. Formation alkaline silicate, carbonaceous and sulfidic melts, phase relationship, behaviour of the ti-tan, phosphorus, sulphur and zircon has been experimentally studied at pressure 3.9 GPa, temperature 1250°С in system peridotit-basalt (eclogite)-alcalic-carbonaceous fluid with additives in quality acces-sory minerals, apatite, nickel-containing pyrrhotite, ilmenite, zircon. Experiments were carried out using of apparatus high pressure (piston cilinder and anvil with hole) by a quenching technique. It was used two ampoules (platinum and peridotite, content basalt powder) method. Duration of experiments was 6-8 hours. Products of experiments were studied on electronic scanning microscope Tescan VEGA TS 5130MM with YAG detector of secondary and reflected elec-tron and energy-dispersive the x-ray microanalyzer with semi-conductor Si (Li) detector INCA Energy 350. The morphology, structure and relationship of glass, inclusions of carbonatic and sulfidic globules specify in existence in the conditions of experiment immiscibility silicate, carbonate and sulfidic melts. The composition of silicate melt answered phonolite, carbonaceous melts it is essential calciferous composition with an impurity of alkaline metals and silicate components. Solubility of zircon in silicate melts reached 0.8 wt.% ZrO2, in co-existing carbonaceous melt - 1.5 wt.%. Concentration TiO2 and Р2О5 in silicate melt reached 2 wt.%, in carbonaceous melt - 1.7 wt.% TiO2 and up to 14 wt.% Р2О5. Concentration of sulphur in these melts did not exceed 0.2 мас. %. From minerals of liqudus the main concentrators of the titan and phosphorus were the X-phase and phlogopite - up to 8 wt.% TiO2 and up to 3 wt.% Р2О5 in the X-phase, up to 6 wt. % TiO2 and to 2.5 wt. %

  9. 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)

    2015-09-01

    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.

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

    International Nuclear Information System (INIS)

    Agarwal, Vivek; Cai, Guowei; Gribok, Andrei V.; Mahadevan, Sankaran

    2015-01-01

    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.

  11. Measurement of alkali-silica reaction progression by ultrasonic waves attenuation

    International Nuclear Information System (INIS)

    Saint-Pierre, Francois; Rivard, Patrice; Ballivy, Gerard

    2007-01-01

    Development of non-destructive methods, developed specifically for assessing the damage induced by alkali-silica reaction (ASR) in concrete structures, is needed in order to carry out a systematic evaluation of the concrete condition. The aim of this study is to monitor the evolution of the ASR-damage in laboratory with concrete samples with ultrasonic pulse velocity and attenuation of ultrasonic waves methods. For this study, results of both methods were compared with expansion and mass variation. One reactive concrete mixture was made with reactive aggregate, and one other mixture, incorporating non-reactive aggregate, was made as a control. Specimens were kept at 38 deg. C in a 1 mol l -1 NaOH solution to accelerate the reaction. Attenuation of transmitted ultrasonic waves appeared to be more appropriate for the evaluation of ASR-damage compared with pulse velocity. The attenuation of accelerated reactive concrete cylinders increased by 90% after 1 year while it increased by 40% for the non-reactive concrete used as a control. Major part of the attenuation increase in the non-reactive concrete is due to liquid absorption. This work suggests that in-situ non-destructive techniques based on ultrasonic wave attenuation, like ultrasonic attenuation tomography, should be developed in order to evaluate the development of ASR in concrete structures. Petrographic examination confirmed that damage to concrete is associated with ASR

  12. Method for the safe disposal of alkali metal

    Science.gov (United States)

    Johnson, Terry R.

    1977-01-01

    Alkali metals such as those employed in liquid metal coolant systems can be safely reacted to form hydroxides by first dissolving the alkali metal in relatively inert metals such as lead or bismuth. The alloy thus formed is contacted with a molten salt including the alkali metal hydroxide and possibly the alkali metal carbonate in the presence of oxygen. This oxidizes the alkali metal to an oxide which is soluble within the molten salt. The salt is separated and contacted with steam or steam-CO.sub.2 mixture to convert the alkali metal oxide to the hydroxide. These reactions can be conducted with minimal hydrogen evolution and with the heat of reaction distributed between the several reaction steps.

  13. Method for the safe disposal of alkali metal

    International Nuclear Information System (INIS)

    Johnson, T.R.

    1977-01-01

    Alkali metals such as those employed in liquid metal coolant systems can be safely reacted to form hydroxides by first dissolving the alkali metal in relatively inert metals such as lead or bismuth. The alloy thus formed is contacted with a molten salt including the alkali metal hydroxide and possibly the alkali metal carbonate in the presence of oxygen. This oxidizes the alkali metal to an oxide which is soluble within the molten salt. The salt is separated and contacted with steam or steam--CO 2 mixture to convert the alkali metal oxide to the hydroxide. These reactions can be conducted with minimal hydrogen evolution and with the heat of reaction distributed between the several reaction steps. 5 claims, 1 figure

  14. Use of Fly Ash in the Mitigation of Alkali-Silica Reaction in Concrete

    Science.gov (United States)

    2010-11-12

    Leemann, A., B. Lothenbach, and C. Thalmann, Influence of superplasticizers on pore solution composition and on expansion of concrete due to alkali...B. Lothenbach, and C. Thalmann, Influence of superplasticizers on pore solution composition and on expansion of concrete due to alkali-silica

  15. An alkali treating strategy for the colloidization of graphitic carbon nitride and its excellent photocatalytic performance.

    Science.gov (United States)

    Cheng, Fuxing; Yan, Jing; Zhou, Chenjuan; Chen, Binhe; Li, Peiran; Chen, Zhi; Dong, Xiaoping

    2016-04-15

    The colloid of graphitic carbon nitride (g-C3N4) was of great importance for practical application. Herein we introduced an alkali treatment route to efficiently colloidize g-C3N4 under mild conditions by destroying the hydrogen bonds between linearly polymeric melon chains and hydrolyzing partial C−NH−C bonds linked two tri-s-triazine units. The obtained colloidal suspension was extremely stable due to its negative charges on surface, and the particle size of several hundred nanometers and the nanobelt-like morphology were revealed by electron microscopy and dynamic light scattering technologies. The structural, optical and functional group analysis demonstrated that the structure of CN heterocycles was preserved after the alkali treatment, and the produced colloidal g-C3N4 can be re-assembled by an electrostatic interaction. Moreover, contributing to the reduced electron-hole recombination, the photocatalytic performance of restacked carbon nitride colloids had more enhanced photocatalytic performance than bulk g-C3N4. Copyright © 2016 Elsevier Inc. All rights reserved.

  16. A Demonstration of Concrete Structural Health Monitoring Framework for Degradation due to Alkali-Silica Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mahadevan, Sankaran [Idaho National Lab. (INL), Idaho Falls, ID (United States); Agarwal, Vivek [Idaho National Lab. (INL), Idaho Falls, ID (United States); Neal, Kyle [Idaho National Lab. (INL), Idaho Falls, ID (United States); Nath, Paromita [Idaho National Lab. (INL), Idaho Falls, ID (United States); Bao, Yanqing [Idaho National Lab. (INL), Idaho Falls, ID (United States); Cai, Guowei [Idaho National Lab. (INL), Idaho Falls, ID (United States); Orme, Peter [Idaho National Lab. (INL), Idaho Falls, ID (United States); Adams, Douglas [Idaho National Lab. (INL), Idaho Falls, ID (United States); Kosson, David [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2016-04-01

    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 ongoing research project is seeking to develop a probabilistic framework for health diagnosis and prognosis of aging concrete structures in a nuclear power plant that is subjected to physical, chemical, environment, and mechanical degradation. The proposed framework consists of four elements: monitoring, data analytics, uncertainty quantification and prognosis. This report focuses on degradation caused by ASR (alkali-silica reaction). Controlled specimens were prepared to develop accelerated ASR degradation. Different monitoring techniques – thermography, digital image correlation (DIC), mechanical deformation measurements, nonlinear impact resonance acoustic spectroscopy (NIRAS), and vibro-acoustic modulation (VAM) -- were used to detect the damage caused by ASR. Heterogeneous data from the multiple techniques was used for damage diagnosis and prognosis, and quantification of the associated uncertainty using a Bayesian network approach. Additionally, MapReduce technique has been demonstrated with synthetic data. This technique can be used in future to handle large amounts of observation data obtained from the online monitoring of realistic structures.

  17. Modeling Time-Dependent Behavior of Concrete Affected by Alkali Silica Reaction in Variable Environmental Conditions.

    Science.gov (United States)

    Alnaggar, Mohammed; Di Luzio, Giovanni; Cusatis, Gianluca

    2017-04-28

    Alkali Silica Reaction (ASR) is known to be a serious problem for concrete worldwide, especially in high humidity and high temperature regions. ASR is a slow process that develops over years to decades and it is influenced by changes in environmental and loading conditions of the structure. The problem becomes even more complicated if one recognizes that other phenomena like creep and shrinkage are coupled with ASR. This results in synergistic mechanisms that can not be easily understood without a comprehensive computational model. In this paper, coupling between creep, shrinkage and ASR is modeled within the Lattice Discrete Particle Model (LDPM) framework. In order to achieve this, a multi-physics formulation is used to compute the evolution of temperature, humidity, cement hydration, and ASR in both space and time, which is then used within physics-based formulations of cracking, creep and shrinkage. The overall model is calibrated and validated on the basis of experimental data available in the literature. Results show that even during free expansions (zero macroscopic stress), a significant degree of coupling exists because ASR induced expansions are relaxed by meso-scale creep driven by self-equilibriated stresses at the meso-scale. This explains and highlights the importance of considering ASR and other time dependent aging and deterioration phenomena at an appropriate length scale in coupled modeling approaches.

  18. Microscopy and Cathodoluminescence Spectroscopy Characterization of Quartz Exhibiting Different Alkali-Silica Reaction Potential.

    Science.gov (United States)

    Kuchařová, Aneta; Götze, Jens; Šachlová, Šárka; Pertold, Zdeněk; Přikryl, Richard

    2016-02-01

    Different quartz types from several localities in the Czech Republic and Sweden were examined by polarizing microscopy combined with cathodoluminescence (CL) microscopy, spectroscopy, and petrographic image analysis, and tested by use of an accelerated mortar bar test (following ASTM C1260). The highest alkali-silica reaction potential was indicated by very fine-grained chert, containing significant amounts of fine-grained to cryptocrystalline matrix. The chert exhibited a dark red CL emission band at ~640 nm with a low intensity. Fine-grained orthoquartzites, as well as fine-grained metamorphic vein quartz, separated from phyllite exhibited medium expansion values. The orthoquartzites showed various CL of quartz grains, from blue through violet, red, and brown. Two CL spectral bands at ~450 and ~630 nm, with various intensities, were detected. The quartz from phyllite displayed an inhomogeneous dark red CL with two CL spectral bands of low intensities at ~460 and ~640 nm. The massive coarse-grained pegmatite quartz from pegmatite was assessed to be nonreactive and displayed a typical short-lived blue CL (~480 nm). The higher reactivity of the fine-grained hydrothermal quartz may be connected with high concentrations of defect centers, and probably with amorphized micro-regions in the quartz, respectively; indicated by a yellow CL emission (~570 nm).

  19. Study on the influence of Alkali-Silica reaction on mechanical properties of reinforced concrete members

    International Nuclear Information System (INIS)

    Murazumi, Y.; Hosokawa, T.; Matsumoto, N.; Mitsugi, S.; Takiguchi, K.; Masuda, Y.

    2005-01-01

    Expansion produced by alkali-silica reaction (ASR) has been observed in the turbine generator foundation of the unit 1, Ikata nuclear power station, Japan. The foundation is a reinforced concrete frame structure. This paper, as a part of the series of investigation and experiments, discusses tests on mechanical properties of concrete members affected by ASR. The purpose of the study is to investigate the influence of expansion rate by ASR, reinforcing ratio, specimen dimension on elastic modulus, and compressive strength of concrete; to get appropriate input data for analysis model which is to be carried out to simulate actual behavior of the turbine foundation. Compressive tests were carried out on concrete cylinder test pieces, core samples, and reinforced concrete member specimens. From the results of the test on the member specimens, the specimens with more reinforcement ratio showed less expansion and larger elastic modulus. It is considered that restraint by rebars made the expansion small and restrained the drop of the elastic modulus by ASR. Restraint by rebars on ASR specimens did not affect much compressive strength. The data helped to fix input material properties for the analyses representing the actual foundation conditions. (authors)

  20. Vibration measurement and simulation analysis on a reinforced concrete structure with alkali-silica reaction

    International Nuclear Information System (INIS)

    Murazumi, Y.; Watanabe, Y.; Hosokawa, T.; Takakazu Ishi; Katsuki Takiguchi; Masuda, Y.

    2005-01-01

    This paper discusses vibration test and measurement of elastic wave velocity, and simulation analyses on the vibration test concerning the turbine generator foundation of the Ikata nuclear power station unit no. 1, Japan, where expansion produced by alkali-silica reaction (ASR) has been observed. Under the vibration test, vertical excitation test of the beams and microtremor measurement were conducted to estimate Eigen frequency/mode and examine time-dependent change of the stiffness of the foundation by comparing with the results in the previous test done in the same way. Elastic wave velocity was measured to observe the difference of material properties among places of the foundation. Simulation analyses on the vibration test were done to estimate the elastic modulus of the members where ASR is induced. We obtained the following conclusions: (1) The time-dependant change of the stiffness and ASR have very low effect on the entire structure of the unit no.1 (2) It is estimated that ASR has not developed since 1989 because the reduction of the Eigen frequencies of the foundation is small. (3) The reduction of the elastic modulus of the table-deck stands out by comparison of the elastic modulus of the unit no.1 and no.2 from the measurement of elastic wave velocity. (4) The elastic modulus ratio of the members with ASR to the members without ASR is estimated from 0.5 to 0.6 by the simulation analyses. (authors)

  1. A Demonstration of Concrete Structural Health Monitoring Framework for Degradation due to Alkali-Silica Reaction

    International Nuclear Information System (INIS)

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

    2016-01-01

    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 ongoing research project is seeking to develop a probabilistic framework for health diagnosis and prognosis of aging concrete structures in a nuclear power plant that is subjected to physical, chemical, environment, and mechanical degradation. The proposed framework consists of four elements: monitoring, data analytics, uncertainty quantification and prognosis. This report focuses on degradation caused by ASR (alkali-silica reaction). Controlled specimens were prepared to develop accelerated ASR degradation. Different monitoring techniques - thermography, digital image correlation (DIC), mechanical deformation measurements, nonlinear impact resonance acoustic spectroscopy (NIRAS), and vibro-acoustic modulation (VAM) -- were used to detect the damage caused by ASR. Heterogeneous data from the multiple techniques was used for damage diagnosis and prognosis, and quantification of the associated uncertainty using a Bayesian network approach. Additionally, MapReduce technique has been demonstrated with synthetic data. This technique can be used in future to handle large amounts of observation data obtained from the online monitoring of realistic structures.

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

    OpenAIRE

    James Sarfo-Ansah; Eugene Atiemo

    2015-01-01

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

    KAUST Repository

    Liang, Yin

    2014-03-24

    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.

  4. Quantitative diagnosis and prognosis framework for concrete degradation due to alkali-silica reaction

    Science.gov (United States)

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

    2017-02-01

    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.

  5. Study of absorption spectra for alkali and alkaline earth metal salts in flameless atomic absorption spectrometry using a carbon tube atomizer

    International Nuclear Information System (INIS)

    Yasuda, Seiji; Kakiyama, Hitoo

    1975-01-01

    Absorption spectra of various salts such as alkali metal salts, alkaline earth dichlorides, and ammonium halides were investigated and absorptions of some molecular species produced in the carbon tube were identified. The aqueous solution (20 μl) containing 1.0 mg/ml of each salt was placed in the carbon tube atomizer and heated in a similar manner to usual flameless atomic absorption method. D 2 -lamp was used as a continuous light source and argon gas was employed as an inert sheath gas. The spectra were obtained over the range of wavelength 200 to 350 nm. When alkali halides were feeded, the absorption spectra agreed with those of alkali halide vapors. Therefore, in such cases vapors of the alkali halides were probably produced by the sublimation or vaporization in the atomizer. The spectra of alkali perchlorates were considered to be those of alkali chlorides produced by the pyrolysis of the perchlorates in the atomizer. The absorptions of alkaline earth chlorides below 250 nm were probably due to their gaseous states. Sulfur dioxide was found to be produced by the pyrolysis of alkali sulfates, bisulfates and sulfites in the atomizer, Alkali phosphates and pyrophosphates gave almost identical spectra below 300 nm. Gamma band spectrum of nitrogen monoxide was observed from 200 to 240 nm during ashing at bout 330 0 C for alkali nitrates and nitrites. Ammonia vapor was produced from ammonium halides during drying at about 170 0 C. Although the absorptions of alkali carbonates and hydroxides were almost undetectable, the same spectra as those of alkali halides were observed by the addition of ammonium halides to the solutions of alkali compounds. This shows that alkali halides are produced in the atomizer by the addition of halide ions. (auth.)

  6. Comparative study of the alkali-silica reaction (ASR in granitic aggregates

    Directory of Open Access Journals (Sweden)

    Velasco-Torres, A.

    2010-06-01

    Full Text Available The reaction between certain reactive components of aggregates (like opal and metaestable silica and concrete pore solution is well documented. Nevertheless, in this study it has been shown that some aggregates, like granite, could develop a rapid or slow alkali-silica reaction (ASR depending on the deleterious component involved. Mortar bars were cast with two granitic aggregates extracted from concrete cores drilled in two Spanish Dams affected by ASR, being classified as granitic rocks. The main difference between them is the reactive component: microcrystalline quartz in one case and strained and microcracked quartz in the other case. A petrographic examination was carried out in the mortar bars. Thin sections were cut and the alkalisilica gel was stained for an easier detection. Then, the thin sections were examinated with a stereomicroscope comparing the differences in the progress of the ASR for both aggregates. It can be concluded that the main mechanism of formation and storage of gel is associated to the micro-cracks instead of the subgrain boundaries.

    La reacción entre los componentes de la fase intersticial del hormigón y áridos con minerales como el ópalo o la sílice metaestable, se encuentra bien documentada. Sin embargo, en este estudio, se ha detectado que dentro de un mismo tipo de roca, como es el granito, puede haber diferencias en el tipo de reacción (lenta o rápida dependiendo del componente reactivo que aparezca en la misma. Se han fabricado barras de mortero con los áridos extraídos de dos presas españolas afectadas por la reacción álcali-sílice. Estos áridos son rocas graníticas y la diferencia entre ambos reside en que una de las muestras contiene cuarzo microcristalino como componente reactivo y, la otra, cuarzo deformado. Mediante el estudio petrográfico de barras de mortero y el teñido del gel álcali-sílice se ha podido observar la evolución y progreso de la reacción para cada

  7. Chemo-mechanical modeling for prediction of alkali silica reaction (ASR) expansion

    International Nuclear Information System (INIS)

    Multon, Stephane; Sellier, Alain; Cyr, Martin

    2009-01-01

    The effect of the size of the aggregate on ASR expansion has already been well illustrated. This paper presents a microscopic model to analyze the development of ASR expansion of mortars containing reactive aggregate of different sizes. The attack of the reactive silica by alkali was determined through the mass balance equation, which controls the diffusion mechanism in the aggregate and the fixation of the alkali in the ASR gels. The mechanical part of the model is based on the damage theory in order to assess the decrease of stiffness of the mortar due to cracking caused by ASR and to calculate the expansion of a Representative Elementary Volume (REV) of concrete. Parameters of the model were estimated by curve fitting the expansions of four experimental mortars. The paper shows that the decrease of expansion with the size of the aggregate and the increase of the expansion with the alkali content are reproduced by the model, which is able to predict the expansions of six other mortars containing two sizes of reactive aggregate and cast with two alkali contents.

  8. Prestressing of reinforcing bars in concrete slabs due to concrete expansion induced by Alkali-Silica Reaction

    DEFF Research Database (Denmark)

    Gustenhoff Hansen, Søren; Antonio Barbosa, Ricardo; Hoang, Linh Cao

    2017-01-01

    Alkali-silica reactions (ASR) in concrete bridges have been a major concern worldwide for many decades. In Denmark, several bridges are severely damaged due to ASR and over 600 bridges have the potential to develop ASR in the future. The majority of these bridges are slab-bridges. Despite the many...... based on relatively small laboratory specimens or beams and structural elements with shear reinforcement. This paper provides the first plausible explanation on why these results are unrepresentative for slab elements. Additionally, this paper quantifies the prestressing effect by analysing full...

  9. Chemical reactions confined within carbon nanotubes.

    Science.gov (United States)

    Miners, Scott A; Rance, Graham A; Khlobystov, Andrei N

    2016-08-22

    In this critical review, we survey the wide range of chemical reactions that have been confined within carbon nanotubes, particularly emphasising how the pairwise interactions between the catalysts, reactants, transition states and products of a particular molecular transformation with the host nanotube can be used to control the yields and distributions of products of chemical reactions. We demonstrate that nanoscale confinement within carbon nanotubes enables the control of catalyst activity, morphology and stability, influences the local concentration of reactants and products thus affecting equilibria, rates and selectivity, pre-arranges the reactants for desired reactions and alters the relative stability of isomeric products. We critically evaluate the relative advantages and disadvantages of the confinement of chemical reactions inside carbon nanotubes from a chemical perspective and describe how further developments in the controlled synthesis of carbon nanotubes and the incorporation of multifunctionality are essential for the development of this ever-expanding field, ultimately leading to the effective control of the pathways of chemical reactions through the rational design of multi-functional carbon nanoreactors.

  10. Reactions on carbon anodes in aluminium electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Eidet, Trygve

    1997-12-31

    The consumption of carbon anodes and energy in aluminium electrolysis is higher than what is required theoretically. This thesis studies the most important of the reactions that consume anode materials. These reactions are the electrochemical anode reaction and the airburn and carboxy reactions. The first part of the thesis deals with the kinetics and mechanism of the electrochemical anode reaction using electrochemical impedance spectroscopy. The second part deals with air and carboxy reactivity of carbon anodes and studies the effects of inorganic impurities on the reactivity of carbon anodes in the aluminium industry. Special attention is given to sulphur since its effect on the carbon gasification is not well understood. Sulphur is always present in anodes, and it is expected that the sulphur content of available anode cokes will increase in the future. It has also been suggested that sulphur poisons catalyzing impurities in the anodes. Other impurities that were investigated are iron, nickel and vanadium, which are common impurities in anodes which have been reported to catalyze carbon gasification. 88 refs., 92 figs., 24 tabs.

  11. Correction: A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

    Science.gov (United States)

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

    2016-12-22

    Correction for 'A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide' by Chee Koon Ng et al., Chem. Commun., 2016, 52, 11842-11845.

  12. Alkali aggregate reactivity in concrete structures in western Canada

    International Nuclear Information System (INIS)

    Morgan, D.R.; Empey, D.

    1989-01-01

    In several regions of Canada, particularly parts of Ontario, Quebec and the Maritime Provinces, research, testing and evaluation of aged concrete structures in the field has shown that alkali aggregate reactivity can give rise to pronounced concrete deterioration, particularly in hydraulic structures subjected to saturation or alternate wetting and drying such as locks, dams, canals, etc. Concrete deterioration is mainly caused by alkali-silica reactions and alkali-carbonate reactions, but a third type of deterioration involves slow/late expanding alkali-silicate/silica reactivity. The alkalies NaOH and KOH in the concrete pore solutions are mainly responsible for attack on expansive rocks and minerals in concrete. Methods for evaluating alkali-aggregate reaction potential in aggregates, and field and laboratory methods for detecting deterioration are discussed. Examples of alkali-aggregate reactions in structures is western Canada are detailed, including a water reservoir at Canadian Forces Base Chilliwack in British Columbia, the Oldman River diversion and flume, the Lundbreck Falls Bridge, and the St Mary's Reservoir spillway, all in southern Alberta. Mitigative measures include avoidance of use of suspect aggregates, but if this cannot be avoided it is recommended to keep the total alkalies in the concrete as low as possible and minimize opportunities for saturation of concrete by moisture. 16 refs., 19 figs., 1 tab

  13. Effects of Alkali and Counter Ions in Sn-Beta Catalyzed Carbohydrate Conversion

    DEFF Research Database (Denmark)

    Elliot, Samuel G.; Tolborg, Søren; Madsen, Robert

    2018-01-01

    and are herein addressed experimentally through kinetic experiments and isotope tracking. Alkali ions have a differential effect in competing reaction pathways: they promote the rate of carbon-carbon bond breakage of carbohydrate substrates, but decrease the rates of competing dehydration pathways. Further......Alkali ions have been shown to strongly influence the catalytic behavior of stannosilicates in the conversion of carbohydrates. An effect of having alkali ions present is a pronounced increase in selectivity towards methyl lactate. Mechanistic details of this effect have remained obscure...... addition of alkali inhibits activity of Sn-Beta in all major reaction pathways. The alkali effects on product distributions and on rates of product formation are similar, thus pointing to a kinetic reaction control and to irreversible reaction steps in the main pathways. Additionally, an effect...

  14. ALKALI FUSION OF ROSETTA ZIRCON

    International Nuclear Information System (INIS)

    DAHER, A.

    2008-01-01

    The decomposition of Rosetta zircon by fusion with different types of alkalis has been investigated. These alkalis include sodium hydroxide, potassium hydroxide and eutectic mixture of both. The influences of the reaction temperature, zircon to alkalis ratio, fusion time and the stirring of the reactant on the fusion reaction have been evaluated. The obtained results favour the decomposition of zircon with the eutectic alkalis mixture by a decomposition efficiency of 96% obtained at 500 0 C after one hour

  15. Diffusion with chemical reaction: An attempt to explain number density anomalies in experiments involving alkali vapor

    Science.gov (United States)

    Snow, W. L.

    1974-01-01

    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.

  16. Microwave NDE method for health-monitoring of concrete structures containing alkali-silica reaction (ASR) gel

    Science.gov (United States)

    Hashemi, A.; Hatfield, S.; Donnell, K. M.; Zoughi, R.; Kurtis, K. E.

    2014-02-01

    The presence of reactive aggregates combined with sufficient moisture and concentration of alkalis are the three basic requirements for damage due alkali-silica reaction (ASR) gel formation and expansion in concrete. For health-monitoring of concrete structures, and in order to investigate the potential for detecting ASR gel formation in existing structures, one potential technique involves studying changes in the temporal complex dielectric constant of concrete structures. In this paper, a microwave nondestructive testing approach is proposed which involves soaking two hardened mortar samples and measuring the change in their temporal complex dielectric constant in order to distinguish between the sample containing ASR gel and the one devoid of it. Part of the free water becomes bound in the sample containing ASR gel and since a portion of the microcracks in this sample contain ASR gel, the rate of evaporation of water of the two samples is expected to be different. The complex dielectric constant of the samples is significantly dependent upon the volumetric level and movement (in and out of the samples) of free water. Therefore, studying the relative different temporal rate of change in this parameter is expected to yield information about the presence or absence of ASR gel.

  17. A chemo-mechanical model for the acoustic nonlinearity change in concrete with alkali-silica reactions

    Science.gov (United States)

    Liu, M.; Jacobs, L. J.; Qu, J.

    2013-01-01

    Experimental data have demonstrated that damage induced by alkali-silica reaction (ASR) in concrete, even in its very early stage, can cause changes in the acoustic nonlinearity parameter β. This provides a means to characterize ASR damage in concrete nondestructively. However, there is currently no model that explains the relationship between the acoustic nonlinearity parameter and ASR damage. In this work, we present a micromechanics-based chemo-mechanical model that relates the acoustic nonlinearity parameter to ASR damage. The mechanical part of the model is developed based on a modified version of the generalized self-consistent theory. The chemical part of the model accounts for two opposing diffusion processes. One is the diffusion of alkali ions in the pore solution into aggregates, and the other is the permeation of ASR gel from the aggregate surface into the surrounding porous cement matrix. Furthermore, a fracture model is used to simulate crack initiation and growth, so that the crack density and total expansion can be obtained. Finally, the acoustic nonlinearity parameter is determined as a function of exposure time by accounting for the gel pressure and the crack density. This model provides a way to quantitatively predict the changes in the acoustic nonlinearity parameter due to ASR damage, which can be used to guide experimental measurements for nondestructive evaluation of ASR damage.

  18. Tuning indium tin oxide work function with solution-processed alkali carbonate interfacial layers for high-efficiency inverted organic photovoltaic cells.

    Science.gov (United States)

    Chen, Fei; Chen, Qi; Mao, Lin; Wang, Yixin; Huang, Xun; Lu, Wei; Wang, Bing; Chen, Liwei

    2013-12-06

    Selective electron collection by an interfacial layer modified indium tin oxide cathode is critically important for achieving high-efficiency inverted structure organic photovoltaic (OPV) cells. Here, we demonstrate that solution-processed alkali carbonates, such as Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, are good interfacial layer materials. Both carbonate concentration and annealing conditions can affect cathode work function and surface roughness. By proper optimization, different alkali carbonates can be almost equally effective as the cathode interfacial layer. Furthermore, good device performance can be achieved at a low annealing temperature (<50 ° C), which allows for potential applications in solution-processed inverted OPV cells on plastic substrates. This work indicates that alkali carbonates, not just cesium carbonate, are valid choices as the cathode interlayer in inverted OPV devices.

  19. The effect of calcium hydroxide, alkali dilution and calcium concentration in mitigating the alkali silica reaction using palm oil fuel ash

    Science.gov (United States)

    Asrah, Hidayati; Mirasa, Abdul Karim; Bolong, Nurmin

    2018-02-01

    This study investigated the mechanism of how POFA mitigated the ASR expansion. Two types of POFA; the UPOFA and GPOFA with different fineness were used to replace the cement at 20% and 40% and their effects on the mortar bar expansion, calcium hydroxide, alkali dilution, and calcium concentration were investigated. The results showed that UPOFA has a significant ability to mitigate the ASR, even at a lower level of replacement (20%) compared to GPOFA. The mechanism of UPOFA in mitigating the ASR expansion was through a reduction in the calcium hydroxide content, which produced low calcium concentration within the mortar pore solution. Low pore solution alkalinity signified that UPOFA had good alkali dilution effect. Meanwhile, a higher dosage of GPOFA was required to mitigate the ASR expansion. An increase in the pore solution alkalinity of GPOFA mortar indicated higher penetration of alkalis from the NaOH solution, which reduced the alkali dilution effect. However, this was compensated by the increase in the cement dilution effect at higher GPOFA replacement, which controlled the mortar bar expansion below the ASTM limit.

  20. Kinetics and mechanisms of iron redox reactions in silicate melts: The effects of temperature and alkali cations

    Energy Technology Data Exchange (ETDEWEB)

    Magnien, V.; Pinet, O. [CEA VALRHO, SCDV/LEBV, F-30207 Bagnols Sur Ceze, (France); Magnien, V.; Neuville, D. R.; Roux, J.; Richet, P. [IPGP, CNRS, Physique des Mineraux et Magmas, F-75252 Paris 05, (France); Cormier, L. [Univ Paris 06, IMPMC, F-75015 Paris, (France); Hazemann, J. L. [CNRS, Inst Neel, F-38043 Grenoble, (France); De Ligny, D. [Univ Lyon 1, LMLC, CNRS, UMR 5620, F-69622 Villeurbanne, (France); Pascarelli, S. [European Synchrotron Radiat Facil, F-38043 Grenoble, (France); Vickridge, I. [Univ Paris 06, INSP, F-75015 Paris, (France)

    2008-07-01

    The kinetics and the mechanisms of iron redox reactions in molten Fe-bearing pyroxene compositions have been investigated by Raman spectroscopy and X-ray absorption Near Edge Structure (XANES) experiments at the iron K-edge. The former experiments have been made only near the glass transition whereas the latter have also been performed from about 1300 to 2100 K. The same kinetics are observed with both techniques. They are described by characteristic times that depend primarily on temperature and not on the initial redox state. At high temperatures, where both kinds of reactions could be investigated, these times are similar for oxidation and reduction. From these characteristic times we have calculated as a function of temperature and composition a parameter termed effective redox diffusivity. For a given melt, the diffusivities follow two distinct Arrhenius laws, which indicate that the mechanisms of the redox reaction are not the same near the glass transition and at high temperatures. As is now well established, diffusion of divalent cations is the dominant mechanism at low temperatures but the enhanced kinetics observed for alkali-bearing melts indicate that Li{sup +} and Na{sup +} also participate in ionic transport. At super-liquidus temperatures, in contrast, diffusion of oxygen represents the dominant mechanism. (authors)

  1. Reaction of aluminium selenites with alkali metal selenites in hydrothermal conditions

    International Nuclear Information System (INIS)

    Tananaev, I.V.; Volodina, A.N.; Bol'shakova, N.K.; Petrov, K.I.

    1976-01-01

    In the course of hydrothermal crystallization (T from 150 deg to 200 deg C, P=20 atm) of Al 2 (SeO 3 ) 3 x6H 2 O in solutions of cesium and rubidium trihydroselenites, which contain an excess of the alkali metals, there form the isostructural mixed selenites Cssub(0.5)Hsub(0.5)Al(SeO 3 ) 2 xH 2 O and Rbsub(0.6)Hsub(0.4)Al(SeO 3 ) 2 x2H 2 O. Under the same conditions, in the solutions of lithium, sodium and potassium trihydroselenites, Al 2 (SeO 3 ) 3 x6H 2 O fails to form the mixed selenites. The IR-spectroscopic study of the mixed selenites Al has been carried out and their thermal decomposition has been investigated. The obtained data make it possible to represent the mixed selenites by the formula Msub(x)Hsub(1-x)Al(SeO 3 ) 2 xnH 2 O and to regard them as compounds of variable composition [ru

  2. Effect of alkali ions (Na+, K+, Cs+) on reaction mechanism of CZTS nano-particles synthesis

    Science.gov (United States)

    Kumar, Suresh; Altosaar, Mare; Grossberg, Maarja; Mikli, Valdek

    2018-04-01

    The control of morphology, elemental composition and phase composition of Cu2ZnSnS4 (CZTS) nano-crystals depends on the control of complex formation and surface stabilization of nano-particles in solution-based synthesis in oleylamine. At temperatures ≥280 °C, the control of nano-crystal's morphology and homogenous growth is difficult because of fast poly-nuclear growth occurring at higher temperatures. In the present work the effect of oleylamine complex formation with different alkali ions (Na+, K+ and Cs+) on nano-crystals growth at synthesis temperature of 280 °C was studied. It was found that nano-powders synthesized in the presence of Na+ and K+ ions showed the formation of crystals of different sizes - small nano-particles (18 nm-30 nm), large aggregated crystals (few nm to 1 μm) and large single crystals (1 μm - 4 μm). The presence of Cs+ ions in the nano-powder synthesis in oleylamine-metal precursor-CsOH solution promoted growth of nano-crystals of homogenous size. It is proposed that the formed oleylamine-Cs complexes a) enhance the formation and stabilization of oleylamine-metal (Cu, Zn and Sn) complexes before the injection of sulphur precursor into the oleylamine-metal precursor solution and b) after addition of sulphur stabilize the fast nucleated nano-particles and promote diffusion limited growth.

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

    Directory of Open Access Journals (Sweden)

    Olague, C.

    2002-12-01

    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. Thermal stability and oxidizing properties of mixed alkaline earth-alkali molten carbonates: A focus on the lithium-sodium carbonate eutectic system with magnesium additions

    International Nuclear Information System (INIS)

    Frangini, Stefano; Scaccia, Silvera

    2013-01-01

    Highlights: • TG/DSC analysis was conducted on magnesium-containing eutectic Li/Na eutectic carbonates. • Magnesium influence on the oxygen solubility properties of carbonate was also experimentally determined at 600 °C and 650 °C. • A reproducible partial decarbonation process in premelting region caused formation of magnesium oxycarbonate-like phases. • The acidobase buffering action of magnesium oxycarbonate species could explain the high basic/oxidizing properties of such carbonate melts. • A general correlation between thermal instability in premelting region and basic/oxidizing melt properties was established. - Abstract: A comparative study on thermal behavior and oxygen solubility properties of eutectic 52/48 lithium/sodium carbonate salt containing minor additions of magnesium up to 10 mol% has been made in order to determine whether a general correlation between these two properties can be found or not. Consecutive TG/DSC heating/cooling thermal cycles carried out under alternating CO 2 and N 2 gas flows allowed to assign thermal events observed in the premelting region to a partial decarbonation process of the magnesium-alkali mixed carbonates. The observed decarbonation process at 460 °C is believed to come from initial stage of thermal decomposition of magnesium carbonate resulting in the metastable formation of magnesium oxycarbonate-like phases MgO·2MgCO 3 , in a similar manner as previously reported for lanthanum. Reversible formation and decomposition of the magnesium carbonate phase has been observed under a CO 2 gas atmosphere. The intensity of the decomposition process shows a maximum for a 3 mol% MgO addition that gives also the highest oxygen solubility, suggesting therefore that instability thermal analysis in the premelting region can be considered as providing an effective measure of the basicity/oxidizing properties of alkali carbonate melts with magnesium or, in more general terms, with cations that are strong modifiers of

  5. Evaluation on an influence to turbine generator installed on a concrete foundation structure affected by alkali-silica reaction

    International Nuclear Information System (INIS)

    Takeo Takakura; Takashi Momoo; Shigeru Harada; Yoshihisa Asai; Takashi Hosokawa

    2005-01-01

    A turbine generator to be evaluated is a one with 566 MW capacity installed on a reinforced concrete supporting structure having a table deck portion where equipments are installed and columns to support on the table deck. After the initial operation of this turbine generator started, a difference from the initial setting at an installation stage was found at turbine generator in the annual inspection on 1979. The turbine generator foundation (herein after TG foundation) had expanded mainly longitudinal direction, and it was confirmed this expansion occurred due to affected by Alkali-Silica reaction (herein after ASR) according to concrete core samples tests. The measurement for TG foundation such as displacements started at this time. On the other hand, bearing metal temperatures and shaft vibration for the turbine generator have been continuously monitored by supervisory from initial operation. No abnormal alarm or trips by extraordinary metal temperature or axle vibration of the turbine generator due to TG foundation expansion affected by ASR have been arisen. However it is required to confirm sounding of this turbine generator in order to safely operation. The purpose of this paper checked and examined allowable capacity of turbine generator and TG foundation, in order to operate continuously and safely. (authors)

  6. Quantitative assessment of alkali silica reaction potential of quartz-rich aggregates: comparison of chemical test and accelerated mortar bar test improved by SEM-PIA

    Czech Academy of Sciences Publication Activity Database

    Šachlová, Š.; Kuchařová, A.; Pertold, Z.; Přikryl, R.; Fridrichová, Michaela

    2017-01-01

    Roč. 76, č. 1 (2017), s. 133-144 ISSN 1435-9529 R&D Projects: GA ČR(CZ) GAP104/12/0915 Institutional support: RVO:67985831 Keywords : accelerated mortar bar test * Alkali silica reaction * chemical test * electron microscopy * petrographic image analysis Subject RIV: DD - Geochemistry OBOR OECD: Environmental and geological engineering, geotechnics Impact factor: 1.901, year: 2016

  7. Effect of natural carbonation on the pore structure and elastic modulus of the alkali-activated fly ash and slag pastes

    NARCIS (Netherlands)

    Nedeljkovic, M.; Šavija, B.; Zuo, Y.; Lukovic, M.; Ye, G.

    2018-01-01

    The aim of this paper was to investigate the effect of natural carbonation on the pore structure, and elastic modulus (E-m) of alkali-activated fly ash (FA) and ground granulated blast furnace slag (GBFS) pastes after one year of exposure in the natural laboratory conditions. The chemical changes

  8. Effect of natural carbonation on the pore structure and elastic modulus of the alkali-activated fly ash and slag pastes

    NARCIS (Netherlands)

    Nedeljkovic, M.; Šavija, B.; Zuo, Y.; Lukovic, M.; Ye, G.

    2018-01-01

    The aim of this paper was to investigate the effect of natural carbonation on the pore structure, and elastic modulus (Em) of alkali-activated fly ash (FA) and ground granulated blast furnace slag (GBFS) pastes after one year of exposure in the natural laboratory conditions. The

  9. On the effect of addition of carbon nanotubes on the electric conductivity of alkali-activated slag mortars

    Science.gov (United States)

    Kusak, I.; Lunak, M.

    2017-09-01

    This paper presents basic electric properties of laboratory prepared alkali-activated composite materials on the basis of finely ground granular high furnace slag to which various quantities of carbon nanotubes (CNT) have been added. Impedance spectroscopy in the frequency range from 40 Hz to 1 MHz was used to measure the specimens. Electric resistivity ρ versus frequency and electric resistivity ρ versus CNT content relationships were examined on our specimens R&S ZNC vector analyser with DAK-12 coaxial probe (made by Speag) was used to carry out the measurements at higher frequencies (from 100 MHz to 3 GHz). Electric conductivity σ as a function of the frequency and as a function of the specimen CNT content was studied in this frequency range. Up-to-date instruments and a unique approach have evidently been employed to carry out non-destructive measurement of mortar materials.

  10. Assessment of the Alteration of Granitic Rocks and its Influence on Alkalis Release

    Science.gov (United States)

    Ferraz, Ana Rita; Fernandes, Isabel; Soares, Dora; Santos Silva, António; Quinta-Ferreira, Mário

    2017-12-01

    Several concrete structures had shown signs of degradation some years after construction due to internal expansive reactions. Among these reactions there are the alkali-aggregate reactions (AAR) that occur between the aggregates and the concrete interstitial fluids which can be divided in two types: the alkali-silica reaction (ASR) and alkali-carbonate reaction (ACR). The more common is the ASR which occurs when certain types of reactive silica are present in the aggregates. In consequence, an expansive alkali-silica gel is formed leading to the concrete cracking and degradation. Granites are rocks composed essentially of quartz, micas and feldspars, the latter being the minerals which contain more alkalis in their structure and thus, able to release them in conditions of high alkalinity. Although these aggregates are of slow reaction, some structures where they were applied show evidence of deterioration due to ASR some years or decades after the construction. In the present work, the possible contribution of granitic aggregates to the interstitial fluids of concrete by alkalis release was studied by performing chemical attack with NaOH and KOH solutions. Due to the heterogeneity of the quarries in what concerns the degree of alteration and/or fracturing, rock samples with different alteration were analysed. The alteration degree was characterized both under optical microscope and image analysis and compared with the results obtained from the chemical tests. It was concluded that natural alteration reduces dramatically the releasable alkalis available in the rocks.

  11. Alkali-Assisted Synthesis of Nitrogen Deficient Graphitic Carbon Nitride with Tunable Band Structures for Efficient Visible-Light-Driven Hydrogen Evolution.

    Science.gov (United States)

    Yu, Huijun; Shi, Run; Zhao, Yunxuan; Bian, Tong; Zhao, Yufei; Zhou, Chao; Waterhouse, Geoffrey I N; Wu, Li-Zhu; Tung, Chen-Ho; Zhang, Tierui

    2017-04-01

    A facile synthetic strategy for nitrogen-deficient graphitic carbon nitride (g-C 3 N x ) is established, involving a simple alkali-assisted thermal polymerization of urea, melamine, or thiourea. In situ introduced nitrogen vacancies significantly redshift the absorption edge of g-C 3 N x , with the defect concentration depending on the alkali to nitrogen precursor ratio. The g-C 3 N x products show superior visible-light photocatalytic performance compared to pristine g-C 3 N 4 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Alkali-aggregate reactivity (AAR) facts book.

    Science.gov (United States)

    2013-03-01

    This document provides detailed information on alkali-aggregate reactivity (AAR). It primarily discusses alkali-silica reaction (ASR), covering the chemistry, symptoms, test methods, prevention, specifications, diagnosis and prognosis, and mitigation...

  13. Cleavage reactions of the complex ions derived from self-complementary deoxydinucleotides and alkali-metal ions using positive ion electrospray ionization with tandem mass spectrometry.

    Science.gov (United States)

    Xiang, Yun; Abliz, Zeper; Takayama, Mitsuo

    2004-05-01

    The dissociation reactions of the adduct ions derived from the four self-complementary deoxydinucleotides, d(ApT), d(TpA), d(CpG), d(GpC), and alkali-metal ions were studied in detail by positive ion electrospray ionization multiple-stage mass spectrometry (ESI-MS(n)). For the [M + H](+) ions of the four deoxydinucleotides, elimination of 5'-terminus base or loss of both of 5'-terminus base and a deoxyribose were the major dissociation pathway. The ESI-MS(n) spectra showed that Li(+), Na(+), and Cs(+) bind to deoxydinucleotides mainly by substituting the H(+) of phosphate group, and these alkali-metal ions preferred to bind to pyrimidine bases rather than purine bases. For a given deoxydinucleotide, the dissociation pathway of [M + K](+) ions differed clearly from that of [M + Li](+), [M + Na](+), and [M + Cs](+) ions. Some interesting and characteristic cleavage reactions were observed in the product-ion spectra of [M + K](+) ions, including direct elimination of deoxyribose and HPO(3) from molecular ions. The fragmentation behavior of the [M + K](+) and [M + W](+) (W = Li, Na, Cs) adduct ions depend upon the sequence of bases, the interaction between alkali-metal ions and nucleobases, and the steric hindrance caused by bases.

  14. The composition of primary carbonate melts and their evolution through wallrock reaction in the mantle

    Science.gov (United States)

    Dalton, John A.; Wood, Bernard J.

    1993-10-01

    We have experimentally determined the composition of near-soldus melts from depleted natural Iherzolite at pressures greater than 25 kbar. The melts are carbontitic with low alkali contents and Ca/(Ca + Mg) ratios of 0.72-0.74. Primary carbonate melts from fertile mantle are more sodic with Ca/(Ca + Mg + Fe + Na) of 0.52 and Na/(Na + Ca + Mg + Fe) up to 0.15. The melt compositions are similar to many natural magnesio-carbonatites, but differ substantially from the more abundant calcio-carbonatites. Experimentally we find that calcio-carbonatites are produced by wallrock reaction of primary melts with harzburgite at pressures of less than 25 kbar. At 15 kbar we have obtained a Ca/(Ca + Mg + Fe + Na) ratio of up to 0.87 and very low Na contents generated by this process. Values of Ca/(Ca + Mg + Fe + Na) up to 0.95 are possible at lower pressures. Low pressure wallrock reaction of primary carbonate melt with fertile Iherzolite produces melts richer in Na2CO3, corresponding to possible parental magmas of natrocarbonatite. Wallrock reaction at low pressures transforms the bulk peridotite composition from that of a harzburgite or Iherzolite to wehrlite. Examples of such carbonatite metasomatism are now widely documented. Our experiments show that the calcium content of olivine and the jadeite content of clinopyroxene may be used to constrain the Ca and Na contents respectively of the cabonatite melt responsible for metasomatism.

  15. Process for the disposal of alkali metals

    International Nuclear Information System (INIS)

    Lewis, L.C.

    1979-01-01

    The invention describes a method of disposing of alkali metals by forming a solid waste for storage. The method comprises preparing an aqueous disposal solution of at least 55 weight percent alkali metal hydroxide, heating the alkali metal to melting temperature to form a feed solution, and spraying the molten feed solution into the disposal solution. The alkali metal reacts with the water in the disposal solution in a controlled reaction which produces alkali metal hydroxide, hydrogen and heat and thereby forms a solution of alkali metal hydroxides. Water is added to the solution in amounts sufficient to maintain the concentration of alkali metal hydroxides in the solution at 70 to 90 weight percent, and to maintain the temperature of the solution at about the boiling point. Removing and cooling the alkali metal hydroxide solution thereby forms a solid waste for storage. The method is particularly applicable to radioactive alkali metal reactor coolant. (auth)

  16. Properties of solvated electrons, alkali anions and other species in metal solutions and kinetics of cation and electron exchange reactions. Final report

    International Nuclear Information System (INIS)

    Dye, J.L.

    1979-01-01

    The properties of solutions of alkali metals in amine solvents were studied by optical, ETR, NMR and electrochemical methods. Complexation of the alkali cations by crown ethers and cryptands permitted the preparation of concentrated solutions of alkali metals in amine and ether solvents. Extensive alkali metal NMR studies of the exchange of M + with crown-ethers and cryptands and of the alkali metal anion, M - , were made. The first crystalline salt of an alkali metal anion, Na + Cryptand [2.2.2]Na - was synthesized and characterized and led to the preparation of other alkali metal anion salts. This research provided the foundation for continuing studies of crystalline alkalide salts

  17. Complex formation during dissolution of metal oxides in molten alkali carbonates

    DEFF Research Database (Denmark)

    Li, Qingfeng; Borup, Flemming; Petrushina, Irina

    1999-01-01

    Dissolution of metal oxides in molten carbonates relates directly to the stability of materials for electrodes and construction of molten carbonate fuel cells. In the present work the solubilities of PbO, NiO, Fe2O3,and Bi2O3 in molten Li/K carbonates have been measured at 650 degrees C under...... carbon dioxide atmosphere. It is found that the solubilities of NiO and PbO decrease while those of Fe2O3 and Bi2O3 remain approximately constant as the lithium mole fraction increases from 0.43 to 0.62 in the melt. At a fixed composition of the melt, NiO and PbO display both acidic and basic dissolution...... as the partial pressure of carbon dioxide varies. By combination of solubility and electromotive force measurements, a model is constructed assuming the dissolution involves complex formation. The possible species for lead are proposed to be [Pb(CO3)(2)](-2) and/or [Pb(CO3)(3)](-4). A similar complex chemistry...

  18. Effects of Alkali-Metal Ions and Counter Ions in Sn-Beta-Catalyzed Carbohydrate Conversion.

    Science.gov (United States)

    Elliot, Samuel G; Tolborg, Søren; Madsen, Robert; Taarning, Esben; Meier, Sebastian

    2018-02-26

    Alkali-metal ions have recently been shown to strongly influence the catalytic behavior of stannosilicates in the conversion of carbohydrates. An effect of having alkali-metal ions present is a pronounced increase in selectivity towards methyl lactate. Mechanistic details of this effect have remained obscure and are herein addressed experimentally through kinetic experiments and isotope tracking. The presence of alkali-metal ions has a differential effect in competing reaction pathways and promotes the rate of carbon-carbon bond breakage of carbohydrate substrates, but decreases the rates of competing dehydration pathways. Further addition of alkali-metal ions inhibits the activity of Sn-Beta in all major reaction pathways. The alkali-metal effects on product distribution and on the rate of product formation are similar, thus pointing to a kinetic reaction control and to irreversible reaction steps in the main pathways. Additionally, an effect of the accompanying basic anions is shown, supposedly facilitating the cation exchange and eliciting a different concentration-dependent effect to that of neutral alkali-metal salts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Efficient destruction of CF4 through in situ generation of alkali metals from heated alkali halide reducing mixtures.

    Science.gov (United States)

    Lee, Myung Churl; Choi, Wonyong

    2002-03-15

    Perfluorocarbons (PFCs) are the most potent green house gases that are very recalcitrant at destruction. An effective way of converting PFCs using hot solid reagents into safe products has been recently introduced. By investigating the thermal reductive destruction of tetrafluoromethane (CF4) we provided new insight and more physicochemical consideration on this novel process. The complete destruction of CF4was successfully achieved by flowing the gas through a heated reagent bed (400-950 degrees C) that contained powder mixtures of alkali halides, CaO, and Si. The silicon acted as a reducing agent of alkali halides for the in-situ production of alkali metals, and the calcium oxide played the role of a halide ion acceptor. The absence of any single component in this ternary mixture drastically reduced the destruction efficiency of CF4. The CF4 destruction efficiencies with the solid reagent containing the alkali halide, MX, increased in the order of Li approximately Na < K < Cs for alkali cations and I < Br < Cl < F for halide anions. This trend agreed with the endothermicity of the alkali metal generation reaction: the higher the endothermicity, the lower the destruction efficiency. Alkali metal generation was indirectly detected by monitoring H2 production from its reaction with water. The production of alkali metals increased with NaF, KF, and CsF in this order. The CsF/CaO/Si system exhibited the complete destruction of CF4 at as low as 600 degrees C. The solid product analysis by X-ray diffraction (XRD) showed the formation of CaF2 and the depletion of Si with black carbon particles formed in the solid reagent residue. No CO/CO2 and toxic HF and SiF4 formation were detected in the exhaust gas.

  20. Demixing and effective volatility of molten alkali carbonate melts in MCFCs

    Energy Technology Data Exchange (ETDEWEB)

    Brenscheidt, T.; Wendt, H. [Institut fuer Chemische Technologie, Darmstadt (Germany)

    1996-12-31

    Since the early investigation of A. Klemm, the demixing of the cations of molten binary salt mixtures with a common anion due to the different mobilities of two different cations had been investigated in numerous experiments and the respective results interpreted in terms of structural features of the melts. 1-1 electrolytes had been preferentially investigated. Okada also reported investigations on lithium carbonate/potassium carbonate mixtures in the temperature range from 980 to 1070 K. From this investigation it is known that the heavier potassium cation is faster than lithium in mixtures which are more concentrated in potassium than x{sub K2CO3} = 0,32 (Chemla effect) whereas below this isotachic concentration lithium is faster. This paper investigates demixing in molten carbonate fuel cells.

  1. Reaction of titanium polonides with carbon dioxide

    International Nuclear Information System (INIS)

    Abakumov, A.S.; Malyshev, M.L.; Reznikova, N.F.

    1987-01-01

    It has been ascertained that heating titanium and tantalum in carbon dioxide to temperatures of 500 or 800 0 C alters the composition of the gas phase, causing the advent of carbon monoxide and lowering the oxygen content. Investigation of the thermal stability of titanium polonides in a carbon dioxide medium has shown that titanium mono- and hemipolonides are decomposed at temperatures below 350 0 C. The temperature dependence of the vapor pressure of polonium produced in the decomposition of these polonides in a carbon dioxide medium have been determined by a radiotensimetric method. The enthalpy of the process, calculated from this relationship, is close to the enthalpy of vaporization of elementary polonium in vacuo

  2. $MNO_2$ catalyzed carbon electrodes for dioxygen reduction in concentrated alkali

    OpenAIRE

    Manoharan, R; Shulka, AK

    1984-01-01

    A process to deposit $\\gamma-MnO_2$ catalytic oxide onto coconut-shell charcoal substrate is described. Current-potential curves for electroreduction of dioxygen with electrodes fabricated from this catalyzed substrate are obtained in 6M KOH under ambient conditions. The performance of these electrodes is competitive with platinized carbon electrodes.

  3. Combined reactions and separations using ionic liquids and carbon dioxide

    NARCIS (Netherlands)

    Kroon, M.C.

    2006-01-01

    A new and general type of process for the chemical industry is presented using ionic liquids and supercritical carbon dioxide as combined reaction and separation media. In this process, the carbon dioxide pressure controls the miscibility of reactants, products, catalyst and ionic liquid, enabling

  4. On reaction of titanium polonides with carbon dioxide

    International Nuclear Information System (INIS)

    Abakumov, A.S.; Malyshev, M.L.; Reznikova, N.F.

    1986-01-01

    The reaction between titanium polonides and carbon dioxide has been studied by comparing titanium polonide thermal resistance in vacuum and in carbon dioxide. The investigation has shown that titanium mono- and semipolonides fail at temperatures below 350 deg C. Temperature dependence of polonium vapor pressure prepared at failure of the given polonides is determined by the radiotensiometry in carbon dioxide. Enthalpy calculated for this dependence is close to the enthalpy of elementary polonium evaporation in vacuum

  5. Dynamics of alkali ions-neutral molecules reactions: Radio frequency-guided beam experimental cross-sections and direct quasiclassical trajectory studies

    Energy Technology Data Exchange (ETDEWEB)

    Aguilar, J.; Andres, J. de; Lucas, J. M.; Alberti, M.; Huarte-Larranaga, F.; Bassi, D.; Aguilar, A. [Departament de Quimica Fisica, Institut de Quimica Teorica i Computacional (IQTCUB), Universitat de Barcelona, Marti i Franques, 1, 08028 Barcelona (Spain); Dipartimento di Fisica, Universita degli Studi di Trento, 38123 Povo-Trento (Italy); Departament de Quimica Fisica, Institut de Quimica Teorica i Computacional (IQTCUB), Universitat de Barcelona, Marti i Franques, 1, 08028 Barcelona (Spain)

    2012-11-27

    Different reactive processes taking place in collisions between alkali ions and neutral i-C{sub 3}H{sub 7}Cl molecules in the low (center of mass frame) energy range have been studied using an octopole radiofrequency guided-ion-beam apparatus developed in our laboratory. Cross-section energy dependences for all these reactions have been obtained in absolute units. Ab initio electronic structure calculations for those colliding systems evolving on the ground single potential surface have given relevant information on the main topological features of the surfaces. For some of the reactions a dynamic study by 'on the fly' trajectories has complemented the available experimental and electronic structure information.

  6. Corrosion-electrochemical behavior of zirconium in molten alkali metal carbonates

    Science.gov (United States)

    Nikitina, E. V.

    2016-08-01

    The corrosion and electrochemical characteristics of zirconium during its interaction with molten lithium, sodium, and potassium carbonates containing from 1 to 5 wt % additives to the salt phase are studied in a temperature range of 500-800°C using gravimetry, corrosion potential measurement, and anodic polarization. The substances decreasing the corrosion losses due to the strengthening and thickening of an oxide film (lithium, sodium, potassium hydroxides) are used as passivators. Sodium chloride, fluoride, and sulfate serve as corrosion stimulators (activators).

  7. Alkali control of high-grade metamorphism and granitization

    Directory of Open Access Journals (Sweden)

    Oleg G. Safonov

    2014-09-01

    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.

  8. Extreme alkali bicarbonate- and carbonate-rich fluid inclusions in granite pegmatite from the Precambrian Rønne granite, Bornholm Island, Denmark

    Science.gov (United States)

    Thomas, Rainer; Davidson, Paul; Schmidt, Christian

    2011-02-01

    Our study of fluid and melt inclusions in quartz and feldspar from granite pegmatite from the Precambrian Rønne granite, Bornholm Island, Denmark revealed extremely alkali bicarbonate- and carbonate-rich inclusions. The solid phases (daughter crystals) are mainly nahcolite [NaHCO3], zabuyelite [Li2CO3], and in rare cases potash [K2CO3] in addition to the volatile phases CO2 and aqueous carbonate/bicarbonate solution. Rare melt inclusions contain nahcolite, dawsonite [NaAl(CO3)(OH)2], and muscovite. In addition to fluid and melt inclusions, there are primary CO2-rich vapor inclusions, which mostly contain small nahcolite crystals. The identification of potash as a naturally occurring mineral would appear to be the first recorded instance. From the appearance of high concentrations of these carbonates and bicarbonates, we suggest that the mineral-forming media were water- and alkali carbonate-rich silicate melts or highly concentrated fluids. The coexistence of silicate melt inclusions with carbonate-rich fluid and nahcolite-rich vapor inclusions indicates a melt-melt-vapor equilibrium during the crystallization of the pegmatite. These results are supported by the results of hydrothermal diamond anvil cell experiments in the pseudoternary system H2O-NaHCO3-SiO2. Additionally, we show that boundary layer effects were insignificant in the Bornholm pegmatites and are not required for the origin of primary textures in compositionally simple pegmatites at least.

  9. Wetting of a Charged Surface of Glassy Carbon by Molten Alkali-Metal Chlorides

    Science.gov (United States)

    Stepanov, V. P.

    2018-03-01

    Values of the contact angle of wetting of a surface of glassy carbon by molten chlorides of lithium, sodium, potassium, and cesium are measured by the meniscus weight method to determine the common factors of wettability of solid surfaces by ionic melts upon a change in the salt phase composition and a jump in electric potential. It is found that with a potential shift in the positive direction the shape of the curve of the contact angle's dependence on the potential varies upon substitution of one salt by another: the angle of wetting shrinks monotonously in lithium chloride but remains constant in molten cesium chloride. This phenomenon is explained by the hypothesis that the nature of the halide anion adsorption on the positively charged surface of an electrode is chemical and not electrostatic. It is shown that the adsorption process is accompanied by charge transfer through the interface, with covalent bonding between the adsorbent and adsorbate.

  10. Examination of the effects of LiOH, LiCl, and LiNO3 on alkali-silica reaction

    International Nuclear Information System (INIS)

    Collins, C.L.; Ideker, J.H.; Willis, G.S.; Kurtis, K.E.

    2004-01-01

    Lithium additives have been shown to reduce expansion associated with alkali-silica reaction (ASR), but the mechanism(s) by which they act have not been understood. The aim of this research is to assess the effectiveness of three lithium additives--LiOH, LiCl, and LiNO 3 --at various dosages, with a broader goal of improving the understanding of the means by which lithium acts. The effect of lithium additives on ASR was assessed using mortar bar expansion testing and quantitative elemental analysis to measure changes in concentrations of solution phase species (Si, Na, Ca, and Li) in filtrates obtained at different times from slurries of silica gel and alkali solution. Results from mortar bar tests indicate that each of the lithium additives tested was effective in reducing expansion below an acceptable limit of 0.05% at 56 days. However, different lithium additive threshold dosages ([Li 2 O]/[Na 2 O e ]) were required to accomplish this reduction in expansion; these were found to be approximately 0.6 for LiOH, 0.8 for LiNO 3 , and 0.9 for LiCl. Quantitative elemental analysis indicated that sodium and lithium were both bound in reaction products formed within the silica gel slurry. It is also believed that lithium may have been preferentially bound over sodium in at least one of the reaction products because a greater percent decrease in dissolved lithium than dissolved sodium was observed within the first 24 h. It appears that lithium additives either decreased silica dissolution, or promoted precipitation of silica-rich products (some of which may be nonexpansive), because the dissolved silica concentration decreased with increasing dosage of lithium nitrate or lithium chloride additive

  11. Comparison studies of surface cleaning methods for PAN-based carbon fibers with acetone, supercritical acetone and subcritical alkali aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Meng Linghui; Fan Dapeng [School of Chemical Engineering and Technology, Harbin Institute of Technology, P.O. Box 410, Harbin 150001 (China); Huang Yudong, E-mail: ydhuang.hit1@yahoo.com.cn [School of Chemical Engineering and Technology, Harbin Institute of Technology, P.O. Box 410, Harbin 150001 (China); Jiang Zaixing; Zhang Chunhua [School of Chemical Engineering and Technology, Harbin Institute of Technology, P.O. Box 410, Harbin 150001 (China)

    2012-11-15

    Highlights: Black-Right-Pointing-Pointer Cleaning with supercritical acetone is appropriate to wipe off the oxygenated contaminants. Black-Right-Pointing-Pointer Cleaning with supercritical acetone causes smaller damage to bulk strength of carbon fibers. Black-Right-Pointing-Pointer Cleaning with subcritical alkali aqueous solution can thoroughly remove silicious contaminants. - Abstract: Four kinds of polyacrylonitrile-based carbon fibers were cleaned by three methods and were characterized by X-ray photoelectron spectroscopy, monofilament tensile strength test and atomic force microscopy (AFM). Experimental results of these tests reveal that the method using supercritical acetone or subcritical potassium hydroxide aqueous solution act as the processing medium shows a better cleaning effect compared to the traditional method, Soxhlet extraction with acetone. The method using supercritical acetone is more appropriate to wipe off the oxygenated contaminants on carbon fibers' surfaces and causes a relatively smaller damage to the bulk strength of each carbon fiber. As far as treating method using the subcritical alkali aqueous solution, it can thoroughly remove silicious contaminants on the surfaces of treated fibers.

  12. Comparison studies of surface cleaning methods for PAN-based carbon fibers with acetone, supercritical acetone and subcritical alkali aqueous solutions

    International Nuclear Information System (INIS)

    Meng Linghui; Fan Dapeng; Huang Yudong; Jiang Zaixing; Zhang Chunhua

    2012-01-01

    Highlights: ► Cleaning with supercritical acetone is appropriate to wipe off the oxygenated contaminants. ► Cleaning with supercritical acetone causes smaller damage to bulk strength of carbon fibers. ► Cleaning with subcritical alkali aqueous solution can thoroughly remove silicious contaminants. - Abstract: Four kinds of polyacrylonitrile-based carbon fibers were cleaned by three methods and were characterized by X-ray photoelectron spectroscopy, monofilament tensile strength test and atomic force microscopy (AFM). Experimental results of these tests reveal that the method using supercritical acetone or subcritical potassium hydroxide aqueous solution act as the processing medium shows a better cleaning effect compared to the traditional method, Soxhlet extraction with acetone. The method using supercritical acetone is more appropriate to wipe off the oxygenated contaminants on carbon fibers’ surfaces and causes a relatively smaller damage to the bulk strength of each carbon fiber. As far as treating method using the subcritical alkali aqueous solution, it can thoroughly remove silicious contaminants on the surfaces of treated fibers.

  13. The effect of alkali promoters on Cu-Na-ZSM-5 catalysts in the oxidation of benzyl alcohol

    Energy Technology Data Exchange (ETDEWEB)

    Hayashibara, Hirofuni; Nishiyama, Satoru; Tsuruya, Shigeru [Kobe Univ. (Japan)] [and others

    1995-05-01

    The oxidation activities of alkali-added Cu-Na-ZSM-5 zeolites in the gas-phase catalytic oxidation of benzyl alcohol were studied. The main products were benzaldehyde and carbon oxides (carbon dioxide and carbon monoxide). The partial oxidation activity was found to markedly increase when an alkali-metal-added Cu-Na-ZSM-5 was used, in comparison with that obtained when the Cu-Na-ZSM-5 zeolite itself was used. On the other hand, the increase in yield of deep oxidation products (CO{sub 2} + CO) catalyzed by the alkali-added Cu-Na-ZSM-5 was rather low. The alkali added to the Cu-Na-ZSM-5 zeolite was thus found to selectively promote catalytic activity for the partial oxidation of benzyl alcohol. Certain types of alkali salts were used as the additive with the results that Na{sup +}, K{sup +}, and Rb{sup +}, but not Li{sup +}, had similar behavior for benzyl alcohol oxidation. An alkali oxide such as Na;{sub 2}O, rather than the alkali salt itself, was suggested to substantially function as an active promoter for the oxidation of benzyl alcohol as judged from the pretreatment condition of the alkali-added Cu-Na-ZSM-5 zeolite and its similar catalytic activity in the oxidation of alkali salts with the same alkali cation but different counteranions. The added alkali was found to act more effectively as a promoter for oxidation when alkali and Cu ions were accessible to each other; therefore the alkali was suggested to interact directly with the Cu ion to promote the oxidation of benzyl alcohol, rather than this promotion being a separate function of the alkali itself. One of the roles of the alkali added to the Cu-Na-ZSM-5 zeolite was promoting the dissociation of the oxygen molecule, as evidenced by the results of the exchange reaction of the oxygen molecule. The alkali was also suggested to neutralize the acid sites in the Cu-Na-ZSM-5 zeolite and prevent its deactivation by retarding the formation of coke-like material on the zeolite. 30 refs., 12 figs., 5 tabs.

  14. How does the carbon fusion reaction happen in stars?

    Directory of Open Access Journals (Sweden)

    X. Tang

    2013-09-01

    Full Text Available The 12C + 12C fusion reaction is one of the most important reactions in the stellar evolution. Due to its compli-cated reaction mechanism, there is great uncertainty in the reaction rate which limits our understanding of vari-ous stellar objects, such as explosions on the surface of neutron stars, white dwarf (type Ia supernovae, and massive stellar evolution. In this paper, I will review the challenges in the study of carbon burning. I will also report recent re-sults from our studies: 1 an upper limit for the 12C + 12C fusion cross sections, 2 measurement of the 12C + 12C at deep sub-barrier energies, 3 a new measurement of the 12C(12C, n reaction. The outlook for the studies of the astrophysical heavy-ion fusion reactions will also be presented.

  15. Study on material properties in order to apply for structural analysis of turbine generator foundation affected by Alkali-Silica reaction

    International Nuclear Information System (INIS)

    Shimizu, H.; Watanabe, Y.; Ishikawa, T.; Sekimoto, H.; Sato, K.; Takiguchi, K.; Masuda, Y.; Nishiguchi, I.

    2005-01-01

    It is well known that material properties (compressive strength, elastic modulus) of a concrete core specimen taken from a structure, which has been affected by alkali-silica reaction (ASR), are reduced significantly in comparison to those of sound concrete. On the other hand, in-situ tests of reinforcement concrete structures also affected by ASR are reported to show only insignificant reduction of rigidity and strength capacities of the structures. The difference of the affect of ASR on a core and a structure is understood to be occurred due to pre-stress effect caused by ASR on the concrete. However, there are only a few reports which show a quantitative evaluation of this effect. Material properties of concrete structure affected by ASR are studied quantitatively by literature review, in-situ tests of actual foundation and model tests. (authors)

  16. Reactions of carbon atoms in pulsed molecular beams

    Energy Technology Data Exchange (ETDEWEB)

    Reisler, H. [Univ. of Southern California, Los Angeles (United States)

    1993-12-01

    This research program consists of a broad scope of experiments designed to unravel the chemistry of atomic carbon in its two spin states, P and D, by using well-controlled initial conditions and state-resolved detection of products. Prerequisite to the proposed studies (and the reason why so little is known about carbon atom reactions), is the development of clean sources of carbon atoms. Therefore, in parallel with the studies of its chemistry and reaction dynamics, the authors continuously explore new, state-specific and efficient ways of producing atomic carbon. In the current program, C({sup 3}P) is produced via laser ablation of graphite, and three areas of study are being pursued: (i) exothermic reactions with small inorganic molecules (e.g., O{sub 2}, N{sub 2}O, NO{sub 2}) that can proceed via multiple pathways; (ii) the influence of vibrational and translational energy on endothermic reactions involving H-containing reactants that yield CH products (e.g., H{sub 2}O H{sub 2}CO); (iii) reactions of C({sup 3}P) with free radicals (e.g., HCO, CH{sub 3}O). In addition, the authors plan to develop a source of C({sup 1}D) atoms by exploiting the pyrolysis of diazotetrazole and its salts in the ablation source. Another important goal involves collaboration with theoreticians in order to obtain relevant potential energy surfaces, rationalize the experimental results and predict the roles of translational and vibrational energies.

  17. Reaction microtextures in entrapped xenoliths in alkali basalts from the Deccan large igneous province, India: Implications to the origin and evolution

    Science.gov (United States)

    Chattopadhaya, Soumi; Ghosh, Biswajit; Morishita, Tomoaki; Nandy, Sandip; Tamura, Akihiro; Bandyopadhyay, Debaditya

    2017-05-01

    The onset of the end-Mesozoic continental rift magmatism in the Deccan volcanic province (DVP), India is marked by alkali magmatism. Lithospheric fragments occurring as xenoliths/xenocrysts entrapped in alkaline basalts from the Kutch area of the DVP preserve reaction microtextures giving an insight into the processes linked to their origin. We interpret the flower texture, an aggregate of systematically arranged tiny diopside crystals, as a product of interactions between ghost quartz xenocrysts with alkaline silica-undersaturated melt. The mantle xenoliths, mostly represented by spinel lherzolites and wehrlites have been infiltrated by melt. The orthopyroxenes present at the margin of the xenoliths or in contact with infiltrated melt exhibit a coronal texture composed of olivine, clinopyroxene and glass around them. The compositions of cores of primary olivines at places retain mantle signatures, whereas, the margins are reequilibrated. Secondary olivines and clinopyroxenes at reaction coronas have a wide range of compositions. Primary clinopyroxenes and spinels in close vicinity to the orthopyroxene corona display a sieve texture defined by clear inclusion-free cores and a compositionally different spongy altered rim with worm-shaped or bubbly inclusions dominantly filled with glass. The rims are marked with higher Ca, Mg-lower Na, Al for clinopyroxenes and higher Ti, Cr-lower Mg, Al for spinels in comparison to their cores. The coronal texture around orthopyroxenes and spongy texture in clinopyroxenes and spinels in these xenoliths are interpreted to be genetically linked. The silicate glasses in the xenoliths show large compositional variations and they are much more siliceous and alkali-rich in comparison to the host basalts. The petrography and mineral chemistry suggest host magma-peridotite interaction during or after the entrainment of the xenoliths, corroborating well with the experimental findings.

  18. Upgrading platform using alkali metals

    Science.gov (United States)

    Gordon, John Howard

    2014-09-09

    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.

  19. Process for the disposal of alkali metals

    International Nuclear Information System (INIS)

    Lewis, L.C.

    1977-01-01

    Large quantities of alkali metals may be safely reacted for ultimate disposal by contact with a hot concentrated caustic solution. The alkali metals react with water in the caustic solution in a controlled reaction while steam dilutes the hydrogen formed by the reaction to a safe level. 6 claims

  20. Alkali content of fly ash : measuring and testing strategies for compliance : [tech transfer summary].

    Science.gov (United States)

    2015-04-01

    This study investigated the test methods used to determine the : alkali content of fly ash. It also evaluated if high-alkali fly ash : exacerbates alkali-silica reaction in laboratory tests and field : concrete.

  1. Alkali content of fly ash : measuring and testing strategies for compliance.

    Science.gov (United States)

    2015-04-01

    Sodium and potassium are the common alkalis present in fly ash. Excessive amounts of fly ash alkalis can cause efflorescence : problems in concrete products and raise concern about the effectiveness of the fly ash to mitigate alkali-silica reaction (...

  2. Kinetic study of the aroxyl radical-scavenging reaction of alpha-tocopherol in methanol solution: notable effect of the alkali and alkaline earth metal salts on the reaction rates.

    Science.gov (United States)

    Ouchi, Aya; Nagaoka, Shin-ichi; Abe, Kouichi; Mukai, Kazuo

    2009-10-08

    A kinetic study of the aroxyl (ArO*) radical-scavenging reaction of alpha-tocopherol (alpha-TocH) has been performed in the presence of six kinds of alkali and alkaline earth metal salts (LiI, LiClO(4), NaI, NaClO(4), KI, and Mg(ClO(4))(2)) in methanol solution, using stopped-flow spectrophotometry. The decay rate of the ArO* for the reaction of alpha-TocH with ArO* increased linearly with increasing concentration of metal salts. The second-order rate constants (k(s)) for the reaction of alpha-TocH with ArO* increased in the order of no metal salt concentration of metal salts. For example, the k(s) values in methanol solution including 4.00 x 10(-1) M of LiI and Mg(ClO(4))(2) were 3.04 and 1.30 times larger than that in the absence of metal salts, respectively. The alkali and alkaline earth metal salts having smaller ionic radius of cation and anion and larger charge of cation gave larger rate constants (k(s)). Effects of metal cations on the UV-vis absorption spectra of the alpha-Toc* (and ArO*) radical were negligible in methanol solution, suggesting that the complex formation between the alpha-Toc* (and ArO*) radical molecule and metal cations is hindered by the hydrogen bond between radical and methanol molecules. The results indicate that the hydrogen transfer reaction of alpha-TocH proceeds via an electron transfer intermediate from alpha-TocH to ArO* radicals followed by proton transfer. Both the coordinations of metal cations to the one-electron reduced anions of ArO* (ArO: (-)) and of counteranions to the one-electron oxidized cations of alpha-TocH (alpha-TocH(+)*) may stabilize the intermediate, resulting in the acceleration of electron transfer. On the other hand, the effect of metal salts on the rate of bimolecular self-reaction (2k(d)) of the alpha-Toc* radical was not observed. The result suggests that the hydrogen transfer reaction between two alpha-Toc* radical molecules proceeds via a one-step hydrogen atom transfer mechanism rather than via an

  3. Comparison studies of surface cleaning methods for PAN-based carbon fibers with acetone, supercritical acetone and subcritical alkali aqueous solutions

    Science.gov (United States)

    Meng, Linghui; Fan, Dapeng; Huang, Yudong; Jiang, Zaixing; Zhang, Chunhua

    2012-11-01

    Four kinds of polyacrylonitrile-based carbon fibers were cleaned by three methods and were characterized by X-ray photoelectron spectroscopy, monofilament tensile strength test and atomic force microscopy (AFM). Experimental results of these tests reveal that the method using supercritical acetone or subcritical potassium hydroxide aqueous solution act as the processing medium shows a better cleaning effect compared to the traditional method, Soxhlet extraction with acetone. The method using supercritical acetone is more appropriate to wipe off the oxygenated contaminants on carbon fibers' surfaces and causes a relatively smaller damage to the bulk strength of each carbon fiber. As far as treating method using the subcritical alkali aqueous solution, it can thoroughly remove silicious contaminants on the surfaces of treated fibers.

  4. Pattern Formation and Reaction Textures during Dunite Carbonation

    Science.gov (United States)

    Lisabeth, H. P.; Zhu, W.

    2015-12-01

    Alteration of olivine-bearing rocks by fluids is one of the most pervasive geochemical processes on the surface of the Earth. Serpentinized and/or carbonated ultramafic rocks often exhibit characteristic textures on many scales, from polygonal mesh textures on the grain-scale to onion-skin or kernel patterns on the outcrop scale. Strong disequilibrium between pristine ultramafic rocks and common geological fluids such as water and carbon dioxide leads to rapid reactions and coupled mechanical and chemical feedbacks that manifest as characteristic textures. Textural evolution during metasomatic reactions can control effective reaction rates by modulating dynamic porosity and therefore reactant supply and reactive surface area. We run hydrostatic experiments on thermally cracked dunites saturated with carbon dioxide bearing brine at 15 MPa confining pressure and 150°C to explore the evolution of physical properties and reaction textures as carbon mineralization takes place in the sample. Compaction and permeability reduction are observed throughout experiments. Rates of porosity and permeability changes are sensitive to pore fluid chemistry. After reaction, samples are imaged in 3-dimension (3D) using a dual-beam FIB-SEM. Analysis of the high resolution 3D microstructure shows that permeable, highly porous domains are created by olivine dissolution at a characteristic distance from pre-existing crack surfaces while precipitation of secondary minerals such as serpentine and magnesite is limited largely to the primary void space. The porous dissolution channels provide an avenue for fluid ingress, allow reactions to continue and could lead to progressive hierarchical fracturing. Initial modeling of the system indicates that this texture is the result of coupling between dissolution-precipitation reactions and the local stress state of the sample.

  5. The reaction of carbon disulphide with -haloketones and primary ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 5. The reaction of carbon disulphide with -haloketones and primary amines in the presence of potassium iodide as catalyst. Javad Safaei-Ghomi Fariba Salimi Ali Ramazani. Volume 125 Issue 5 September 2013 pp 1087-1092 ...

  6. Lewis-acid catalysis of carbon carbon bond forming reactions in water

    NARCIS (Netherlands)

    Engberts, JBFN; Feringa, BL; Keller, E; Otto, S

    1996-01-01

    In this article, we review the recent progress that has been made in the field of Lewis-acid catalysis of carbon carbon-bond-forming reactions in aqueous solution. Since water hampers the hard hard interactions between the catalyst and the reactant, it often complicates catalysis. However, once

  7. Ab Initio Study of Chemical Reactions of Cold SrF and CaF Molecules with Alkali-Metal and Alkaline-Earth-Metal Atoms: The Implications for Sympathetic Cooling.

    Science.gov (United States)

    Kosicki, Maciej Bartosz; Kędziera, Dariusz; Żuchowski, Piotr Szymon

    2017-06-01

    We investigate the energetics of the atom exchange reaction in the SrF + alkali-metal atom and CaF + alkali-metal atom systems. Such reactions are possible only for collisions of SrF and CaF with the lithium atoms, while they are energetically forbidden for other alkali-metal atoms. Specifically, we focus on SrF interacting with Li, Rb, and Sr atoms and use ab initio methods to demonstrate that the SrF + Li and SrF + Sr reactions are barrierless. We present potential energy surfaces for the interaction of the SrF molecule with the Li, Rb, and Sr atoms in their energetically lowest-lying electronic spin states. The obtained potential energy surfaces are deep and exhibit profound interaction anisotropies. We predict that the collisions of SrF molecules in the rotational or Zeeman excited states most likely have a strong inelastic character. We discuss the prospects for the sympathetic cooling of SrF and CaF molecules using ultracold alkali-metal atoms.

  8. Kinetic study of the α-tocopherol-regeneration reaction of ubiquinol-10 in methanol and acetonitrile solutions: notable effect of the alkali and alkaline earth metal salts on the reaction rates.

    Science.gov (United States)

    Mukai, Kazuo; Oi, Masanori; Ouchi, Aya; Nagaoka, Shin-ichi

    2012-03-01

    A kinetic study of regeneration reaction of α-tocopherol (α-TocH) by ubiquinol-10 has been performed in the presence of four kinds of alkali and alkaline earth metal salts (LiClO(4), NaClO(4), NaI, and Mg(ClO(4))(2)) in methanol and acetonitrile solutions, using double-mixing stopped-flow spectrophotometry. The second-order rate constants (k(r)'s) for the reaction of α-tocopheroxyl (α-Toc•) radical with ubiquinol-10 increased and decreased notably with increasing concentrations of metal salts in methanol and acetonitrile, respectively. The k(r) values increased in the order of no metal salt NaClO(4) ~ NaI > LiClO(4) > Mg(ClO(4))(2) at the same concentration of metal salts. The metal salts having a smaller ionic radius of cation and a larger charge of cation gave a larger k(r) value in methanol, and a smaller k(r) value in acetonitrile. The effect of anion was almost negligible in both the solvents. Notable effects of metal cations on the UV-vis absorption spectrum of α-Toc• radical were observed in aprotic acetonitrile solution, suggesting complex formation between α-Toc• and metal cations. On the other hand, effects of metal cations were negligible in protic methanol, suggesting that the complex formation between α-Toc• and metal cations is hindered by the hydrogen bond between α-Toc• and methanol molecules. The difference between the reaction mechanisms in methanol and acetonitrile solutions was discussed on the basis of the results obtained. High concentrations of alkali and alkaline earth metal salts coexist with α-TocH and ubiquinol-10 in plasma, blood, and many tissues, suggesting the contribution of the metal salts to the above regeneration reaction in biological systems.

  9. Heterogeneously Catalysed Chemical Reactions in Carbon Dioxide Medium

    DEFF Research Database (Denmark)

    Musko, Nikolai E.

    the selective hydrogenation of unsaturated aldehydes in carbon dioxide medium. It was found that supported tungstosilicic acid catalysts and acidic resin Amberlyst-15 are very effective for performing aldol reactions. The positive influence of temperature and CO2-content on catalyst activity was studied....... Furthermore, the “one-pot” synthesis with 2-butenal was performed using bifunctional and mixed catalysts. The reactions were studied in different reactor types and reaction conditions were optimised using CPA calculations. Extensive catalyst characterisation was carried out in order to understand the catalyst...... shown that CPA can satisfactorily describe any type of phase equilibria for the quaternary reaction mixture as well as ternaries and binaries that comprise it. This makes CPA a universal and very useful model for many practical applications. All aforementioned studies have shown that supercritical...

  10. Eight-phase alkali feldspars: low-temperature cryptoperthite, peristerite and multiple replacement reactions in the Klokken intrusion

    Science.gov (United States)

    Parsons, Ian; Fitz Gerald, John D.; Heizler, Matthew T.; Heizler, Lynn L.; Ivanic, Tim; Lee, Martin R.

    2013-05-01

    Eight feldspar phases have been distinguished within individual alkali feldspar primocrysts in laminated syenite members of the layered syenite series of the Klokken intrusion. The processes leading to the formation of the first four phases have been described previously. The feldspars crystallized as homogeneous sodian sanidine and exsolved by spinodal decomposition, between 750 and 600 °C, depending on bulk composition, to give fully coherent, strain-controlled braid cryptoperthites with sub-μm periodicities. Below ~500 °C, in the microcline field, these underwent a process of partial mutual replacement in a deuteric fluid, producing coarse (up to mm scale), turbid, incoherent patch perthites. We here describe exsolution and replacement processes that occurred after patch perthite formation. Both Or- and Ab-rich patches underwent a new phase of coherent exsolution by volume diffusion. Or-rich patches began to exsolve albite lamellae by coherent nucleation in the range 460-340 °C, depending on patch composition, leading to film perthite with ≤1 μm periodicities. Below ~300 °C, misfit dislocation loops formed, which were subsequently enlarged to nanotunnels. Ab-rich patches (bulk composition ~Ab91Or1An8), in one sample, exsolved giving peristerite, with one strong modulation with a periodicity of ~17 nm and a pervasive tweed microtexture. The Ab-rich patches formed with metastable disorder below the peristerite solvus and intersected the peristerite conditional spinodal at ~450 °C. This is the first time peristerite has been imaged using TEM within any perthite, and the first time peristerite has been found in a relatively rapidly cooled geological environment. The lamellar periodicities of film perthite and peristerite are consistent with experimentally determined diffusion coefficients and a calculated cooling history of the intrusion. All the preceding textures were in places affected by a phase of replacement correlating with regions of extreme optical

  11. Olefination reactions of phosphorus-stabilized carbon nucleophiles.

    Science.gov (United States)

    Gu, Yonghong; Tian, Shi-Kai

    2012-01-01

    A range of phosphorus-stabilized carbon nucleophiles have been employed for alkene synthesis with high chemo-, regio-, and stereoselectivity. The Wittig, Horner-Wadsworth-Emmons, Horner-Wittig, and Evans-Akiba reactions utilize phosphonium-, phosphonate-, phosphine oxide-, and pentacoordinated phosphorane-stabilized carbanions as nucleophiles, respectively, to undergo olefination with aldehydes or ketones, and each of these transformations has its own advantages and limitations. Modifying the structures of these nucleophiles along with optimizing reaction conditions results in the formation of a wide variety of polysubstituted alkenes in a highly stereoselective manner. The olefination of imines with phosphonium ylides has recently emerged as a useful approach to tune the stereoselectivity for alkene synthesis. This review focuses on recent advances in the stereoselective olefination of phosphorus-stabilized carbon nucleophiles.

  12. Effective Permeability Change in Wellbore Cement with Carbon Dioxide Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Um, Wooyong; Jung, Hun Bok; Martin, Paul F.; McGrail, B. Peter

    2011-11-01

    Portland cement, a common sealing material for wellbores for geological carbon sequestration was reacted with CO{sub 2} in supercritical, gaseous, and aqueous phases at various pressure and temperature conditions to simulate cement-CO{sub 2} reaction along the wellbore from carbon injection depth to the near-surface. Hydrated Portland cement columns (14 mm diameter x 90 mm length; water-to-cement ratio = 0.33) including additives such as steel coupons and Wallula basalt fragments were reacted with CO{sub 2} in the wet supercritical (the top half) and dissolved (the bottom half) phases under carbon sequestration condition with high pressure (10 MPa) and temperature (50 C) for 5 months, while small-sized hydrated Portland cement columns (7 mm diameter x 20 mm length; water-to-cement ratio = 0.38) were reacted with CO{sub 2} in dissolved phase at high pressure (10 MPa) and temperature (50 C) for 1 month or with wet CO{sub 2} in gaseous phase at low pressure (0.2 MPa) and temperature (20 C) for 3 months. XMT images reveal that the cement reacted with CO{sub 2} saturated groundwater had degradation depth of {approx}1 mm for 1 month and {approx}3.5 mm for 5 month, whereas the degradation was minor with cement exposure to supercritical CO{sub 2}. SEM-EDS analysis showed that the carbonated cement was comprised of three distinct zones; the innermost less degraded zone with Ca atom % > C atom %, the inner degraded zone with Ca atom % {approx} C atom % due to precipitation of calcite, the outer degraded zone with C atom % > Ca atom % due to dissolution of calcite and C-S-H, as well as adsorption of carbon to cement matrix. The outer degraded zone of carbonated cement was porous and fractured because of dissolution-dominated reaction by carbonic acid exposure, which resulted in the increase in BJH pore volume and BET surface area. In contrast, cement-wet CO{sub 2}(g) reaction at low P (0.2 MPa)-T (20 C) conditions for 1 to 3 months was dominated by precipitation of micron

  13. Use of alkali metal salts to prepare high purity single-walled carbon nanotube solutions and thin films

    Science.gov (United States)

    Ashour, Rakan F.

    Single-walled carbon nanotubes (SWCNTs) display interesting electronic and optical properties desired for many advanced thin film applications, such as transparent conductive electrodes or thin-film transistors. Large-scale production of SWCNTs generally results in polydispersed mixtures of nanotube structures. Since SWCNT electronic character (conducting or semiconducting nature) depends on the nanotube structure, application performance is being held back by this inability to discretely control SWCNT synthesis. Although a number of post-production techniques are able to separate SWCNTs based on electronic character, diameter, or chirality, most still suffer from the disadvantage of high costs of materials, equipment, or labor intensity to be relevant for large-scale production. On the other hand, chromatographic separation has emerged as a method that is compatible with large scale separation of metallic and semiconducting SWCNTs. In this work, SWCNTs, in an aqueous surfactant suspension of sodium dodecyl sulfate (SDS), are separated by their electronic character using a gel chromatography process. Metallic SWCNTs (m-SWCNTs) are collected as initial fractions since they show minimum interaction with the gel medium, whereas, semiconducting SWCNTs (sc- SWCNTs) remain adsorbed to the gel. The process of sc-SWCNT retention in the gel is found to be driven by the packing density of SDS around the SWCNTs. Through a series of separation experiments, it is shown that sc-SWCNTs can be eluted from the gel simply by disturbing the configuration of the SDS/SWCNT micellar structure. This is achieved by either introducing a solution containing a co-surfactant, such as sodium cholate (SC), or solutions of alkali metal ionic salts. Analysis of SWCNT suspensions by optical absorption provides insights into the effect of changing the metal ion (M+ = Li+, Na+, and K+) in the eluting solution. Salts with smaller metal ions (e.g. Li+) require higher concentrations to achieve

  14. Chemical Reactions in the Processing of Mosi2 + Carbon Compacts

    Science.gov (United States)

    Jacobson, Nathan S.; Lee, Kang N.; Maloy, Stuart A.; Heuer, Arthur H.

    1993-01-01

    Hot-pressing of MoSi2 powders with carbon at high temperatures reduces the siliceous grain boundary phase in the resultant compact. The chemical reactions in this process were examined using the Knudsen cell technique. A 2.3 wt pct oxygen MoSi2 powder and a 0.59 wt pct oxygen MoSi2 powder, both with additions of 2 wt pct carbon, were examined. The reduction of the siliceous grain boundary phase was examined at 1350 K and the resultant P(SiO)/P(CO) ratios interpreted in terms of the SiO(g) and CO(g) isobars on the Si-C-O predominance diagram. The MoSi2 + carbon mixtures were then heated at the hot-pressing temperature of 2100 K. Large weight losses were observed and could be correlated with the formation of a low-melting eutectic and the formation and vaporization of SiC.

  15. Electrode reaction mechanisms in molten carbonate fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Selman, J.R.; Nishina, T.; Lin, Y.P.; Yeager, E.B.; Tryk, D.A.

    1989-07-01

    This report describes the results of a joint research effort at Illinois Institute of Technology (IIT) and Case Western Reserve University (CWRU) to elucidate the reaction mechanism of oxygen reduction at the cathode of the molten carbonate fuel cell (MCFC). This research project was aimed at developing novel experimental approaches to the chemistry and electrode kinetics of oxygen reduction under MCFC conditions, and improving our fundamental understanding of the reaction mechanism as it applies to the MCFC. IIT's contribution was focused on developing and using rotating electrodes with well-defined mass-transfer properties, to characterize the electrode kinetics of oxygen reduction in molten carbonate. CWRU's contribution was focused on developing and using micro-electrodes for the same purpose, and also on developing spectroscopic cells and carrying out various types of spectroscopic measurements to characterize the oxygen species in molten carbonate under MCFC conditions. This report is divided into two main parts. Part 1 provides the technical background of the questions concerning oxygen reduction in molten carbonate as they apply to the MCFC system. The methodological approach and the objectives of the research are also presented. The second part describes the development of the rotating electrodes, micro-electrodes and spectroscopic cells and the results of measurements, as well as the interpretation of the data. Conclusions of this project, including some recommendations for further research, are also given in this part. 111 refs., 69 figs., 7 tabs.

  16. Reaction rate for carbon burning in massive stars

    Science.gov (United States)

    Jiang, C. L.; Santiago-Gonzalez, D.; Almaraz-Calderon, S.; Rehm, K. E.; Back, B. B.; Auranen, K.; Avila, M. L.; Ayangeakaa, A. D.; Bottoni, S.; Carpenter, M. P.; Dickerson, C.; DiGiovine, B.; Greene, J. P.; Hoffman, C. R.; Janssens, R. V. F.; Kay, B. P.; Kuvin, S. A.; Lauritsen, T.; Pardo, R. C.; Sethi, J.; Seweryniak, D.; Talwar, R.; Ugalde, C.; Zhu, S.; Bourgin, D.; Courtin, S.; Haas, F.; Heine, M.; Fruet, G.; Montanari, D.; Jenkins, D. G.; Morris, L.; Lefebvre-Schuhl, A.; Alcorta, M.; Fang, X.; Tang, X. D.; Bucher, B.; Deibel, C. M.; Marley, S. T.

    2018-01-01

    Carbon burning is a critical phase for nucleosynthesis in massive stars. The conditions for igniting this burning stage, and the subsequent isotope composition of the resulting ashes, depend strongly on the reaction rate for 12C+12C fusion at very low energies. Results for the cross sections for this reaction are influenced by various backgrounds encountered in measurements at such energies. In this paper, we report on a new measurement of 12C+12C fusion cross sections where these backgrounds have been minimized. It is found that the astrophysical S factor exhibits a maximum around Ecm=3.5 -4.0 MeV, which leads to a reduction of the previously predicted astrophysical reaction rate.

  17. The Emissions of Carbon Dioxide, Methane, and Nitrous Oxide during Winter without Cultivation in Local Saline-Alkali Rice and Maize Fields in Northeast China

    Directory of Open Access Journals (Sweden)

    Hao Zhang

    2017-10-01

    Full Text Available Agricultural ecosystems are important contributors to atmospheric greenhouse gasses (GHGs; however, in situ winter emission data in saline-alkali fields are scarce. Gas samples were collected during different periods, from three rice (R1–R3 and three maize (M1–M3 fields with different soil pH levels and salinity conditions. Carbon dioxide (CO2 emissions in the rice and maize fields decreased with decreasing temperature during the freezing period and increased with the rising temperature during the thawing period, with the majority of winter CO2 emissions occurring during these two periods. Peaks in methane (CH4 emissions were observed during the freezing period in the rice fields and during the snow-melting period in the rice and maize fields. CH4 emissions in the rice fields and CH4 uptake rates in the maize fields were significantly (P < 0.05 related to surface soil temperature. Nitrous oxide (N2O emissions remained relatively low, except for during the peaks observed during the snow-melting period in both the rice and maize fields, leading to the high GHG contribution of the snow-melting period throughout the winter. Higher pH and salinity conditions consistently resulted in lower CO2, CH4, and N2O emissions, CH4 uptake, and lower global warming potential (GWP. These results can contribute to the assessment of the GWP during winter in saline-alkali regions.

  18. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

    Science.gov (United States)

    Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI

    2011-01-18

    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  19. 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

    2016-01-01

    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.

  20. 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)

    2015-09-01

    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

  1. Absorption of carbon dioxide and isotope exchange rate of carbon in a reaction system between carbon dioxide and carbamic acid

    International Nuclear Information System (INIS)

    Takeshita, Kenji; Kitamoto, Asashi

    1985-01-01

    The performance of isotope separation of carbon-13 by chemical exchange between carbon dioxide and carbamic acid was studied. The working fluid used in the study was a solution of DNBA, (C 4 H 9 ) 2 NH and n-octane mixture. Factors related to the isotope exchange rate were measured, such as the absorption rate of carbon dioxide into the solution of DNBA and n-octane, the isotope exchange rate and the separation factor in the reaction between CO 2 and carbamic acid. The absorption of CO 2 into the working fluid was the sum of chemical absorption by DNBA and physical absorption by n-octane. The absorption of carbon dioxide into the working fluid was negligible at temperatures over 90 0 C, but increased gradually at lower temperatures. Carbon dioxide was absorbed into DNBA by chemical absorption, and DNBA was converted to carbamic acid by the reaction. The reaction for synthesis and decomposition of carbamic acid was reversible. The separation factor in equilibrium reached a large value at lower temperatures. The isotope exchange rate between gas and liquid was proportional to the product of the concentration of carbamic acid and the concentration of CO 2 by physical absorption. The isotope separation of carbon by chemical exchange reaction is better operated under the conditions of lower temperature and higher pressure. (author)

  2. Kinetics of iron redox reaction in silicate melts: A high temperature Xanes study on an alkali basalt

    Energy Technology Data Exchange (ETDEWEB)

    Cochain, B; Neuville, D R; Roux, J; Strukelj, E; Richet, P [Physique des Mineraux et Magmas, Geochimie-Cosmochimie, CNRS-IPGP, 4 place Jussieu, 75005 Paris (France); Ligny, D de [Universite Claude Bernard Lyon 1, LPCML, F-69622 Villeurbanne (France); Baudelet, F, E-mail: cochain@ipgp.jussieu.f [Synchrotron SOLEIL, L' Orme des Merisiers, Saint Aubin (France)

    2009-11-15

    In Earth and Materials sciences, iron is the most important transition element. Glass and melt properties are strongly affected by iron content and redox state with the consequence that some properties (i.e. viscosity, heat capacity, crystallization...) depend not only on the amounts of Fe{sup 2+} and Fe{sup 3+}, but also on the coordination state of these ions. In this work we investigate iron redox reactions through XANES experiments at the K-edge of iron. Using a high-temperature heating device, pre-edge of XANES spectra exhibits definite advantages to make in-situ measurements and to determine the evolution of redox state with time, temperature and composition of synthetic silicate melts. In this study, new kinetics measurements are presented for a basalt melt from the 31,000-BC eruption of the Puy de Lemptegy Volcano in France. These measurements have been made between 773 K and at superliquidus temperatures up to 1923 K.

  3. Analysis of carbon partitioning during ausferritic reaction in ADI

    Directory of Open Access Journals (Sweden)

    Z. Ławrynowicz

    2008-10-01

    Full Text Available The investigation was carried out to examine the influence of temperature and times of austempering process on the maximum extend towhich the ausferritic reaction can proceed and the carbon content in retained austenite. Specimens prepared from ductile cast iron wereaustenitised at 950oC for 60 minutes and austempered at four temperatures: 250, 300, 350 and 400oC. The samples were austempered atthese temperatures for 15, 30, 60, 120 and 240 minutes and finally quenched to ambient temperature. Volume fractions of retainedaustenite and carbon concentration in the residual austenite have been observed by using X-ray diffraction. Additionally, carbonconcentration in the residual austenite was calculated using volume fraction data of austenite and a model developed by Bhadeshia basedon the McLellan and Dunn quasi-chemical thermodynamic model. It was found that the obtained extend of ausferritic transformation isonly possible when the microstructure consists of not only ausferrite but additionally precipitated carbides.

  4. Reaction between molybdenum and carbon, and several carbides

    International Nuclear Information System (INIS)

    Morozumi, Shotaro; Kikuchi, Michio; Sugai, Shinzo; Hayashi, Masaaki.

    1980-01-01

    Diffusion couples of molybdenum with carbon and several carbides, i.e. B 4 C, SiC, TiC, and TaC, respectively, were heated for up to 3.6 x 10 5 s at various temperatures ranging from 1373 to 2223 K. The couples were then examined for composition, growth rate, structure, and hardness of reaction layers. Main results obtained are as follows: (1) In the Mo-C system, only Mo 2 C layer was formed at below 1873 K, while two sub- layers consisted of Mo 2 C and eta (MoC sub(1-x)), respectively, were found at above 1873 K. The activation energy for growth of total layer was 374 kJ/mol. (2) In the Mo-B 4 C system, two sub-layers consisted of Mo 2 B and MoB, respectively, with dispersed carbon particles were formed. (3) In the Mo-SiC system, Mo 2 C layer, including eta (MoC sub(1-x)) phase at high temperature, mixture of Mo 2 C and Mo 3 Si 2 phases, and Mo 3 Si 2 phase in order from the Mo side were formed. The activation energy for growth of total layer was 477 kJ/mol. (4) In the Mo-TiC system, two kinds of TiC in point of view of free carbon content were used; one is with 0.2% free carbon and the other is with 0.01%. In the Mo-TiC with 0.2% free carbon system, two sub-layers, i.e. relatively thick Mo 2 C layer and thin (Ti, Mo)C layer, were formed, while in the Mo-TiC with 0.01% free carbon system two thin sub-layers, Mo 2 C and (Ti, Mo)C, were formed; the Mo 2 C layer in the latter case was very thin and was not found after short time heating at low temperature. The activation energy for growth of Mo 2 C layer in the former system was 393 kJ/mol. (5) In the Mo-TaC with 0.02% free carbon system, two thin sub-layers, (Mo, Ta) 2 C and (Ta, Mo)C, were observed. (6) TEM studies on the interface between Mo (bcc) and Mo 2 C (hcp) showed that there was the following orientation relation, called as the Burgers relation, between these two phases; (110)sub(Mo)//(0001)sub(Mo 2 C), sub(Mo)// - 0>sub(Mo 2 C). (author)

  5. Oxidation of guanine in G, GG, and GGG sequence contexts by aromatic pyrenyl radical cations and carbonate radical anions: relationship between kinetics and distribution of alkali-labile lesions.

    Science.gov (United States)

    Lee, Young Ae; Durandin, Alexander; Dedon, Peter C; Geacintov, Nicholas E; Shafirovich, Vladimir

    2008-02-14

    Oxidatively generated DNA damage induced by the aromatic radical cation of the pyrene derivative 7,8,9,10-tetrahydroxytetrahydrobenzo[a]pyrene (BPT), and by carbonate radicals anions, was monitored from the initial one-electron transfer, or hole injection step, to the formation of hot alkali-labile chemical end-products monitored by gel electrophoresis. The fractions of BPT molecules bound to double-stranded 20-35-mer oligonucleotides with noncontiguous guanines G and grouped as contiguous GG and GGG sequences were determined by a fluorescence quenching method. Utilizing intense nanosecond 355 nm Nd:YAG laser pulses, the DNA-bound BPT molecules were photoionized to BPT*+ radicals by a consecutive two-photon ionization mechanism. The BPT*+ radicals thus generated within the duplexes selectively oxidize guanine by intraduplex electron-transfer reactions, and the rate constants of these reactions follow the trend 5'-..GGG.. > 5'-..GG.. > 5'-..G... In the case of CO3*- radicals, the oxidation of guanine occurs by intermolecular collision pathways, and the bimolecular rate constants are independent of base sequence context. However, the distributions of the end-products generated by CO3*- radicals, as well as by BPT*+, are base sequence context-dependent and are greater than those in isolated guanines at the 5'-G in 5'-...GG... sequences, and the first two 5'- guanines in the 5'-..GGG sequences. These results help to clarify the conditions that lead to a similar or different base sequence dependence of the initial hole injection step and the final distribution of oxidized, alkali-labile guanine products. In the case of the intermolecular one-electron oxidant CO3*-, the rate constant of hole injection is similar for contiguous and isolated guanines, but the subsequent equilibration of holes by hopping favors trapping and product formation at contiguous guanines, and the sequence dependence of these two phenomena are not correlated. In contrast, in the case of the DNA

  6. kinetics of the coupled gas-iron reactions involving silicon and carbon

    African Journals Online (AJOL)

    user

    1985-09-01

    Sep 1, 1985 ... The rate-limiting factors seem to be the surface chemical reactions, with rate of supply of silicon monoxide probably contributing. 1. INTRODUCTION. In order to gain an insight into the nature of the coupled reactions existing between carbon and silicon when a gas phase containing carbon dioxide, carbon.

  7. Initial reaction between CaO and SO2 under carbonating and non-carbonating conditions

    DEFF Research Database (Denmark)

    Rasmussen, Martin Hagsted; Wedel, Stig; Pedersen, Kim H.

    2015-01-01

    The initial kinetics of the CaO/SO2 reaction have been investigated for reaction times shorter than 1s and in the temperature interval between 450 and 600°C under both carbonating and non-carbonating conditions (0-20 vol% CO2) to clarify how recirculating CaO influences the emission of SO2 from a...

  8. The synthesis of PdPt/carbon paper via surface limited redox replacement reactions for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Motsoeneng, RG

    2015-09-01

    Full Text Available Surface-limited redox replacement reactions using the electrochemical atomic layer deposition (EC-ALD) technique were used to synthesize PdPt bimetallic electrocatalysts on carbon paper substrate. Electrocatalysts having different Pd:Pt ratio were...

  9. Carbon nanotube synthesis via the catalytic CVD method: a review on the effect of reaction parameters

    OpenAIRE

    Öncel, Çınar; Oncel, Cinar; Yürüm, Yuda; Yurum, Yuda

    2006-01-01

    This review covers the results obtained in carbon nanotube synthesis by chemical vapor deposition. Parameters such as catalysts, supports, carbon precursors, reaction time, temperature and gas flow rates that are used in the production of carbon nanotubes are discussed throughout the text. Purification of the synthesized carbon nanotubes and methods utilized for cost reduction were also explored.

  10. Synthesis of beta carbon nitride nanosized crystal through mechanochemical reaction

    CERN Document Server

    Yin Long Wei; Liu Yu Xian; Sui Jin Ling; Wang Jing Min

    2003-01-01

    Nanosized beta carbon nitride (beta-C sub 3 N sub 4), of grain size several tens of nanometres, has been synthesized by mechanochemical reaction processing. The low-cost synthetic method developed facilitates the novel and effective synthesis of nanosized crystalline beta-C sub 3 N sub 4 (a = 6.36 A, c = 4.648 A) powders. The graphite powders were first milled to a nanoscale state, then the nanosized graphite powders were milled in an atmosphere of NH sub 3 gas. It was found that nanosized beta-C sub 3 N sub 4 was formed after high-energy ball milling under an NH sub 3 atmosphere. After thermal annealing, the shape of the beta-C sub 3 N sub 4 changes from flake-like to sphere-like. The nanosized beta-C sub 3 N sub 4 formed was characterized by x-ray diffraction, Fourier transformation infrared spectroscopy, and transmission electron microscopy. A solid-gas reaction mechanism was proposed for the formation of nanosized beta-C sub 3 N sub 4 at room temperature induced by mechanochemical activation.

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

    Science.gov (United States)

    Shrimer, Fred H.

    2005-01-01

    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

  12. Alkali metal and alkali metal hydroxide intercalates of the layered transition metal disulfides

    International Nuclear Information System (INIS)

    Kanzaki, Y.; Konuma, M.; Matsumoto, O.

    1981-01-01

    The intercalation reaction of some layered transition metal disulfides with alkali metals, alkali metal hydroxides, and tetraalkylammonium hydroxides were investigated. The alkali metal intercalates were prepared in the respective metal-hexamethylphosphoric triamide solutions in vaccuo, and the hydroxide intercalates in aqueous hydroxide solutions. According to the intercalation reaction, the c-lattice parameter was increased, and the increase indicated the expansion of the interlayer distance. In the case of alkali metal intercalates, the expansion of the interlayer distance increased continuously, corresponding to the atomic radius of the alkali metal. On the other hand, the hydroxide intercalates showed discrete expansion corresponding to the effective ionic radius of the intercalated cation. All intercalates of TaS 2 amd NbS 2 were superconductors. The expansion of the interlayer distance tended to increase the superconducting transition temperature in the intercalates of TaS 2 and vice versa in those of NbS 2 . (orig.)

  13. Milk-alkali syndrome

    Science.gov (United States)

    Calcium-alkali syndrome; Cope syndrome; Burnett syndrome; Hypercalcemia; Calcium metabolism disorder ... Milk-alkali syndrome is almost always caused by taking too many calcium supplements, usually in the form of calcium ...

  14. Ability of an alkali-tolerant mutant strain of the microalga Chlorella sp. AT1 to capture carbon dioxide for increasing carbon dioxide utilization efficiency.

    Science.gov (United States)

    Kuo, Chiu-Mei; Lin, Tsung-Hsien; Yang, Yi-Chun; Zhang, Wen-Xin; Lai, Jinn-Tsyy; Wu, Hsi-Tien; Chang, Jo-Shu; Lin, Chih-Sheng

    2017-11-01

    An alkali-tolerant Chlorella sp. AT1 mutant strain was screened by NTG mutagenesis. The strain grew well in pH 6-11 media, and the optimal pH for growth was 10. The CO 2 utilization efficiencies of Chlorella sp. AT1 cultured with intermittent 10% CO 2 aeration for 10, 20 and 30min at 3-h intervals were approximately 80, 42 and 30%, respectively. In alkaline medium (pH=11) with intermittent 10% CO 2 aeration for 30min at 3-, 6- and 12-h intervals, the medium pH gradually changed to 10, and the biomass productivities of Chlorella sp. AT1 were 0.987, 0.848 and 0.710gL -1 d -1 , respectively. When Chlorella sp. AT1 was aerated with 10% CO 2 intermittently for 30min at 3-h intervals in semi-continuous cultivation for 21days, the biomass concentration and biomass productivity were 4.35gL -1 and 0.726gL -1 d -1 , respectively. Our results show that CO 2 utilization efficiency can be markedly increased by intermittent CO 2 aeration and alkaline media as a CO 2 -capturing strategy for alkali-tolerant microalga cultivation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Reaction of uranium oxides with chlorine and carbon or carbon monoxide to prepare uranium chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Haas, P.A.; Lee, D.D.; Mailen, J.C.

    1991-11-01

    The preferred preparation concept of uranium metal for feed to an AVLIS uranium enrichment process requires preparation of uranium tetrachloride (UCI{sub 4}) by reacting uranium oxides (UO{sub 2}/UO{sub 3}) and chlorine (Cl{sub 2}) in a molten chloride salt medium. UO{sub 2} is a very stable metal oxide; thus, the chemical conversion requires both a chlorinating agent and a reducing agent that gives an oxide product which is much more stable than the corresponding chloride. Experimental studies in a quartz reactor of 4-cm ID have demonstrated the practically of some chemical flow sheets. Experimentation has illustrated a sequence of results concerning the chemical flow sheets. Tests with a graphite block at 850{degrees}C demonstrated rapid reactions of Cl{sub 2} and evolution of carbon dioxide (CO{sub 2}) as a product. Use of carbon monoxide (CO) as the reducing agent also gave rapid reactions of Cl{sub 2} and formation of CO{sub 2} at lower temperatures, but the reduction reactions were slower than the chlorinations. Carbon powder in the molten salt melt gave higher rates of reduction and better steady state utilization of Cl{sub 2}. Addition of UO{sub 2} feed while chlorination was in progress greatly improved the operation by avoiding the plugging effects from high UO{sub 2} concentrations and the poor Cl{sub 2} utilizations from low UO{sub 2} concentrations. An UO{sub 3} feed gave undesirable effects while a feed of UO{sub 2}-C spheres was excellent. The UO{sub 2}-C spheres also gave good rates of reaction as a fixed bed without any molten chloride salt. Results with a larger reactor and a bottom condenser for volatilized uranium show collection of condensed uranium chlorides as a loose powder and chlorine utilizations of 95--98% at high feed rates. 14 refs., 7 figs., 14 tabs.

  16. Template-free synthesis of porous graphitic carbon nitride/carbon composite spheres for electrocatalytic oxygen reduction reaction.

    Science.gov (United States)

    Fu, Xiaorui; Hu, Xiaofei; Yan, Zhenhua; Lei, Kaixiang; Li, Fujun; Cheng, Fangyi; Chen, Jun

    2016-01-28

    Porous graphitic carbon nitride/carbon composite spheres were synthesized using melamine and cyanuric acid, and glucose as the carbon nitride and carbon precursor, respectively. The 3D hierarchical composites efficiently catalyzed the oxygen reduction reaction with an onset potential of 0.90 V and a kinetic current density of 23.92 mA cm(-2). These merit their promising applications in fuel cells and metal-air batteries.

  17. Investigation of Reactions between Glauconite and Carbon Dioxide, with Implications for Carbon Sequestration

    Science.gov (United States)

    Nguyen, A. V.; Gabitov, R. I.; Beckingham, L. E.; Toghiani, H.; Fei, Y.; Kirkland, B. L.

    2017-12-01

    Mineral trapping is one potentially effective technology for long-term storage of carbon dioxide in a subsurface environment that has high temperature and pressure. Conceptually, upon injection of CO2 as a supercritical fluid into geological formations, the CO2 will react with the host rock to form a secondary carbonate mineral that is stable, thus creating a long-term carbon sink under thermodynamic condition of the reaction. Previous studies have demonstrated crystallization of magnesite by reactivity of CO2 and olivine-bearing basalt. Glauconite, a Fe/Ca/Mg bearing aluminosilicate mineral, a potential candidate for reaction with CO2 is common in sedimentary rock formations. The objectives of this study are to 1) develop a protocol for testing mineral trapping in the subsurface and 2) use that protocol to test the reactivity and effectiveness of the mineral glauconite in carbon sequestration. A sample from the Cambrian Riley Formation of Central Texas was selected for this study because it is extremely rich in glauconite. Mineral composition of the powdered sample was investigated by X-ray diffraction (XRD), which revealed that the glauconitic sandstone contains glauconite 20.4%, quartz 71%, and celadonite 8.6%. In the first experiment, 1.5 g of 0.01- 0.5 cm diameter grains reacted with a supercritical CO2 fluid in 30 g of sea water. The laboratory experiment was conducted in a stainless steel vessel in situ reservoir conditions at 120 degrees Celsius and 100 bars. After CO2 injection, pH of the brine decreased from 8.23 to 7. Scanning electron microscopy (SEM) and X-ray diffraction method showed no carbonate formed after 10 days of reaction. However, further experimental modifications facilitated formation of calcite at higher pH. In the second experiment, 0.7 g of 10-75 μm grains presumably reacted with CO2 formed by ammonium carbonate decomposition in a brine of NaCl 0.5 and CaCl2 0.25M; pH after the end of experiment was 7.74. The autoclave was set at 120

  18. [Characteristics of 'salt island' and 'fertile island' for Tamarix chinensis and soil carbon, nitrogen and phosphorus ecological stoichiometry in saline-alkali land].

    Science.gov (United States)

    Zhang, Li-hua; Chen, Xiao-bing

    2015-03-01

    To clarify the nutrient characteristics of 'salt island' and 'fertile island' effects in saline-alkali soil, the native Tamarix chinensis of the Yellow River Delta (YRD) was selected to measure its soil pH, electrical conductivity (EC), organic carbon (SOC), total nitrogen (N), total phosphorus (P) and their stoichiometry characteristics at different soil depths. The results showed that soil pH and EC increased with the increasing soil depth. Soil EC and P in the 0-20 cm layer decreased and increased from canopied area to interspace, respectively. SOC, N, N/P and C/P in the 20-40 cm soil layer decreased, and C/N increased from the shrub center to interspace. SOC and N contents between island and interspace both decreased but P content decreased firstly and then increased with the increasing soil depth. Soil pH correlated positively with EC. In addition, pH and EC correlated negatively with C, N, P contents and their ecological stoichiometry.

  19. Study on Utilization of Carboxyl Group Decorated Carbon Nanotubes and Carbonation Reaction for Improving Strengths and Microstructures of Cement Paste

    Directory of Open Access Journals (Sweden)

    Xiantong Yan

    2016-08-01

    Full Text Available Carbon nanotubes (CNTs have excellent mechanical properties and can be used to reinforce cement-based materials. On the other hand, the reaction product of carbonation with hydroxides in hydrated cement paste can reduce the porosity of cement-based materials. In this study, a novel method to improve the strength of cement paste was developed through a synergy of carbon nanotubes decorated with carboxyl group and carbonation reactions. The experimental results showed that the carboxyl group (–COOH of decorated carbon nanotubes and the surfactant can control the morphology of the calcium carbonate crystal of carbonation products in hydrated cement paste. The spindle-like calcium carbonate crystals showed great morphological differences from those observed in the conventional carbonation of cement paste. The spindle-like calcium carbonate crystals can serve as fiber-like reinforcements to reinforce the cement paste. By the synergy of the carbon nanotubes and carbonation reactions, the compressive and flexural strengths of cement paste were significantly improved and increased by 14% and 55%, respectively, when compared to those of plain cement paste.

  20. A high-performance mesoporous carbon supported nitrogen-doped carbon electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Xu, Jingjing; Lu, Shiyao; Chen, Xu; Wang, Jianan; Zhang, Bo; Zhang, Xinyu; Xiao, Chunhui; Ding, Shujiang

    2017-12-01

    Investigating low-cost and highly active electrocatalysts for oxygen reduction reactions (ORR) is of crucial importance for energy conversion and storage devices. Herein, we design and prepare mesoporous carbon supported nitrogen-doped carbon by pyrolysis of polyaniline coated on CMK-3. This electrocatalyst exhibits excellent performance towards ORR in alkaline media. The optimized nitrogen-doped mesoporous electrocatalyst show an onset potential (E onset) of 0.95 V (versus reversible hydrogen electrode (RHE)) and half-wave potential (E 1/2) of 0.83 V (versus RHE) in 0.1 M KOH. Furthermore, the as-prepared catalyst presents superior durability and methanol tolerance compared to commercial Pt/C indicating its potential applications in fuel cells and metal-air batteries.

  1. A Semi-Empirical Two Step Carbon Corrosion Reaction Model in PEM Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Young, Alan; Colbow, Vesna; Harvey, David; Rogers, Erin; Wessel, Silvia

    2013-01-01

    The cathode CL of a polymer electrolyte membrane fuel cell (PEMFC) was exposed to high potentials, 1.0 to 1.4 V versus a reversible hydrogen electrode (RHE), that are typically encountered during start up/shut down operation. While both platinum dissolution and carbon corrosion occurred, the carbon corrosion effects were isolated and modeled. The presented model separates the carbon corrosion process into two reaction steps; (1) oxidation of the carbon surface to carbon-oxygen groups, and (2) further corrosion of the oxidized surface to carbon dioxide/monoxide. To oxidize and corrode the cathode catalyst carbon support, the CL was subjected to an accelerated stress test cycled the potential from 0.6 VRHE to an upper potential limit (UPL) ranging from 0.9 to 1.4 VRHE at varying dwell times. The reaction rate constants and specific capacitances of carbon and platinum were fitted by evaluating the double layer capacitance (Cdl) trends. Carbon surface oxidation increased the Cdl due to increased specific capacitance for carbon surfaces with carbon-oxygen groups, while the second corrosion reaction decreased the Cdl due to loss of the overall carbon surface area. The first oxidation step differed between carbon types, while both reaction rate constants were found to have a dependency on UPL, temperature, and gas relative humidity.

  2. Alkali metal ion storage properties of sulphur and phosphorous molecules encapsulated in nanometer size carbon cylindrical pores

    Directory of Open Access Journals (Sweden)

    Yosuke Ishii

    2016-03-01

    Full Text Available We investigated the physical and chemical stabilities of sulfur and phosphorus molecules encapsulated in a mesoporous carbon (MPC and two kinds of single-walled carbon nanotubes (SWCNTs having different cylindrical pore diameters. The sublimation temperatures of sulfur molecules encapsulated in MPC and the two kinds of SWCNTs were measured by thermo-gravimetric measurements. It was found that the sublimation temperature of sulfur molecules encapsulated in SWCNTs having mean tube diameter of 1.5 nm is much higher than any other molecules encapsulated in larger pores. It was also found that the capacity fading of lithium-sulfur battery can be diminished by encapsulation of sulfur molecules in SWCNTs. We also investigated the electrochemical properties of phosphorus molecules encapsulated in SWCNTs (P@SWCNTs. It was shown that P@SWCNT can adsorb and desorb both Li and Na ions reversibly.

  3. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

    KAUST Repository

    Stoltz, Brian

    2010-06-14

    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

  4. Geochemical insights into the lithology of mantle sources for Cenozoic alkali basalts in West Qinling, China

    Science.gov (United States)

    Dai, Li-Qun; Zheng, Fei; Zhao, Zi-Fu; Zheng, Yong-Fei

    2018-03-01

    Although alkali basalts are common in oceanic islands and continental rifts, the lithology of their mantle sources is still controversial. While the peridotite is usually viewed as a common source lithology, there are increasing studies suggesting significant contributions from ultramafic metasomatites such as carbonated peridotite, pyroxenite and hornblendite to the origin of alkali basalts. The present study indicates that carbonated peridotite plus hornblendite would have served as the mantle sources of Cenozoic alkali basalts from the West Qinling orogen in China. The target basalts show low SiO2 contents of 36.9 to 40.8 wt% and highly variable Na2O + K2O contents from 0.86 to 4.77 wt%, but high CaO contents of 12.5 to 16.3 wt% and CaO/Al2O3 ratios of 1.42 to 2.19. They are highly enriched in the majority of incompatible trace elements, but depleted in Rb, K, Pb, Zr, Hf, and Ti. Furthermore, they exhibit high (La/Yb)N, Zr/Hf, Ce/Pb and Nb/Ta ratios, but low Ti/Eu and Hf/Sm ratios. Generally, with increasing (La/Yb)N and CaO/Al2O3 ratios, their Ti/Eu and Hf/Sm ratios decrease whereas their Zr/Hf, Ce/Pb and Nb/Ta ratios increase. These major and trace element features are similar to those of carbonatites and hornblendite-derived melts to some extent, but significantly different from those of mid-ocean ridge basalts (MORB). This suggests that the alkali basalts would be originated from metasomatic mantle sources. A comparison of the major-trace elements in the alkali basalts with those of some representative mantle-derived melts indicates that the source lithology of alkali basalts is a kind of ultramafic metasomatites that are composed of carbonated peridotite and hornblendite. Such metasomatites would be generated by reaction of the depleted MORB mantle peridotite with hydrous, carbonate-bearing felsic melts derived from partial melting of the subducted Paleotethyan oceanic crust. Therefore, the melt-peridotite reaction at the slab-mantle interface in the

  5. Nitrogen-doped carbon dots decorated on graphene: a novel all-carbon hybrid electrocatalyst for enhanced oxygen reduction reaction.

    Science.gov (United States)

    Hu, Chao; Yu, Chang; Li, Mingyu; Wang, Xiuna; Dong, Qiang; Wang, Gang; Qiu, Jieshan

    2015-02-25

    An all-carbon hybrid, composed of coal-based nitrogen-doped carbon dots decorated on graphene, was prepared via hydrothermal treatment. The hybrid possesses comparable electrocatalytic activity, better durability and methanol tolerance than those of the commercial Pt-based electrocatalysts for oxygen reduction reaction, indicative of its great potential in fuel cells.

  6. Defect-induced Catalysis toward the Oxygen Reduction Reaction in Single-walled Carbon Nanotube: Nitrogen doped and Non-nitrogen doped

    International Nuclear Information System (INIS)

    Lu, Di; Wu, Dan; Jin, Jian; Chen, Liwei

    2016-01-01

    Single-walled carbon nanotubes (SWNTs) are post-treated by argon (Ar) or ammonia (NH 3 ) plasma irradiation to introduce defects that are potentially related to catalysis towards the oxygen reduction reaction (ORR). Electrochemical characterization in alkali medium suggests that the plasma irradiated SWNTs demonstrate enhanced catalytic activity toward the ORR with a positively shifted threshold potential. Moreover the enhanced desired four-electron pathway catalytic activity, which exhibited as the positive shifted threshold potential, is independent of the nitrogen dopant. The nature of the defects is probed with Raman and X-ray photoelectron spectroscopy. The results indicate that the non-nitrogen doped defects of SWNTs contribute to the actual active site for the ORR.

  7. Kinetic study of the reaction of uranium with various carbon-containing gases

    International Nuclear Information System (INIS)

    Feron, G.

    1963-09-01

    The kinetic study of the reaction U + CO 2 and U + CO has been performed by a thermogravimetric method on a spherical uranium powder, in temperature ranges respectively from 460 to 690 deg. C and from 570 to 850 deg. C. The reaction with carbon dioxide leads to uranium dioxide. A carbon deposition takes place at the same time. The global reactions is the result of two reactions: U + 2 CO 2 → UO 2 + 2 CO U + CO 2 → UO 2 + C The reaction with carbon monoxide leads to a mixture of dioxide UO 2 , dicarbide UC 2 and free carbon. The main reaction can be written. U + CO → 1/2 UO 2 + 1/2 UC 2 The free carbon results of the disproportionation of the carbon monoxide. A remarkable separation of the two phases UO 2 and UC 2 can be observed. A mechanism accounting for the phenomenon has been proposed. The two reactions U + CO 2 and U + CO begin with a long germination period, after which, the reaction velocity seems to be limited in both cases by the ionic diffusion of oxygen through the uranium dioxide. (author) [fr

  8. Alkali metal hydride formation

    International Nuclear Information System (INIS)

    1976-01-01

    The present invention relates to a method of producing alkali metal hydrides by absorbing hydrogen gas under pressure into a mixture of lower alkyl mono amines and alkali metal alkyl amides selected from sodium and potassium amides formed from said amines. The present invention also includes purification of a mixture of the amines and amides which contain impurities, such as is used as a catalytic exchange liquid in the enrichment of deuterium, involving the formation of the alkali metal hydride

  9. Alkaline direct ethanol fuel cell performance using alkali-impregnated polyvinyl alcohol/functionalized carbon nano-tube solid electrolytes

    Science.gov (United States)

    Huang, Chien-Yi; Lin, Jia-Shiun; Pan, Wen-Han; Shih, Chao-Ming; Liu, Ying-Ling; Lue, Shingjiang Jessie

    2016-01-01

    This study investigates the application of a polyvinyl alcohol (PVA)/functionalized carbon nano-tubes (m-CNTs) composite in alkaline direct ethanol fuel cells (ADEFC). The m-CNTs are functionalized with PVA using the ozone mediation method, and the PVA composite containing the modified CNTs is prepared. Adding m-CNT into the PVA matrix enhances the alkaline uptake and the ionic conductivity of the KOH-doped electrolyte. Meanwhile, the m-CNT-containing membrane exhibited a lower swelling ratio and suppressed ethanol permeability compared to the pristine PVA film. The optimal condition for the ADEFC is determined to be under operation at an anode feed of 3 M ethanol in a 5 M KOH solution (at a flow rate of 5 cm3 min-1) with a cathode feed of moisturized oxygen (with a flow rate of 100 cm3 min-1) and the KOH-doped PVA/m-CNT electrolyte. We achieved a peak power density value of 65 mW cm-2 at 60 °C, which is the highest among the ADEFC literature data and several times higher than the proton-exchange direct ethanol fuel cells using sulfonated membrane electrolytes. Therefore, the KOH-doped PVA/m-CNT electrolyte is a suitable solid electrolyte for ADEFCs and has potential for commercialization in alkaline fuel cell applications.

  10. Metal doped carbon nanoneedles and effect of carbon organization with activity for hydrogen evolution reaction (HER).

    Science.gov (United States)

    Araujo, Rafael A; Rubira, Adley F; Asefa, Tewodros; Silva, Rafael

    2016-02-10

    Cellulose nanowhiskers (CNW) from cotton, was prepared by acid hydrolysis and purified using a size selection process to obtain homogeneous samples with average particle size of 270 nm and 85.5% crystallinity. Purified CNW was used as precursor to carbon nanoneedles (CNN) synthesis. The synthesis of CNN loaded with different metals dopants were carried out by a nanoreactor method and the obtained CNNs applied as electrocatalysts for hydrogen evolution reaction (HER). In the carbon nanoneedles synthesis, Ni, Cu, or Fe worked as graphitization catalyst and the metal were found present as dopants in the final material. The used metal appeared to have direct influence on the degree of organization of the particles and also in the surface density of polar groups. It was evaluated the influence of the graphitic organization on the general properties and nickel was found as the more appropriate metal since it leads to a more organized material and also to a high activity toward HER. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. The Path of Carbon in Photosynthesis IX. Photosynthesis, Photoreduction, and the Hydrogen-Oxygen-Carbon Dioxide Dark Reaction

    Science.gov (United States)

    Badin, E. J.; Calvin, M.

    1950-02-01

    A comparison of the rates of fixation of Carbon 14 dioxide in algae for the processes of photosynthesis, photoreduction and the hydrogen-oxygen-carbon dioxide dark reaction has been made. For the same series of experiments, rates of incorporation of tracer carbon into the separate soluble components using the radiogram method have been determined. The mechanism of carbon dioxide uptake has been shown to occur via two distinct paths. In all cases studied, essentially the same compounds appear radioactive. The distribution with time, however, differs markedly.

  12. ALKALI RESISTANT CATALYST

    DEFF Research Database (Denmark)

    2008-01-01

    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...

  13. Neutral-neutral reactions in the interstellar medium. I. Formation of carbon hydride radicals via reaction of carbon atoms with unsaturated hydrocarbons

    International Nuclear Information System (INIS)

    Kaiser, R.I.

    1997-01-01

    The reactions of ground-state atomic carbon with acetylene, C 2 H 2 (1), methylacetylene, CH 3 CCH (2), ethylene, C 2 H 4 (3), and propylene, C 3 H 6 (4), are investigated at relative collision energies between 8.8 and 45kJmol -1 in crossed-beam experiments to elucidate the reaction products and chemical dynamics of atom-neutral encounters relevant to the formation of carbon-bearing molecules in the interstellar medium (ISM). Reactive scattering signal is found for C 3 H (1), as well as the hitherto unobserved interstellar radicals C 4 H 3 (2), C 3 H 3 (3), and C 4 H 5 (4). All reactions proceed on the triplet surface via addition of the carbon atom to the molecular π-bond. The initial collision complexes undergo hydrogen migration (1/2) or ring opening (3/4) and decompose via C-H-bond rupture to 1/c-C 3 H (1), n-C 4 H 3 (2), propargyl (3), and methylpropargyl (4). The explicit identification of the carbon-hydrogen exchange channel under single collision conditions identifies this class of reaction as a potential pathway to carbon-bearing species in the ISM. Especially, the formation of 1/c-C 3 H correlates with actual astronomical observations and explains a higher [c-C 3 H]/[l-C 3 H] ratio in the dark cloud TMC-1 as compared to the carbon star IRC+10216. Our findings strongly demand the incorporation of distinct structural isomers in prospective chemical models of interstellar clouds, hot cores, and circumstellar envelopes around carbon stars. copyright 1997 The American Astronomical Society

  14. Hydrothermal carbonization of rice husk for fuel upgrading

    Science.gov (United States)

    Suteerawattananonda, N.; Kongkaew, N.; Patumsawad, S.

    2018-01-01

    The biomass is popularly used as renewable energy. In Thailand rice is the most consume agricultural products. Agricultural residues from rice husk can be an energy resource. However, alkali and alkali earth materials (AAEMs) in biomass ash are the causes of corrosion and erosion problem in the heat exchanger equipment, while the acidity of ash affects the slagging agglomeration problem. Reduction of alkali and alkali earth materials can minimize the problem. In order to challenge the reduction of alkali and alkali earth materials in biomass ash, hydrothermal carbonization process was selected. Thai rice husk was used as sample to compare the result of treatment. The rice husk was heated under the condition of different temperature ranged from 180°C to 250°C, at operate pressure ranges from 12 bar to 42 bar with residence holding reaction time 1 hour. The results of proximate analysis show that the percentage by mass of fixed carbon are increased 2 times, but volatile matter is decreased by 40% and ash content is decreased by 11% due to the increment of temperature. Meanwhile, the X-Ray fluorescence (XRF) analysis results show the decreasing of alkali and alkali earth materials are reduced.

  15. Enhanced interfacial properties of carbon fiber composites via aryl diazonium reaction “on water”

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yuwei [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006 (China); Meng, Linghui [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Fan, Liquan [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006 (China); Ma, Lichun; Qi, Meiwei; Yu, Jiali [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Huang, Yudong, E-mail: ydhuang.hit1@yahoo.com.cn [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China)

    2014-10-15

    Highlights: • Carbon fibers are grafted with phenyl amine group via aryl diazonium reaction. • Interfacial shear strength of the carbon fibers increases by 73%. • Tensile strength of the carbon fibers does not decrease distinctly. • Using water as the reaction medium can avoid pollution from organic solvents. • Grafting via aryl diazonium reaction in one step can improve modification efficiency. - Abstract: Polyacrylonitrile-based carbon fibers were functionalized with phenyl amine group via aryl diazonium reaction “on water” to improve their interfacial bonding with resin matrix. Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were employed to characterize ordered degree, functional groups, chemical states and morphology of carbon fiber surface, respectively. The results showed that phenyl amine groups were grafted on the fiber surface successfully. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 73%, while the tensile strength was down very slightly. Hence aryl diazonium reaction “on water” could be a facile green platform to functionalize carbon fibers for many interesting applications.

  16. Enhanced interfacial properties of carbon fiber composites via aryl diazonium reaction “on water”

    International Nuclear Information System (INIS)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Ma, Lichun; Qi, Meiwei; Yu, Jiali; Huang, Yudong

    2014-01-01

    Highlights: • Carbon fibers are grafted with phenyl amine group via aryl diazonium reaction. • Interfacial shear strength of the carbon fibers increases by 73%. • Tensile strength of the carbon fibers does not decrease distinctly. • Using water as the reaction medium can avoid pollution from organic solvents. • Grafting via aryl diazonium reaction in one step can improve modification efficiency. - Abstract: Polyacrylonitrile-based carbon fibers were functionalized with phenyl amine group via aryl diazonium reaction “on water” to improve their interfacial bonding with resin matrix. Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were employed to characterize ordered degree, functional groups, chemical states and morphology of carbon fiber surface, respectively. The results showed that phenyl amine groups were grafted on the fiber surface successfully. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 73%, while the tensile strength was down very slightly. Hence aryl diazonium reaction “on water” could be a facile green platform to functionalize carbon fibers for many interesting applications

  17. Calcium silicate hydrate: Crystallisation and alkali sorption

    International Nuclear Information System (INIS)

    Hong, S.

    2000-01-01

    Homogeneous single C-S-H gels has been prepared for the investigation of alkali binding potential and crystallisation. A distribution coefficient, R d , was introduced to express the partition of alkali between solid and aqueous phases at 25 deg. C. R d is independent of alkali hydroxide concentration and depends only on Ca:Si ratio over wide ranges of alkali concentration. The trend of numerical values of R d indicates that alkali bonding into the solid improves as its Ca:Si ratio decreases. Reversibility is demonstrated, indicating a possibility of constant R d value of the material. Al has been introduced to form C-A-S-H gels and their alkali sorption properties also determined. Al substituted into C-S-H markedly increases R d , indicating enhancement of alkali binding. However, the dependence of R d on alkali concentration is non-ideal with composition. A two-site model for bonding is presented. Crystallisation both under saturated steam and 1 bar vapour pressure has been investigated. It has been shown that heat treatment by saturated steam causes crystallisation of gels. The principal minerals obtained were (i) C-S-H gel and Ca(OH) 2 at -55 deg. C, (ii) 1.1 nm tobermorite, jennite and afwillite at 85 -130 deg. C, and (iii) xonotlite, foshagite and hillebrandite at 150-180 deg. C. Properties of crystalline C-S-H were also reported for reversible phase transformation, pH conditioning ability, seeding effect and solubility. At 1 bar pressure, crystallisation is slower than in saturated steam due to lower water activity. Tobermorite-like nanodomains develop during reaction at low Ca/Si ratios. In some Ca-rich compositions, Ca(OH) 2 is exsolved and occurs as nano-sized crystallites. (author)

  18. Growth and Destruction of PAH Molecules in Reactions with Carbon Atoms

    Energy Technology Data Exchange (ETDEWEB)

    Krasnokutski, Serge A.; Huisken, Friedrich; Jäger, Cornelia; Henning, Thomas [Laboratory Astrophysics Group of the Max Planck Institute for Astronomy at the Friedrich Schiller University Jena, Helmholtzweg 3, D-07743 Jena (Germany)

    2017-02-10

    A very high abundance of atomic carbon in the interstellar medium (ISM), and the high reactivity of these species toward different hydrocarbon molecules including benzene, raise questions regarding the stability of polycyclic aromatic hydrocarbon (PAH) molecules in space. To test the efficiency of destruction of PAH molecules via reactions with atomic carbon, we performed a set of laboratory and computational studies of the reactions of naphthalene, anthracene, and coronene molecules with carbon atoms in the ground state. The reactions were investigated in liquid helium droplets at T = 0.37 K and by quantum chemical computations. Our studies suggest that all small and all large catacondensed PAHs react barrierlessly with atomic carbon, and therefore should be efficiently destroyed by such reactions in a broad temperature range. At the same time, large compact pericondensed PAHs should be more inert toward such a reaction. In addition, taking into account their higher photostability, much higher abundances of pericondensed PAHs should be expected in various astrophysical environments. The barrierless reactions between carbon atoms and small PAHs also suggest that, in the ISM, these reactions could lead to the bottom-up formation of PAH molecules.

  19. Biocatalytic carbon capture via reversible reaction cycle catalyzed by isocitrate dehydrogenase.

    Science.gov (United States)

    Xia, Shunxiang; Frigo-Vaz, Benjamin; Zhao, Xueyan; Kim, Jungbae; Wang, Ping

    2014-09-12

    The practice of carbon capture and storage (CCS) requires efficient capture and separation of carbon dioxide from its gaseous mixtures such as flue gas, followed by releasing it as a pure gas which can be subsequently compressed and injected into underground storage sites. This has been mostly achieved via reversible thermochemical reactions which are generally energy-intensive. The current work examines a biocatalytic approach for carbon capture using an NADP(H)-dependent isocitrate dehydrogenase (ICDH) which catalyzes reversibly carboxylation and decarboxylation reactions. Different from chemical carbon capture processes that rely on thermal energy to realize purification of carbon dioxide, the biocatalytic strategy utilizes pH to leverage the reaction equilibrium, thereby realizing energy-efficient carbon capture under ambient conditions. Results showed that over 25 mol of carbon dioxide could be captured and purified from its gas mixture for each gram of ICDH applied for each carboxylation/decarboxylation reaction cycle by varying pH between 6 and 9. This work demonstrates the promising potentials of pH-sensitive biocatalysis as a green-chemistry route for carbon capture. Copyright © 2014. Published by Elsevier Inc.

  20. Somewhere beyond the sea? The oceanic - carbon dioxide - reactions

    Science.gov (United States)

    Meisinger, Philipp; Wittlich, Christian

    2014-05-01

    In correlation to climate change and CO2 emission different campaigns highlight the importance of forests and trees to regulate the concentration of carbon dioxide in the earths' atmosphere. Seeing millions of square miles of rainforest cut down every day, this is truly a valid point. Nevertheless, we often tend to forget what scientists like Spokes try to raise awareness for: The oceans - and foremost deep sea sections - resemble the second biggest deposit of carbon dioxide. Here carbon is mainly found in form of carbonate and hydrogen carbonate. The carbonates are needed by corals and other sea organisms to maintain their skeletal structure and thereby to remain vital. To raise awareness for the protection of this fragile ecosystem in schools is part of our approach. Awareness is achieved best through understanding. Therefore, our approach is a hands-on activity that aims at showing students how the carbon dioxide absorption changes in relation to the water temperature - in times of global warming a truly sensitive topic. The students use standard syringes filled with water (25 ml) at different temperatures (i.e. 10°C, 20°C, 40°C). Through a connector students inject carbon dioxide (25ml) into the different samples. After a fixed period of time, students can read of the remaining amount of carbon dioxide in relation to the given water temperature. Just as with every scientific project, students need to closely monitor their experiments and alter their setups (e.g. water temperature or acidity) according to their initial planning. A digital template (Excel-based) supports the analysis of students' experiments. Overview: What: hands-on, minds -on activity using standard syringes to exemplify carbon dioxide absorption in relation to the water temperature (Le Chatelier's principle) For whom: adjustable from German form 11-13 (age: 16-19 years) Time: depending on the prior knowledge 45-60 min. Sources (extract): Spokes, L.: Wie Ozeane CO2 aufnehmen. Environmental

  1. Reaction of phosphorus ylides with carbonyl compounds in supercritical carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Kyung Il; Kim, Hak Do; Shim, Jae Jin; Ra, Choon Sup [Yeungnam Univ., Gyongsan (Korea, Republic of)

    2004-02-15

    The condensation reaction of (benzylene)triphenylphosphoranes with carbonyl compounds in supercritical carbon dioxide was examined. Reactions of (benzylene)phosphoranes (ca. 1 mmol) with several benzaldehydes in a supercritical carbon dioxide (80 .deg. C, 2,000 psi) containing THF entrainer (5%) in a 24 mL reactor proceed smoothly to yield olefination products in fairly good to excellent yields but slower, compared to reactions in a conventional THF solvent. Generally, phosphoranes that are not substituted with a nitro group show more (Z)-selective reactions with aromatic aldehydes under scCO{sub 2} condition than in THF. The reaction of (benzylene)triphenylphosphosphoranes with 4-t-butylcyclohexanone gave the corresponding olefin compounds with a low conversion under both the supercritical carbon dioxide and the organic THF solvent. Our preliminary study showed the Wittig reaction carries out smoothly in supercritical carbon dioxide medium and also a possible tunability of this reaction pathway by adding a entrainer. The results would be useful for devising a novel process for the environmentally friendly Wittig reaction.

  2. Carbon-13 Labeling Used to Probe Cure and Degradation Reactions of High- Temperature Polymers

    Science.gov (United States)

    Meador, Mary Ann B.; Johnston, J. Christopher

    1998-01-01

    High-temperature, crosslinked polyimides are typically insoluble, intractible materials. Consequently, in these systems it has been difficult to follow high-temperature curing or long-term degradation reactions on a molecular level. Selective labeling of the polymers with carbon-13, coupled with solid nuclear magnetic resonance spectrometry (NMR), enables these reactions to be followed. We successfully employed this technique to provide insight into both curing and degradation reactions of PMR-15, a polymer matrix resin used extensively in aircraft engine applications.

  3. Preparation of hollow carbon nanospheres at low temperature via new reaction route

    International Nuclear Information System (INIS)

    Ni Youbao; Shao Mingwang; Tong Yanhua; Qian Guixiang; Wei Xianwen

    2005-01-01

    Hollow carbon nanospheres were obtained at 200 o C via a new reaction route, by using magnesium, hexachloroethane and aluminum trichloride as starting materials and benzene as solvent. The products were characterized with X-ray diffraction pattern, transmission electron microscope, high-resolution transmission electron microscope images and Raman spectrum. The reaction conditions are easy to be maintained and controlled. They may provide a new method to produce other carbonaceous materials. A possible mechanism of reaction was proposed

  4. Preparation of hollow carbon nanospheres at low temperature via new reaction route

    Science.gov (United States)

    Ni, Youbao; Shao, Mingwang; Tong, Yanhua; Qian, Guixiang; Wei, Xianwen

    2005-03-01

    Hollow carbon nanospheres were obtained at 200 °C via a new reaction route, by using magnesium, hexachloroethane and aluminum trichloride as starting materials and benzene as solvent. The products were characterized with X-ray diffraction pattern, transmission electron microscope, high-resolution transmission electron microscope images and Raman spectrum. The reaction conditions are easy to be maintained and controlled. They may provide a new method to produce other carbonaceous materials. A possible mechanism of reaction was proposed.

  5. Influence of reaction parameters on the hydrogenolysis of hydroxymatairesinol over carbon nanofibre supported palladium catalysts

    OpenAIRE

    Bernas, H.; Plomp, A.J.; Bitter, J.H.; Murzin, D.Y.

    2008-01-01

    The influence of catalyst particle size, stirring rate, catalyst mass (0.2–0.6 g), reaction temperature (60–70 C), and reactant concentration (1.3–4 mmol/L, with constant reactant/catalyst ratio) on the hydrogenolysis of the lignan hydroxymatairesinol (HMR) to matairesinol (MAT) was studied under hydrogen atmosphere using a carbon nanofibre supported palladium catalyst. When the temperature or HMR concentration was increased, the reaction rate increased as expected. However, the reaction rate...

  6. Theoretical Studies of Gas Phase Elementary and Carbon Nanostructure Growth Reactions

    Science.gov (United States)

    2013-09-19

    photodissociation reactions of ketene, methylamine, formic acid , methyl ethyl ketone, acetone and NO3. For instance, for NO3, a totally unknown...to photodissociation reactions of ketene, methylamine, formic acid , methyl ethyl ketone, acetone and NO3. For instance, for NO3, a totally unknown...THEORETICAL STUDIES OF GAS PHASE ELEMENTARY AND CARBON NANOSTRUCTURE GROWTH REACTIONS KEIJI MOROKUMA EMORY UNIVERSITY 09/19/2013 Final Report

  7. A kinetic study of the reaction of water vapor and carbon dioxide on uranium

    International Nuclear Information System (INIS)

    Santon, J.P.

    1964-09-01

    The kinetic study of the reaction of water vapour and carbon dioxide with uranium has been performed by thermogravimetric methods at temperatures between 160 and 410 deg G in the first case, 350 and 1050 deg C in the second: Three sorts of uranium specimens were used: uranium powder, thin evaporated films, and small spheres obtained from a plasma furnace. The experimental results led in the case of water vapour, to a linear rate of reaction controlled by diffusion at the lower temperatures, and by a surface reaction at the upper ones. In the case of carbon dioxide, a parabolic law has been found, controlled by diffusional processes. (author) [fr

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

    Directory of Open Access Journals (Sweden)

    J. Węgrzyn

    2015-07-01

    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.

  9. Quasi-elastic neutrino reactions on carbon and lead nuclei

    Science.gov (United States)

    Hedayatipoor, Mohammad; Finlay, James; Massoudi, Soheyl; Nokes, Charles; de Montigny, Marc

    2018-02-01

    We examine neutral-current quasi-elastic neutrino-nucleus reactions on 12C and 208Pb targets. We use the relativistic mean field theory approach to describe the nuclear dynamics. We compute the cross sections for the scattering of 150, 500 and 1000 MeV neutrinos on a 12C target and study the effect of the strange-quark content of the nucleon which appears in these reactions via the isoscalar weak current. We compare our results with the data of the MiniBooNE experiment for mineral oil (CH2). We also calculate the cross section for the quasi-elastic neutron knockout reaction of 20-60 MeV neutrinos on a 208Pb target which is relevant to plans to use lead as a target material in future supernova neutrino detectors.

  10. Buffering dissociation/formation reaction of biogenic calcium carbonate.

    Science.gov (United States)

    Ichikawa, Kazuhiko

    2007-01-01

    The oscillating stability of coral reef seawater pH has been maintained at around physiological pH values over the past 300 years (Pelejero et al., 2005). The stability mechanism of its pH has been interpreted in terms of the buffering dissolution/formation reaction of CaCO(3) as well as the proton consumption/generation reaction in CaCO(3)-saturated water. Here the pH-dependent solubility product [HCO(3)(-)][Ca(2+)] has been derived on the basis of the actual pH-dependent reactions for the atmospheric CO(2)/CO(2 (aq.))/HCO(3)(-)/CO(3)(2-)/Ca(2+)/CaCO(3) system. Overbasic pH peaks appeared between pH approximately 8 and approximately 9.5 during sodium hydroxide titration, as a result of simultaneous CaCO(3) formation and proton generation. The spontaneous and prompt water pH recovery from the acidic to the physiological range has been confirmed by the observation of acid/base time evolution, because of simultaneous CaCO(3) dissolution and proton consumption. The dissolution/formation of CaCO(3) in water at pH 7.5-9 does not take place without a proton consumption/generation reaction, or a buffering chemical reaction of HCO(3)(-)+Ca(2+)right arrow over left arrowCaCO(3)+H(+). SEM images of the CaCO(3) fragments showed that the acid water ate away at the CaCO(3) formed at physiological pH values. Natural coral reefs can thus recover the physiological pH levels of seawater from the acidic range through partial dissolution of their own skeletons.

  11. XPS study on the surface reaction of uranium metal with carbon monoxide at 200 degree C

    International Nuclear Information System (INIS)

    Wang Xiaoling; Fu Yibei; Xie Renshou; Huang Ruiliang

    1996-12-01

    The surface reaction of uranium metal with carbon monoxide at 200 degree C has been studied by X-ray photoelectron spectroscopy (XPS). The carbon monoxide adsorption on the surface oxide layer resulted in U4f peak shifting to the lower binding energy and the content of oxygen in the oxide is decreased. O/U radio decreases with increasing the exposure of carbon monoxide to the surface layer. The investigation indicated the surface layer of uranium metal was further reduced in the atmosphere of carbon monoxide at high temperature. (3 refs., 5 figs.)

  12. Research of Hydrogen Preparation with Catalytic Steam-Carbon Reaction Driven by Photo-Thermochemistry Process

    Directory of Open Access Journals (Sweden)

    Xiaoqing Zhang

    2013-01-01

    Full Text Available An experiment of hydrogen preparation from steam-carbon reaction catalyzed by K2CO3 was carried out at 700°C, which was driven by the solar reaction system simulated with Xenon lamp. It can be found that the rate of reaction with catalyst is 10 times more than that without catalyst. However, for the catalytic reaction, there is no obvious change for the rate of hydrogen generation with catalyst content range from 10% to 20%. Besides, the conversion efficiency of solar energy to chemical energy is more than 13.1% over that by photovoltaic-electrolysis route. An analysis to the mechanism of catalytic steam-carbon reaction with K2CO3 is given, and an explanation to the nonbalanced [H2]/[CO + 2CO2] is presented, which is a phenomenon usually observed in experiment.

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

    DEFF Research Database (Denmark)

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

    1998-01-01

    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....

  14. Radiation-induced addition reaction of carbon tetrachloride onto 1,2-polybutadiene

    Energy Technology Data Exchange (ETDEWEB)

    Okamoto, H.; Adachi, S.; Iwai, T.

    1979-05-01

    The ..gamma..-ray-induced addition reaction of carbon tetrachloride onto syndiotactic 1,2-polybutadiene film and liquid 1,2-polybutadiene was carried out at room temperature. In the film gelation was pronounced and the rate of addition increased as the crystallinity of the polymer decreased. In the liquid gelation, which makes the polymer insoluble in carbon tetrachloride, did not take place, although a definite crosslinking reaction was noticed. In this case the appearance of the product charged from a viscous liquid to a white powder as the reaction proceeded. Its structure was compared with that of chlorinated 1,2-polybutadiene. The addition of carbon tetrachloride to the vinyl group in liquid 1,2-polybutadiene caused an anti-Markownikoff-type reaction and was accompanied by an unexpectedly large vinyl depletion in the polymer. The total decrease in the vinyl group was found to be much larger than that brought about by the addition of carbon tetrachloride. This discrepancy was attributed to a cyclization and crosslinking reaction ascribed to the vinyl group bound by the main chain. Cyclization and crosslinking were less noticeable in the chlorination than in the carbon tetrachloride. 9 figures, 2 tables.

  15. An integrated experimental and first-principles computational study of carbon dioxide mineral carbonation reactions in olivine and serpentine

    Science.gov (United States)

    Gormley, Deirdre Marie

    This dissertation is a unique integration of experimental and theoretical methods. The central issue that is being addressed is to find a long term and economically viable solution to the disposal of carbon dioxide gas from coal power plants. Mineral carbonation reactions have emerged as a permanent solution to the well-known "Greenhouse Gas" issue. Our group here at ASU along with groups at Los Alamos National Laboratory (LANL), National Energy Technology Laboratory (NETL), Pennsylvania State in Utah (SAIC), and the Albany Research Center (ARC) comprise the working group managed by the US Department of Energy (DOE). We have been collaborating to develop a fundamental understanding of the carbonation reactions of candidate minerals which will ultimately be used to develop a pilot plant process. Two of the candidate minerals used in mineral sequestration processes are forsterite (olivine) and lizardite (serpentine). Both candidates require pre-treatment prior to reaction with carbon dioxide. Forsterite requires attrition (grinding), while lizardite requires a pre-heat treatment (dehydroxylation) step which removes chemically bound water. In Chapter 3 of this thesis, the thermodynamic properties of seven primary oxides involved in reactions with forsterite and lizardite are compared. A novel method was developed using a theoretical molecular quantum physics approach which reproduced experimental results with great accuracy. This method can now be used for other systems where experimental thermodynamic data is unavailable. In Chapters 4 and 5, the dehydroxylation mechanism for lizardite is studied using theoretical models in conjunction with experimental results. A possible mechanism for the dehydroxylation pathway is suggested. This long-awaited result may provide new insight regarding carbonation reactions in lizardite. Chapters 6 and 7 explore the carbonation reactions in forsterite. With the help of high resolution electron microscopy images and extremely large

  16. Kinetic Modeling of the Reaction Rate for Quartz and Carbon Pellet

    Science.gov (United States)

    Li, Fei; Tangstad, Merete

    2018-04-01

    Kinetic modeling of quartz and carbon pellet at temperatures of 1898 K, 1923 K, and 1948 K (1625 °C, 1650 °C, and 1675 °C) was investigated in this study. The carbon materials used were charcoal, coke, coal, and preheated coal. The overall SiC producing reaction can be described by the reaction SiO2 + 3C = SiC + 2CO. In the SiC-producing step, the reaction rate of quartz and carbon pellet can be expressed as {d{ pct}}/dt = ( {1 - 0.40 × X_{fix - C}^{ - 0.86} × FC × {pct}} ) × A × \\exp ( { - E/{{RT}}} ) The carbon factor F C was used to describe the influence of different carbon materials that effect the gas-solid interface reaction. For charcoal, coke, coal, and preheated coal, the F C values were 0.83, 0.80, 0.94, and 0.83, respectively. The pre-exponential factor A values for the preceding four carbon materials were 1.06 × 1016 min-1, 4.21 × 1015 min-1, 3.85 × 109 min-1, and 1.00 × 1025 min-1, respectively. The activation energies E for the SiC-producing step were 570, 563, 336, and 913 kJ/mole for charcoal, coke, coal, and preheated coal pellets, respectively.

  17. Kinetic Modeling of the Reaction Rate for Quartz and Carbon Pellet

    Science.gov (United States)

    Li, Fei; Tangstad, Merete

    2018-01-01

    Kinetic modeling of quartz and carbon pellet at temperatures of 1898 K, 1923 K, and 1948 K (1625 °C, 1650 °C, and 1675 °C) was investigated in this study. The carbon materials used were charcoal, coke, coal, and preheated coal. The overall SiC producing reaction can be described by the reaction SiO2 + 3C = SiC + 2CO. In the SiC-producing step, the reaction rate of quartz and carbon pellet can be expressed as {d{ pct}}/dt = ( {1 - 0.40 × X_{fix - C}^{ - 0.86} × FC × {pct}} ) × A × \\exp ( { - E/{{RT}}} ) The carbon factor F C was used to describe the influence of different carbon materials that effect the gas-solid interface reaction. For charcoal, coke, coal, and preheated coal, the F C values were 0.83, 0.80, 0.94, and 0.83, respectively. The pre-exponential factor A values for the preceding four carbon materials were 1.06 × 1016 min-1, 4.21 × 1015 min-1, 3.85 × 109 min-1, and 1.00 × 1025 min-1, respectively. The activation energies E for the SiC-producing step were 570, 563, 336, and 913 kJ/mole for charcoal, coke, coal, and preheated coal pellets, respectively.

  18. Carbon burning in stars - Prospects for underground measurements of the 12C+12C fusion reactions

    International Nuclear Information System (INIS)

    Strieder, Frank

    2010-01-01

    The 12 C+ 12 C fusion reactions are together with the reaction 12 C(a,γ) 16 O the most important nuclear processes in the late stellar evolution. These fusion reactions play a key role in the understanding of various types of astrophysical objects. Thus, a measurement of the 12 C+ 12 C cross section at very low energies can serve as flagship experiment for a future underground accelerator laboratory. It is hoped that an appropriate facility for such a study will be created in the near future somewhere in the world. The prospects for the measurement of the carbon fusion reactions will be discussed in the present work.

  19. Synergistic effect of Nitrogen-doped hierarchical porous carbon/graphene with enhanced catalytic performance for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Dewang; Yuan, Wenjing; Li, Cun; Song, Jiming; Xie, Anjian, E-mail: anjx@163.com; Shen, Yuhua, E-mail: s_yuhua@163.com

    2017-01-30

    Graphical abstract: This work demonstrates an example for turning rubbish into valuable products and addresses the disposal issue of waste biomass simultaneously for environment clean. And the typical sample exhibits excellent catalytic performance toward ORR, which is similar to that of commercial Pt/C. - Highlights: • This work demonstrates an example for turning rubbish into valuable products and addresses the disposal issue of waste biomass. • The HPC/RGO composite not only prevents the aggregation of RGO, but also takes advantage of the synergy between them. • This method was accessible, without using any activator, which is an effective strategy for the large scale application of FCs. - Abstract: Developing efficient and economical catalysts for the oxygen reduction reaction (ORR) is important to promote the commercialization of fuel cells. Here, we report a simple and environmentally friendly method to prepare nitrogen (N) –doped hierarchical porous carbon (HPC)/reduced graphene oxide (RGO) composites by reusing waste biomass (pomelo peel) coupled with graphene oxide (GO). This method is green, low-cost and without using any acid or alkali activator. The typical sample (N-HPC/RGO-1) contains 5.96 at.% nitrogen and larger BET surface area (1194 m{sup 2}/g). Electrochemical measurements show that N-HPC/RGO-1 exhibits not only a relatively positive onset potential and high current density, but also considerable methanol tolerance and long-term durability in alkaline media as well as in acidic media. The electron transfer number is close to 4, which means that it is mostly via a four-electron pathway toward ORR. The excellent catalytic performance of N-HPC/RGO-1 is due to the synergistic effect of the inherent interwoven network structure of HPC, the good electrical conductivity of RGO, and the heteroatom doping for the composite. More importantly, this work demonstrates a good example for turning discarded rubbish into valuable functional products and

  20. Characterization, preparation, and reaction mechanism of hemp stem based activated carbon

    Science.gov (United States)

    Zhang, Ji; Gao, Jianmin; Chen, Yao; Hao, Xinmin; Jin, Xiaojuan

    In this study, hemp stem was used to prepare high surface area activated carbon (AC) by KOH activation. The structure, characterization, thermal and structure analysis on reaction mechanisms of AC were investigated via N2 adsorption-desorption isotherm, Fourier transform infrared (FTIR) spectroscopy and thermogravimetric-mass (TG-MS) spectrometry. Results show that when the impregnation ratio is 4.5:1 (KOH/char), the activation temperature is 800 °C, and the activation time is 1.5 h, AC has the highest specific surface area of 2388 m2·g-1 and exhibits narrow pore size distributions with maxima in the micropore areas. The reaction mechanism of AC from hemp stems by KOH activation is as follows: In the first carbonization stage, it is primarily because of the substitution, scission, and oxidization reactions of methylene. Then in the second activation stage, it is mainly related to polycyclic reactions, reactions between carbon and KOH, and reactions between intermediate potassium oxide species and carbon.

  1. Brown carbon formation by aqueous-phase carbonyl compound reactions with amines and ammonium sulfate.

    Science.gov (United States)

    Powelson, Michelle H; Espelien, Brenna M; Hawkins, Lelia N; Galloway, Melissa M; De Haan, David O

    2014-01-21

    Reactions between small water-soluble carbonyl compounds, ammonium sulfate (AS), and/or amines were evaluated for their ability to form light-absorbing species in aqueous aerosol. Aerosol chemistry was simulated with bulk phase reactions at pH 4, 275 K, initial concentrations of 0.05 to 0.25 M, and UV-vis and fluorescence spectroscopy monitoring. Glycolaldehyde-glycine mixtures produced the most intense absorbance. In carbonyl compound reactions with AS, methylamine, or AS/glycine mixtures, product absorbance followed the order methylglyoxal > glyoxal > glycolaldehyde > hydroxyacetone. Absorbance extended into the visible, with a wavelength dependence fit by absorption Ångstrom coefficients (Å(abs)) of 2 to 11, overlapping the Å(abs) range of atmospheric, water-soluble brown carbon. Many reaction products absorbing between 300 and 400 nm were strongly fluorescent. On a per mole basis, amines are much more effective than AS at producing brown carbon. In addition, methylglyoxal and glyoxal produced more light-absorbing products in reactions with a 5:1 AS-glycine mixture than with AS or glycine alone, illustrating the importance of both organic and inorganic nitrogen in brown carbon formation. Through comparison to biomass burning aerosol, we place an upper limit on the contribution of these aqueous carbonyl-AS-amine reactions of ≤ 10% of global light absorption by brown carbon.

  2. A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

    Science.gov (United States)

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

    2016-09-27

    Binary catalyst systems comprising a cationic Ru-CNC pincer complex and an alkali metal salt were developed for selective hydroboration of CO 2 utilizing pinacolborane at r.t. and 1 atm CO 2 , with the combination of [Ru(CNC Bn )(CO) 2 (H)][PF 6 ] and KOCO 2 t Bu producing formoxyborane in 76% yield. A bicyclic catalytic mechanism was proposed and discussed.

  3. Reactions of carbon radicals generated by 1,5-transposition of reactive centers

    Directory of Open Access Journals (Sweden)

    ZIVORAD CEKOVIC

    2005-03-01

    Full Text Available Radical intermediates can undergo specific reactions, such as intramolecular rearrangements, i.e., the transpositions of radical centers, which are not known in classical ionic organic reactions. 1,5-Transposition of a radical center to a non-activated carbon atom are of great synthetic importance. It can be successfully applied for the introduction of different functional groups (oxygen, nitrogen, sulfur, halogens onto a carbon atom remote from the present functional group. In addition to functionalization of a remote non-activated carbon atom, the formation of new C-C bonds on the d-carbon atom have also been achieved. 1,5-Transposition of the radical centers takes place from alkoxyl, aminyl and carbon radicals to a remote carbon atom. Relocation of the radical centers preferentially involves 1,5-transfer of a hydrogen atom, although migrations of some other groups are known. The reactions of the carbon radical generated by 1,5-relocation of the radical center are presented and their synthetic applications are reviewed.

  4. Oxidative dehydrogenation reaction of short alkanes on nanostructured carbon catalysts: a computational account.

    Science.gov (United States)

    Sun, XiaoYing; Han, Peng; Li, Bo; Mao, ShanJun; Liu, TianFu; Ali, Sajjad; Lian, Zan; Su, DangSheng

    2018-01-23

    Recent progress from first principles computational studies is presented for catalytic properties of nanostructured carbon catalysts in the oxidative dehydrogenation (ODH) reaction of short alkanes. Firstly, a brief introduction is given on the development of carbon catalysts in ODH since 1970. Oxygen functional groups have pivotal importance for ODH on nanostructured carbon catalysts. We discuss the oxidation process by HNO 3 on pristine and defective carbon materials. The interactions between the oxygen molecule (oxidant) and the nanostructured carbon catalysts are quantitatively calibrated. Moreover the different nucleophilic abilities of oxygen functional groups are carefully compared and the strongest nucleophilic sites are proposed. The active sites and detailed reaction pathway are revealed from several computational studies. Diketone/quinone groups are generally considered to be the active centers in ODH. A reaction pathway via radical formation is considered as the favorable path. Furthermore, single ketone and carbon sites are verified to be active in ODH from the analysis of aromaticity. Heteroatom doping effects in ODH are examined. Nitrogen doping is found to be very reactive towards oxygen molecule activation. Other dopants such as boron, phosphorous and sulfur also have positive effects on the reactivity of ODH. Extensive calculations suggest that the BEP relation is applicable for the doped nanostructured carbon catalysts. In the end, an outlook for the future direction of the computational study is supplied.

  5. Investigation of thermochemistry associated with the carbon-carbon coupling reactions of furan and furfural using ab initio methods.

    Science.gov (United States)

    Liu, Cong; Assary, Rajeev S; Curtiss, Larry A

    2014-06-26

    Upgrading furan and small oxygenates obtained from the decomposition of cellulosic materials via formation of carbon-carbon bonds is critical to effective conversion of biomass to liquid transportation fuels. Simulation-driven molecular level understanding of carbon-carbon bond formation is required to design efficient catalysts and processes. Accurate quantum chemical methods are utilized here to predict the reaction energetics for conversion of furan (C4H4O) to C5-C8 ethers and the transformation of furfural (C5H6O2) to C13-C26 alkanes. Furan can be coupled with various C1 to C4 low molecular weight carbohydrates obtained from the pyrolysis via Diels-Alder type reactions in the gas phase to produce C5-C8 cyclic ethers. The computed reaction barriers for these reactions (∼25 kcal/mol) are lower than the cellulose activation or decomposition reactions (∼50 kcal/mol). Cycloaddition of C5-C8 cyclo ethers with furans can also occur in the gas phase, and the computed activation energy is similar to that of the first Diels-Alder reaction. Furfural, obtained from biomass, can be coupled with aldehydes or ketones with α-hydrogen atoms to form longer chain aldol products, and these aldol products can undergo vapor phase hydrocycloaddition (activation barrier of ∼20 kcal/mol) to form the precursors of C26 cyclic hydrocarbons. These thermochemical studies provide the basis for further vapor phase catalytic studies required for upgrading of furans/furfurals to longer chain hydrocarbons.

  6. Characterization of the major reactions during conversion of lignin to carbon fiber

    Directory of Open Access Journals (Sweden)

    Hendrik Mainka

    2015-10-01

    Full Text Available Lightweight design is an essential part of the overall Volkswagen strategy for reducing the CO2 emissions. The use of carbon fiber offers an enormous lightweight potential. In comparison to steel enabling a mass reduction of up to 70% in automotive parts without a degradation of the functionalities is possible. Today, the use of carbon fiber is limited in mass series applications of the automotive industry by the cost of the conventional C-fiber precursor polyacrylonitrile (PAN. 50% of the cost of a conventional carbon fiber already belongs to the cost of the PAN precursor. Lignin as a precursor for carbon fiber production can realize enormous savings in cost. For qualifying lignin-based carbon fiber for automotive mass production a detailed characterization of this new material is necessary. Therefore, nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy are used. Using the results of these experiments, the major reactions during conversion of lignin to carbon fiber are proposed.

  7. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  8. Enhanced interfacial properties of carbon fiber composites via aryl diazonium reaction “on water”

    Science.gov (United States)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Ma, Lichun; Qi, Meiwei; Yu, Jiali; Huang, Yudong

    2014-10-01

    Polyacrylonitrile-based carbon fibers were functionalized with phenyl amine group via aryl diazonium reaction "on water" to improve their interfacial bonding with resin matrix. Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were employed to characterize ordered degree, functional groups, chemical states and morphology of carbon fiber surface, respectively. The results showed that phenyl amine groups were grafted on the fiber surface successfully. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 73%, while the tensile strength was down very slightly. Hence aryl diazonium reaction "on water" could be a facile green platform to functionalize carbon fibers for many interesting applications.

  9. Measurement of Neutron Reaction Cross Sections in Carbon using a Single Crystal Diamond Detector

    Energy Technology Data Exchange (ETDEWEB)

    Pillon, M.; Angelone, M. [Associazione EURATOM-ENEA sulla Fusione, ENEA C.R. Frascati, via E. Fermi, 45 0044 Frascati, Rome (Italy); Krasa, A.; Plompen, A. J. M.; Schillebeeckx, P. [European Commission, Joint Research Centre, Institute for Reference Materials and Measurements, - 2440 Geel (Belgium); Sergi, M. L. [Dipartimento di Fisica e Astronomia, Universita di Catania e INFN-Laboratori Nazionali del Sud, Catania (Italy)

    2011-12-13

    A single crystal diamond detector was exposed to the quasi mono-energetic neutron fields in the energy range from 7 MeV to 20.5 MeV produced by the Van de Graaff neutron generator of the EC-JRC-IRMM. Pulse Height Spectra (PHS) of the neutron interaction with the diamond (carbon) were recorded in order to derive the experimental response function of this detector to neutrons in view of its use as a compact fast neutron spectrometer. Several peaks produced by outgoing charged particles produced when neutrons interact with carbon were identified using the reaction Q-values. The corresponding nuclear reactions, such as (n,{alpha}), (n,p), (n,d) for different excitation states were identified in the PHS. The analysis of the peaks allows the derivation of some neutron reaction cross sections in carbon. The results are presented in this paper together with the associated uncertainties.

  10. Measurement of Neutron Reaction Cross Sections in Carbon using a Single Crystal Diamond Detector

    Science.gov (United States)

    Pillon, M.; Angelone, M.; Krása, A.; Plompen, A. J. M.; Schillebeeckx, P.; Sergi, M. L.

    2011-12-01

    A single crystal diamond detector was exposed to the quasi mono-energetic neutron fields in the energy range from 7 MeV to 20.5 MeV produced by the Van de Graaff neutron generator of the EC-JRC-IRMM. Pulse Height Spectra (PHS) of the neutron interaction with the diamond (carbon) were recorded in order to derive the experimental response function of this detector to neutrons in view of its use as a compact fast neutron spectrometer. Several peaks produced by outgoing charged particles produced when neutrons interact with carbon were identified using the reaction Q-values. The corresponding nuclear reactions, such as (n,α), (n,p), (n,d) for different excitation states were identified in the PHS. The analysis of the peaks allows the derivation of some neutron reaction cross sections in carbon. The results are presented in this paper together with the associated uncertainties.

  11. Heterogeneously Catalysed Aldol Reactions in Supercritical Carbon Dioxide as Innovative and Non-Flammable Reaction Medium

    DEFF Research Database (Denmark)

    Musko, Nikolai; Grunwaldt, Jan-Dierk

    2011-01-01

    hydrogenation of 2-butenal and is therefore a potential catalyst for the “one-pot” synthesis of 2-ethyl-2-hexenal and 2-ethylhexanal via combined hydrogenation and aldol reaction from 2-butenal. A number of characterisation techniques, such as temperature-programmed desorption of ammonia (NH3-TPD), transmission...

  12. Chemical Reaction Equilibrium in Nanoporous Materials: NO Dimerization Reaction in Carbon Slit Nanopores

    Czech Academy of Sciences Publication Activity Database

    Lísal, Martin; Brennan, J.K.; Smith, W.R.

    2006-01-01

    Roč. 124, č. 6 (2006), s. 64712.1-64712.14 ISSN 0021-9606 R&D Projects: GA ČR(CZ) GA203/05/0725; GA AV ČR(CZ) 1ET400720507; GA AV ČR(CZ) 1ET400720409 Institutional research plan: CEZ:AV0Z40720504 Keywords : nanopore * NO dimerization * reaction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.166, year: 2006

  13. Improving the Durability of Methanol Oxidation Reaction Electro-Catalysts Through the Modification of Carbon Architectures

    Science.gov (United States)

    2014-01-01

    containing water) at the anode side. The methanol is then oxidized to CO2, although other reaction intermediates can form (i.e. formic acid and other organic...pyridic- N-oxides 445.1 6 M KOH @.05A/g 183.8 NR (C. Wang et al., 2013) Porous carbon Carbonization of poly- acrylamide and boric acid 8.1% Pyridinic...modified carbons applied to other biosensing applications including ascorbic acid [424], dopamine[424], uric acid [424], proteins[425], and thioridazine

  14. The process of dimethyl carbonate to diphenyl carbonate: Thermodynamics, reaction kinetics and conceptional process design

    NARCIS (Netherlands)

    Haubrock, J.

    2007-01-01

    Diphenyl carbonate (DPC) is a precursor in the production of Polycarbonate (PC), a widely employed engineering plastic. To overcome the drawbacks of the traditional PC process - e.g. phosgene as a reactant and methylene chloride as solvent- a new process route starting from Dimethyl carbonate (DMC)

  15. Ambient Mechanochemical Solid-State Reactions of Carbon Nanotubes and Their Reactions via Covalent Coordinate Bond in Solution

    Science.gov (United States)

    Kabbani, Mohamad A.

    In its first part, this thesis deals with ambient mechanochemical solid-state reactions of differently functionalized multiple walled carbon nanotubes (MWCNTs) while in its second part it investigates the cross-linking reactions of CNTs in solution via covalent coordinate bonds with transitions metals and carboxylate groups decorating their surfaces. In the first part a series of mechanochemical reactions involving different reactive functionalities on the CNTs such as COOH/OH, COOH/NH2 and COCl/OH were performed. The solid-state unzipping of CNTs leading to graphene formation was confirmed using spectroscopic, thermal and electron microscopy techniques. The non-grapheme products were established using in-situ quadruple mass spectroscopy. The experimental results were confirmed by theoretical simulation calculations using the 'hot spots' protocol. The kinetics of the reaction between MWCNT-COOH and MWCNT-OH was monitored using variable temperature Raman spectroscopy. The low activation energy was discussed in terms of hydrogen bond mediated proton transfer mechanism. The second part involves the reaction of MWCNTII COOH with Zn (II) and Cu (II) to form CNT metal-organic frame (MOFs) products that were tested for their effective use as counter-electrodes in dyes sensitized solar cells (DSSC). The thesis concludes by the study of the room temperature reaction between the functionalized graphenes, GOH and G'-COOH followed by the application of compressive loads. The 3D solid graphene pellet product ( 0.6gm/cc) is conductive and reflective with a 35MPa ultimate strength as compared to 10MPa strength of graphite electrode ( 2.2gm/cc).

  16. Effect of reaction temperature on structure and fluorescence properties of nitrogen-doped carbon dots

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yi [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China); Department of Chemistry and Chemical Engineering, Lyuliang University, Lyuliang 033001 (China); Research Center on Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Wang, Yaling [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); Research Center on Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Feng, Xiaoting [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China); Zhang, Feng [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); Research Center on Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Yang, Yongzhen, E-mail: yyztyut@126.com [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); Research Center on Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Liu, Xuguang, E-mail: liuxuguang@tyut.edu.cn [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China)

    2016-11-30

    Highlights: • Nitrogen-doped carbon dots (NCDs) from ammonia solution and citric acid were synthesized at different temperatures. • Quantum yield (QY) of NCDs depends largely on the amount of fluorescent polymer chains (FPC), more FPC gives higher QY. • The law of QY of NCDs first increase and then decrease with the reaction temperature increased is found and explained. • Nitrogen doping plays significant role in getting increased UV–vis absorption and QY. - Abstract: To investigate the effect of reaction temperature and nitrogen doping on the structure and fluorescence properties of carbon dots (CDs), six kinds of nitrogen-doped CDs (NCDs) were synthesized at reaction temperatures of 120, 140, 160, 180, 200 and 220 °C, separately, by using citric acid as carbon source and ammonia solution as nitrogen source. Nitrogen-free CDs (N-free CDs-180) was also prepared at 180 °C by using citric acid as the only carbon source for comparison. Results show that reaction temperature has obvious effect on carbonization degree, quantum yield (QY), ultraviolet-visible (UV–vis) absorption and photoluminescence (PL) spectra but less effect on functional groups, nitrogen doping degree and fluorescence lifetime of NCDs. Compared with N-free CDs-180, NCDs-180 possesses enchanced QY and longer fluorescence lifetime. Doping nitrogen has obvious effect on UV–vis absorption and PL spectra but less effect on particles sizes and carbonization degree. The formation mechanism of NCDs is explored: QY of NCDs depends largely on the number of fluorescent polymer chains (FPC), the competition between FPC formation on the surface of NCDs and carbon core growth leads to the change in number of FPC, and consequently to the NCDs with highest QY at appropriate hydrothermal temperature.

  17. Biogeochemical stability and reactions of iron-organic carbon complexes

    Science.gov (United States)

    Yang, Y.; Adhikari, D.; Zhao, Q.; Dunham-Cheatham, S.; Das, K.; Mejia, J.; Huang, R.; Wang, X.; Poulson, S.; Tang, Y.; Obrist, D.; Roden, E. E.

    2017-12-01

    Our core hypothesis is that the degradation rate of soil organic carbon (OC) is governed by the amount of iron (Fe)-bound OC, and the ability of microbial communities to utilize OC as an energy source and electron shuttle for Fe reduction that in turn stimulates reductive release of Fe-bound labile dissolved OC. This hypothesis is being systematically evaluated using model Fe-OC complexes, natural soils, and microcosm system. We found that hematite-bound aliphatic C was more resistant to reduction release, although hematite preferred to sorb more aromatic C. Resistance to reductive release represents a new mechanism that aliphatic soil OC was stabilized by association with Fe oxide. In other studies, pyrogenic OC was found to facilitate the reduction of hematite, by enhancing extracellular electron transport and sorbing Fe(II). For ferrihydrite-OC co-precipitates, the reduction of Fe and release of OC was closely governed by the C/Fe ratio in the system. Based on the XPS, XANES and XAFS analysis, the transformation of Fe speciation was heterogeneous, depending on the conformation and composition of Fe-OC complexes. For natural soils, we investigated the quantity, characteristics, and reactivity of Fe-bound OC in soils collected from 14 forests in the United States. Fe-bound OC contributed up to 57.8% of total OC in the forest soils. Under the anaerobic conditions, the reduction of Fe was positively correlated to the electron accepting capacity of OC. Our findings highlight the closely coupled dynamics of Fe and OC, with broad implications on the turnover of OC and biogeochemical cycles of Fe.

  18. 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

    2017-03-07

    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.

  19. Alkali metal ion battery with bimetallic electrode

    Science.gov (United States)

    Boysen, Dane A; Bradwell, David J; Jiang, Kai; Kim, Hojong; Ortiz, Luis A; Sadoway, Donald R; Tomaszowska, Alina A; Wei, Weifeng; Wang, Kangli

    2015-04-07

    Electrochemical cells having molten electrodes having an alkali metal provide receipt and delivery of power by transporting atoms of the alkali metal between electrode environments of disparate chemical potentials through an electrochemical pathway comprising a salt of the alkali metal. The chemical potential of the alkali metal is decreased when combined with one or more non-alkali metals, thus producing a voltage between an electrode comprising the molten the alkali metal and the electrode comprising the combined alkali/non-alkali metals.

  20. Surprisingly Different Reaction Behavior of Alkali and Alkaline Earth Metal Bis(trimethylsilyl)amides toward Bulky N-(2-Pyridylethyl)-N'-(2,6-diisopropylphenyl)pivalamidine.

    Science.gov (United States)

    Kalden, Diana; Oberheide, Ansgar; Loh, Claas; Görls, Helmar; Krieck, Sven; Westerhausen, Matthias

    2016-07-25

    N-(2,6-Diisopropylphenyl)-N'-(2-pyridylethyl)pivalamidine (Dipp-N=C(tBu)-N(H)-C2 H4 -Py) (1), reacts with metalation reagents of lithium, magnesium, calcium, and strontium to give the corresponding pivalamidinates [(tmeda)Li{Dipp-N=C(tBu)-N-C2 H4 -Py}] (6), [Mg{Dipp-N=C(tBu)-N-C2 H4 -Py}2 ] (3), and heteroleptic [{(Me3 Si)2 N}Ae{Dipp-N=C(tBu)-N-C2 H4 -Py}], with Ae being Ca (2 a) and Sr (2 b). In contrast to this straightforward deprotonation of the amidine units, the reaction of 1 with the bis(trimethylsilyl)amides of sodium or potassium unexpectedly leads to a β-metalation and an immediate deamidation reaction yielding [(thf)2 Na{Dipp-N=C(tBu)-N(H)}] (4 a) or [(thf)2 K{Dipp-N=C(tBu)-N(H)}] (4 b), respectively, as well as 2-vinylpyridine in both cases. The lithium derivative shows a similar reaction behavior to the alkaline earth metal congeners, underlining the diagonal relationship in the periodic table. Protonation of 4 a or the metathesis reaction of 4 b with CaI2 in tetrahydrofuran yields N-(2,6-diisopropylphenyl)pivalamidine (Dipp-N=C(tBu)-NH2 ) (5), or [(thf)4 Ca{Dipp-N=C(tBu)-N(H)}2 ] (7), respectively. The reaction of AN(SiMe3 )2 (A=Na, K) with less bulky formamidine Dipp-N=C(H)-N(H)-C2 H4 -Py (8) leads to deprotonation of the amidine functionality, and [(thf)Na{Dipp-N=C(H)-N-C2 H4 -Py}]2 (9 a) or [(thf)K{Dipp-N=C(H)-N-C2 H4 -Py}]2 (9 b), respectively, are isolated as dinuclear complexes. From these experiments it is obvious, that β-metalation/deamidation of N-(2-pyridylethyl)amidines requires bases with soft metal ions and also steric pressure. The isomeric forms of all compounds are verified by single-crystal X-ray structure analysis and are maintained in solution. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. A novel method for determination of occurrence order of stabilization reactions in carbon fiber precursor

    Science.gov (United States)

    Arbab, S.; Mirbaha, H.; Zeinolebadi, A.; Nourpanah, P.

    2017-10-01

    Thermal stabilization is an important step in production of carbon fiber from polyacrylonitrile (PAN) precursors. During thermal stabilization step different thermochemical reactions take place almost simultaneously. Understanding the onset and temperature range of the stabilization reactions is a key for adjusting processing parameters such as tension, stretching, etc. However, stabilization reactions are very complex and overlap with each other. In order to separate the stabilization reactions, we combined the results of different thermal analysis techniques, namely Differential Scanning Calorimetry (DSC), Thermogravimetry (TGA) and Thermomechanical Analysis (TMA), to study behaviour of PAN precursors during stabilization. By means of combining the results of these techniques, we were able to determine the temperature range and occurrence order of each of stabilization reactions regardless of the composition of initial PAN fibers and history of fiber formation.

  2. Carbophilic versus thiophilic attack in the reaction of metallated aromates and heteroaromates with carbon disulfide

    NARCIS (Netherlands)

    Verkruijsse, H.D.; Brandsma, L.

    1987-01-01

    Copper(I) halides catalyse the formation of carbodithioates RCSSLi in the reaction of aryl- or heteroaryl-lithium reagents with carbon disulfide. Subsequent addition of methyl iodide gives the dithioesters RCSSCH3 in high yields. Appreciable amounts of the methyl sulfides RSCH3 and tars are obtained

  3. (abstract) Experimental and Modeling Studies of the Exchange Current at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary

    Science.gov (United States)

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

    1993-01-01

    The microscopic mechanism of the alkali ion-electron recombination reaction at the three phase boundary zone formed by a porous metal electrode in the alkali vapor on the surface of an alkali beta'-alumina solid electrolyte (BASE) ceramic has been studied by comparison of the expected rates for the three simplest reaction mechanisms with known temperature dependent rate data; and the physical parameters of typical porous metal electrode/BASE/alkali metal vapor reaction zones. The three simplest reactions are tunneling of electrons from the alkali coated electrode to a surface bound alkali metal ion; emission of an electron from the electrode with subsequent capture by a surface bound alkali metal ion; and thermal emission of an alkali cation from the BASE and its capture on the porous metal electrode surface where it may recombine with an electron. Only the first reaction adequately accounts for both the high observed rate and its temperature dependence. New results include crude modeling of simple, one step, three phase, solid/solid/gas electrochemical reaction.

  4. Coke formation and carbon atom economy of methanol-to-olefins reaction.

    Science.gov (United States)

    Wei, Yingxu; Yuan, Cuiyu; Li, Jinzhe; Xu, Shutao; Zhou, You; Chen, Jingrun; Wang, Quanyi; Xu, Lei; Qi, Yue; Zhang, Qing; Liu, Zhongmin

    2012-05-01

    The methanol-to-olefins (MTO) process is becoming the most important non-petrochemical route for the production of light olefins from coal or natural gas. Maximizing the generation of the target products, ethene and propene, and minimizing the production of byproducts and coke, are major considerations in the efficient utilization of the carbon resource of methanol. In the present work, the heterogeneous catalytic conversion of methanol was evaluated by performing simultaneous measurements of the volatile products generated in the gas phase and the confined coke deposition in the catalyst phase. Real-time and complete reaction profiles were plotted to allow the comparison of carbon atom economy of methanol conversion over the catalyst SAPO-34 at varied reaction temperatures. The difference in carbon atom economy was closely related with the coke formation in the SAPO-34 catalyst. The confined coke compounds were determined. A new type of confined organics was found, and these accounted for the quick deactivation and low carbon atom economy under low-reaction-temperature conditions. Based on the carbon atom economy evaluation and coke species determination, optimized operating conditions for the MTO process are suggested; these conditions guarantee high conversion efficiency of methanol. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Mineral carbonation: energy costs of pretreatment options and insights gained from flow loop reaction studies

    International Nuclear Information System (INIS)

    Penner, Larry R.; O'Connor, William K.; Dahlin, David C.; Gerdemann, Stephen J.; Rush, Gilbert E.

    2004-01-01

    Sequestration of carbon as a stable mineral carbonate has been proposed to mitigate environmental concerns that carbon dioxide may with time escape from its sequestered matrix using alternative sequestration technologies. A method has been developed to prepare stable carbonate products by reacting CO2 with magnesium silicate minerals in aqueous bicarbonate/chloride media at high temperature and pressure. Because this approach is inherently expensive due to slow reaction rates and high capital costs, studies were conducted to improve the reaction rates through mineral pretreatment steps and to cut expenses through improved reactor technology. An overview is given for the estimated cost of the process including sensitivity to grinding and heating as pretreatment options for several mineral feedstocks. The energy costs are evaluated for each pretreatment in terms of net carbon avoided. New studies with a high-temperature, high-pressure flow-loop reactor have yielded information on overcoming kinetic barriers experienced with processing in stirred autoclave reactors. Repeated tests with the flow-loop reactor have yielded insights on wear and failure of system components, on challenges to maintain and measure flow, and for better understanding of the reaction mechanism

  6. Mineral carbonation: energy costs of pretreatment options and insights gained from flow loop reaction studies

    Energy Technology Data Exchange (ETDEWEB)

    Penner, Larry R.; O' Connor, William K.; Dahlin, David C.; Gerdemann, Stephen J.; Rush, Gilbert E.

    2004-01-01

    Sequestration of carbon as a stable mineral carbonate has been proposed to mitigate environmental concerns that carbon dioxide may with time escape from its sequestered matrix using alternative sequestration technologies. A method has been developed to prepare stable carbonate products by reacting CO2 with magnesium silicate minerals in aqueous bicarbonate/chloride media at high temperature and pressure. Because this approach is inherently expensive due to slow reaction rates and high capital costs, studies were conducted to improve the reaction rates through mineral pretreatment steps and to cut expenses through improved reactor technology. An overview is given for the estimated cost of the process including sensitivity to grinding and heating as pretreatment options for several mineral feedstocks. The energy costs are evaluated for each pretreatment in terms of net carbon avoided. New studies with a high-temperature, high-pressure flow-loop reactor have yielded information on overcoming kinetic barriers experienced with processing in stirred autoclave reactors. Repeated tests with the flow-loop reactor have yielded insights on wear and failure of system components, on challenges to maintain and measure flow, and for better understanding of the reaction mechanism.

  7. Reaction Rates Of Olivine Carbonation - An Experimental Study Using Synthetic Fluid Inclusions As Micro-Reactors

    Science.gov (United States)

    Sendula, E.; Lamadrid, H. M.; Bodnar, R. J.

    2017-12-01

    Ultramafic and mafic rocks (e.g. peridotites, serpentinites and basalts) are being considered as possible targets for CO2 sequestration via mineral carbonation. The determination of reaction kinetics and the factors that control mineralization are important in order to understand and predict fluid-rock reactions between the injected CO2 and the host rocks. Here we present results of experiments focused on determining the reaction rates of carbonation of olivine as a function of initial CO2 concentration (20 mol% and 11 mol%) in the aqueous solution and temperature (100°C and 50°C). We used a recently developed experimental method (Lamadrid et al., 2017) that uses synthetic fluid inclusions as micro-reactors. The micro-reactor technique coupled with non-destructive Raman spectroscopy allows us to monitor the reaction progress in situ and in real time, by quantifying the amount of CO2 consumed in the reaction as a function of time. Results show a measurable decrease of CO2 density in the fluid inclusions as a result of the reaction between the CO2-bearing aqueous phase and olivine. Magnesite formation begins within several hours at 100°C and most of the CO2 was consumed within two days. At 50°C, however, magnesite nucleation and precipitation required weeks to months to begin, and the reaction rates were about an order of magnitude slower than in the experiments at 100°C. No significant differences were observed in the reaction rates as a function of initial CO2 concentration. The application of the synthetic fluid inclusion technique as micro-reactors coupled with non-destructive analytical techniques is a promising tool to monitor rates of fluid-rock reactions in situ and in real time, allowing detailed micron-scale investigations. The technique can be applied to a wide variety of chemical systems, host minerals, reaction products, fluid densities, temperatures, and different starting fluid compositions.

  8. Methods of recovering alkali metals

    Science.gov (United States)

    Krumhansl, James L; Rigali, Mark J

    2014-03-04

    Approaches for alkali metal extraction, sequestration and recovery are described. For example, a method of recovering alkali metals includes providing a CST or CST-like (e.g., small pore zeolite) material. The alkali metal species is scavenged from the liquid mixture by the CST or CST-like material. The alkali metal species is extracted from the CST or CST-like material.

  9. A model of hydrogen impact induced chemical erosion of carbon based on elementary reaction steps

    International Nuclear Information System (INIS)

    Wittmann, M.; Kueppers, J.

    1996-01-01

    Based on the elementary reaction steps for chemical erosion of carbon by hydrogen a model is developed which allows to calculate the amount of carbon erosion at a hydrogenated carbon surface under the impact of hydrogen ions and neutrals. Hydrogen ion and neutral flux energy distributions prevailing at target plates in the ASDEX upgrade experiment are chosen in the present calculation. The range of hydrogen particles in the target plates is calculated using TRIDYN code. Based upon the TRIDYN results the extent of the erosion reaction as a function of depth is estimated. The results show that both, target temperature and impinging particle flux energy distribution, determine the hydrogen flux density dependent erosion yield and the location of the erosion below the surface. (orig.)

  10. Fluorescent Carbon Dots Derived from Maillard Reaction Products: Their Properties, Biodistribution, Cytotoxicity, and Antioxidant Activity.

    Science.gov (United States)

    Li, Dongmei; Na, Xiaokang; Wang, Haitao; Xie, Yisha; Cong, Shuang; Song, Yukun; Xu, Xianbing; Zhu, Bei-Wei; Tan, Mingqian

    2018-02-14

    Food-borne nanoparticles have received great attention because of their unique physicochemical properties and potential health risk. In this study, carbon dots (CDs) formed during one of the most important chemical reactions in the food processing field, the Maillard reaction from the model system including glucose and lysine, were investigated. The CDs purified from Maillard reaction products emitted a strong blue fluorescence under ultraviolet light with a fluorescent quantum yield of 16.30%. In addition, they were roughly spherical, with sizes of around 4.3 nm, and mainly composed of carbon, oxygen, hydrogen, and nitrogen. Their surface groups such as hydroxyl, amino, and carboxyl groups were found to possibly enable CDs to scavenge DPPH and hydroxyl radicals. Furthermore, the cytotoxicity assessment of CDs showed that they could readily enter HepG2 cells while causing negligible cell death at low concentration. However, high CDs concentrations were highly cytotoxic and led to cell death via interference of the glycolytic pathway.

  11. Electro-deposition of Pd on carbon paper and Ni foam via surface limited redox-replacement reaction for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Modibedi, RM

    2014-05-01

    Full Text Available Pd nanostructured catalysts were electrodeposited by surface-limited redox replacement reactions usingthe electrochemical atomic layer deposition technique. Carbon paper and Ni foam were used as substratesfor the electrodeposition of the metal...

  12. 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.

    2010-07-01

    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.

  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

    2012-03-01

    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. Spectra of alkali atoms

    International Nuclear Information System (INIS)

    Santoso, Budi; Arumbinang, Haryono.

    1981-01-01

    Emission spectra of alkali atoms has been determined by using spectrometer at the ultraviolet to infra red waves range. The spectra emission can be obtained by absorption spectrophotometric analysis. Comparative evaluations between experimental data and data handbook obtained by spark method were also presented. (author tr.)

  15. Hybrid direct carbon fuel cells and their reaction mechanisms - a review

    DEFF Research Database (Denmark)

    Deleebeeck, Lisa; Kammer Hansen, Kent

    2014-01-01

    As coal is expected to continue to dominate power generation demands worldwide, it is advisable to pursue the development of more efficient coal power generation technologies. Fuel cells show a much higher fuel utilization efficiency, emit fewer pollutants (NOx, SOx), and are more easily combined...... with carbon capture and storage (CCS) due to the high purity of CO2 emitted in the exhaust gas. Direct carbon (or coal) fuel cells (DCFCs) are directly fed with solid carbon to the anode chamber. The fuel cell converts the carbon at the anode and the oxygen at the cathode into electricity, heat and reaction...... (fresh water consumed, solid waste produced, CO2 emitted, ease of combination with CCS) and economics (levelized cost of electricity)....

  16. Reduced Reactivity of Amines against Nucleophilic Substitution via Reversible Reaction with Carbon Dioxide.

    Science.gov (United States)

    Mohammed, Fiaz S; Kitchens, Christopher L

    2015-12-23

    The reversible reaction of carbon dioxide (CO₂) with primary amines to form alkyl-ammonium carbamates is demonstrated in this work to reduce amine reactivity against nucleophilic substitution reactions with benzophenone and phenyl isocyanate. The reversible formation of carbamates has been recently exploited for a number of unique applications including the formation of reversible ionic liquids and surfactants. For these applications, reduced reactivity of the carbamate is imperative, particularly for applications in reactions and separations. In this work, carbamate formation resulted in a 67% reduction in yield for urea synthesis and 55% reduction for imine synthesis. Furthermore, the amine reactivity can be recovered upon reversal of the carbamate reaction, demonstrating reversibility. The strong nucleophilic properties of amines often require protection/de-protection schemes during bi-functional coupling reactions. This typically requires three separate reaction steps to achieve a single transformation, which is the motivation behind Green Chemistry Principle #8: Reduce Derivatives. Based upon the reduced reactivity, there is potential to employ the reversible carbamate reaction as an alternative method for amine protection in the presence of competing reactions. For the context of this work, CO₂ is envisioned as a green protecting agent to suppress formation of n-phenyl benzophenoneimine and various n-phenyl-n-alky ureas.

  17. Zoning and exsolution in cumulate alkali feldspars from the eruption (12.9 Ka) of Laacher see volcano (Western Germany) as an indicator of time-scales and dynamics of carbonate-silicate unmixing

    Science.gov (United States)

    Sourav Rout, Smruti; Wörner, Gerhard

    2017-04-01

    Time-scales extracted from the detailed analysis of chemically zoned minerals provide insights into crystal ages, magma storage and compositional evolution, including mixing and unmixing events. This allows having a better understanding of pre-eruptive history of large and potentially dangerous magma chambers. We present a comprehensive study of chemical diffusion across zoning and exsolution patterns of alkali feldspars in carbonatite-bearing cognate syenites from the 6.3 km3 (D.R.E) phonolitic Laacher See Tephra (LST) eruption 12.9 ka ago. The Laacher See volcano is located in the Quaternary East Eifel volcanic field of the Paleozoic Rhenish Massif in Western Germany and has produced a compositionally variable sequence in a single eruption from a magma chamber that was zoned from mafic phonolite at the base to highly evolved, actively degassing phonolite magma at the top. Diffusion chronometry is applied to major and trace element compositions obtained on alkali feldspars from carbonate-bearing syenitic cumulates. Methods used were laser ablation inductively coupled plasma mass spectrometry (LA ICP-MS) in combination with energy-dispersive and wavelength-dispersive electron microprobe analyses (EDS & WDS-EMPA). The grey scale values extracted from multiple accumulations of back-scattered electron images represent the K/Na ratio owing to the extremely low concentrations of Ba and Sr (grey scale profiles and the quantitative compositional profiles are anatomized using three different fitting models in MATLAB®, Mathematica® and Origin® to estimate related time-scales with minimized error for a temperature range of 750 deg C to 800 deg C (on the basis of existing experimental data on phase transition and phase separation). A distinctive uphill diffusive analysis is used specifically for the phase separation in the case of exsolution features (comprising of albite- and orthoclase-rich phases) in sanidines. The error values are aggregates of propagated error through

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

    Directory of Open Access Journals (Sweden)

    Yasuo Kojima

    2015-12-01

    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.

  19. Carbon dioxide/methanol conversion cycle based on cascade enzymatic reactions supported on superparamagnetic nanoparticles

    Directory of Open Access Journals (Sweden)

    CATERINA G.C. MARQUES NETTO

    2017-10-01

    Full Text Available ABSTRACT The conversion of carbon dioxide into important industrial feedstock is a subject of growing interest in modern society. A possible way to achieve this goal is by carrying out the CO2/methanol cascade reaction, allowing the recycle of CO2 using either chemical catalysts or enzymes. Efficient and selective reactions can be performed by enzymes; however, due to their low stability, immobilization protocols are required to improve their performance. The cascade reaction to reduce carbon dioxide into methanol has been explored by the authors, using, sequentially, alcohol dehydrogenase (ADH, formaldehyde dehydrogenase (FalDH, and formate dehydrogenase (FDH, powered by NAD+/NADH and glutamate dehydrogenase (GDH as the co-enzyme regenerating system. All the enzymes have been immobilized on functionalized magnetite nanoparticles, and their reactions investigated separately in order to establish the best performance conditions. Although the stepwise scheme led to only 2.3% yield of methanol per NADH; in a batch system under CO2 pressure, the combination of the four immobilized enzymes increased the methanol yield by 64 fold. The studies indicated a successful regeneration of NADH in situ, envisaging a real possibility of using immobilized enzymes to perform the cascade CO2-methanol reaction.

  20. Reaction studies of hot silicon, germanium and carbon atoms: Progress report, February 1, 1985-July 31, 1987

    International Nuclear Information System (INIS)

    Gaspar, P.P.

    1987-01-01

    The experimental approach toward attaining the goals of this research program is briefly outlined, and the progress made in the 1985 to 1987 period is reviewed in sections entitled: (1) reactions of recoiling silicon atoms; (2) reactions of recoiling carbon atoms; and (3) reactions of thermally evaporated germanium atoms

  1. Recent developments in enzyme promiscuity for carbon-carbon bond-forming reactions

    NARCIS (Netherlands)

    Miao, Yufeng; Rahimi, Mehran; Geertsema, Edzard M; Poelarends, Gerrit J

    Numerous enzymes have been found to catalyze additional and completely different types of reactions relative to the natural activity they evolved for. This phenomenon, called catalytic promiscuity, has proven to be a fruitful guide for the development of novel biocatalysts for organic synthesis

  2. Divergent Cyclization Reactions of Morita-Baylis-Hillman Carbonates of 2-Cyclohexenone and Isatylidene Malononitriles.

    Science.gov (United States)

    Peng, Jing; Ran, Guang-Yao; Du, Wei; Chen, Ying-Chun

    2015-09-18

    Zwitterionic dienolates generated from Morita-Baylis-Hillman carbonates of cyclohexen-2-one and a phenolic tertiary amine catalyst underwent divergent cyclization reactions with isatylidene malononitriles. A new [4 + 2] stepwise cyclization process was disclosed to deliver complex bridged spirooxindoles after the initial δ'-regioselective Rauhut-Currier-type reaction with N-methyl electrophiles by the catalysis of β-isocupreidine, while spirooxindoles incorporating an aromatic chromene motif were generated with N-MOM acceptors in the presence of α-isocupreine through different domino transformations.

  3. DFT investigations for the reaction mechanism of dimethyl carbonate synthesis on Pd(II)/β zeolites.

    Science.gov (United States)

    Shen, Yongli; Meng, Qingsen; Huang, Shouying; Gong, Jinlong; Ma, Xinbin

    2013-08-21

    Density functional theory (DFT) calculations have been used to investigate the oxidative carbonylation of methanol on Pd(II)/β zeolite. Activation energies for all the elementary steps involved in the commonly accepted mechanism, including the formation of dimethyl carbonate, methyl formate and dimethoxymethane, are presented. Upon conducting the calculations, we identify that the Pd(2+) cation bonded with four O atoms of the zeolite framework acts as the active site of the catalyst. Molecularly adsorbed methanol starts to react with oxygen molecules to produce a methanediol intermediate (CH2(OH)2) and O atom. Then, another methanol can react with the O atom to produce the (CH3O)(OH)-Pd(II)/β zeolite species. (CH3O)(OH)-Pd(II)/β zeolite can further react with carbon monoxide or methanol to give monomethyl carbonate or di-methoxide species ((CH3O)2-Pd(II)/β zeolite). Dimethyl carbonate can form via two distinct reaction pathways: (I) methanol reacts with monomethyl carbonate or (II) carbon monoxide inserts into di-methoxide. Our calculation results show the activation energy of reaction (I) is too high to be achieved. The methanediol intermediate is unstable and can decompose to formaldehyde and H2O immediately. Formaldehyde can either react with an O atom or methanol to form formic acid or a CH3OCH2OH intermediate. Both of them can react with methanol to form the secondary products (methyl formate or dimethoxymethane). Upon conducting calculations, we confirmed that the activation energies for the formation of methyl formate and dimethoxymethane are higher than that of dimethyl carbonate. All these conformations were characterized at the same calculation level.

  4. An Alternative Method for Generating Arynes from ortho-Silylaryl Triflates: Activation by Cesium Carbonate in the Presence of a Crown Ether

    Directory of Open Access Journals (Sweden)

    Suguru Yoshida

    2015-06-01

    Full Text Available An alternative method for generating arynes from ortho-silylaryl triflates using cesium carbonate and 18-crown-6 is reported. The method was efficiently applied to a variety of reactions between several arynes and arynophiles. We also demonstrated that the efficiency of aryne generation is significantly affected by the alkali metal countercation of the carbonate.

  5. Synthesis of Polyaniline (PANI in Nano-Reaction Field of Cellulose Nanofiber (CNF, and Carbonization

    Directory of Open Access Journals (Sweden)

    Yuki Kaitsuka

    2016-02-01

    Full Text Available Polymerization of aniline in the presence of cellulose nano-fiber (CNF is carried out. We used dried CNF, CNF suspension, and CNF treated by enzyme and ultra-sonification to obtain polyaniline (PANI/CNF as a synthetic polymer/natural nano-polymer composite. The polymerization proceeds on the surface of CNF as a nano-reaction field. Resultant composites show extended effective π-conjugation length because CNF as a reaction field in molecular level produced polymer with expanded coil structure with an aid of orientation effect of CNF. Possibility of PANI β-pleats structure in molecular level of PANI on the CNF is also discussed. SEM observation showed that fine structure is easily obtained by combining PANI with CNF. Carbonization of PANI/CNF allows production of nano-fine form with shape preserved carbonization (SPC.

  6. Temporal mapping of photochemical reactions and molecular excited states with carbon specificity.

    Science.gov (United States)

    Wang, K; Murahari, P; Yokoyama, K; Lord, J S; Pratt, F L; He, J; Schulz, L; Willis, M; Anthony, J E; Morley, N A; Nuccio, L; Misquitta, A; Dunstan, D J; Shimomura, K; Watanabe, I; Zhang, S; Heathcote, P; Drew, A J

    2017-04-01

    Photochemical reactions are essential to a large number of important industrial and biological processes. A method for monitoring photochemical reaction kinetics and the dynamics of molecular excitations with spatial resolution within the active molecule would allow a rigorous exploration of the pathway and mechanism of photophysical and photochemical processes. Here we demonstrate that laser-excited muon pump-probe spin spectroscopy (photo-μSR) can temporally and spatially map these processes with a spatial resolution at the single-carbon level in a molecule with a pentacene backbone. The observed time-dependent light-induced changes of an avoided level crossing resonance demonstrate that the photochemical reactivity of a specific carbon atom is modified as a result of the presence of the excited state wavefunction. This demonstrates the sensitivity and potential of this technique in probing molecular excitations and photochemistry.

  7. Interfacial reactions between graphite electrodes and propylene carbonate-based solutions: Electrolyte-concentration dependence of electrochemical lithium intercalation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Soon-Ki [Department of Chemical Engineering, Soonchunhyang University, Asan, Chungnam 336-745 (Korea); Inaba, Minoru [Department of Molecular Science and Technology, Faculty of Engineering, Doshisha University, Kyotanabe, Kyoto 610-0321 (Japan); Iriyama, Yasutoshi; Abe, Takeshi; Ogumi, Zempachi [Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)

    2008-01-03

    This study examines the electrochemical reactions occurring at graphite negative electrodes of lithium-ion batteries in a propylene carbonate (PC) electrolyte that contains different concentrations of lithium salts such as, LiClO{sub 4}, LiPF{sub 6} or LiN(SO{sub 2}C{sub 2}F{sub 5}){sub 2}. The electrode reactions are significantly affected by the electrolyte concentration. In concentrated solutions, lithium ions are reversibly intercalated within the graphite to form stage 1 lithium-graphite intercalation compounds (Li-GICs), regardless of the lithium salt used. On the other hand, electrolyte decomposition and exfoliation of the graphene layers occur continuously in the low-concentration range. In situ analysis with atomic force microscopy reveals that a thin film (thickness of {proportional_to}8 nm) forms on the graphite surface in a concentrated solution, e.g., 3.27 mol kg{sup -1} LiN(SO{sub 2}C{sub 2}F{sub 5}){sub 2}/PC, after the first potential cycle between 2.9 and 0 V versus Li{sup +}/Li. There is no evidence of the co-intercalation of solvent molecules in the concentrated solution. (author)

  8. Mechanism of radiation-induced addition reaction of carbon tetrachloride onto liquid 1,2-polybutadiene accompanied by cyclization

    Energy Technology Data Exchange (ETDEWEB)

    Okamoto, H.; Adachi, S.; Kakada, K.; Iwai, T.

    1979-05-01

    Effects of irradiation conditions were investgated in the ..gamma..-ray-induced addition reaction of carbon tetrachloride onto liquid 1,2-polybutadiene. The rate of addition reaction was proportional to the dose rate, and its apparent activation energy was 1.4 kcal/mole in the range of ca. 20 to 80/sup 0/C; the G values for the addition of carbon tetrachloride and vinyl consumption were high. The addition reactions of methyl isobutylate, isopropyl amine, and bromotrichloromethane to liquid 1,2-polybutadiene by ..gamma.. rays were studied to compare with carbon tetrachloride. Methyl isobutylate and isopropyl amine were added much more slowly. On the other hand, in bromotrichloromethane the rate of addition reacion was much faster but cyclization was less pronounced than in carbon tetrachloride. On the basis of these results a mechanism of a radical chain reaction which includes the addition of carbon tetrachloride, cyclization, and crosslinking, is proposed. 8 figures.

  9. Carbon cryogel as support of platinum nano-sized electrocatalyst for the hydrogen oxidation reaction

    International Nuclear Information System (INIS)

    Babic, B.M.; Vracar, Lj.M.; Radmilovic, V.; Krstajic, N.V.

    2006-01-01

    The kinetics of hydrogen oxidation reaction was studied in perchloric acid solution on carbon-supported Pt nanoparticles using the rotating disk electrode technique. Carbon cryogel and commercial carbon black. Vulcan XC-72 were used as catalyst supports. Pt/C catalysts were prepared by a modified polyol synthesis method in an ethylene glycol (EG) solution. Considerable effect has been observed for the specific surface area of carbon support on the fundamental properties of Pt/C catalyst, such as catalyst particle size distribution and dispersion as well as catalytic activity for the oxidation of hydrogen. X-ray diffraction (XRD) and transmission electron microscopy (TEM) images show that the particle size of the catalyst decreases with the increase of specific surface area of carbon support. Cyclic voltammetry (CV) was used for determination of the actual exposed surface area of catalyst particles. It was found that Pt catalyst prepared by using the novel carbon material displayed better hydrogen electrochemical oxidation activity than the catalyst prepared by using Vulcan XC-72

  10. [Involvement of carbonate/bicarbonate ions in the superoxide-generating reaction of adrenaline autoxidation].

    Science.gov (United States)

    Sirota, T V

    2015-01-01

    An important role of carbonate/bicarbonate ions has been recognized in the superoxide generating reaction of adrenaline autooxidation in an alkaline buffer (a model of quinoid adrenaline oxidation in the body). It is suggested that these ions are directly involved not only in formation of superoxide anion radical (О(2)(-)) but also other radicals derived from the carbonate/bicarbonate buffer. Using various buffers it was shown that the rate of accumulation of adrenochrome, the end product of adrenaline oxidation, and the rate of О(2)(-)· formation depend on concentration of carbonate/bicarbonate ions in the buffer and that these ions significantly accelerate adrenaline autooxidation thus demonstrating prooxidant properties. The detectable amount of diformazan, the product of nitro blue tetrazolium (NBT) reduction, was significantly higher than the amount of adrenochrome formed; taking into consideration the literature data on О(2)(-)· detection by NBT it is suggested that adrenaline autooxidation is accompanied by one-electron reduction not only of oxygen dissolved in the buffer and responsible for superoxide formation but possible carbon dioxide also dissolved in the buffer as well as carbonate/bicarbonate buffer components leading to formation of corresponding radicals. The plots of the dependence of the inhibition of adrenochrome and diformazan formation on the superoxide dismutase concentration have shown that not only superoxide radicals are formed during adrenaline autooxidation. Since carbonate/bicarbonate ions are known to be universally present in the living nature, their involvement in free radical processes proceeding in the organism is discussed.

  11. Free-standing and mechanically flexible mats consisting of electrospun carbon nanofibers made from a natural product of alkali lignin as binder-free electrodes for high-performance supercapacitors

    Science.gov (United States)

    Lai, Chuilin; Zhou, Zhengping; Zhang, Lifeng; Wang, Xiaoxu; Zhou, Qixin; Zhao, Yong; Wang, Yechun; Wu, Xiang-Fa; Zhu, Zhengtao; Fong, Hao

    2014-02-01

    Mechanically flexible mats consisting of electrospun carbon nanofibers (ECNFs) were prepared by first electrospinning aqueous mixtures containing a natural product of alkali lignin together with polyvinyl alcohol (PVA) into composite nanofiber mats followed by stabilization in air and carbonization in an inert environment. Morphological and structural properties, as well as specific surface area, total pore volume, average pore size, and pore size distribution, of the lignin-based ECNF mats were characterized; and their electrochemical performances (i.e., capacitive behaviors) were evaluated by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. The lignin-based ECNF mats exhibited outstanding performance as free-standing and/or binder-free electrodes of supercapacitors. For example, the ECNFs made from the composite nanofibers with mass ratio of lignin/PVA being 70/30 (i.e., ECNFs (70/30)) had the average diameter of ∼100 nm and the Brunauer-Emmett-Teller (BET) specific surface area of ∼583 m2 g-1. The gravimetric capacitance of ECNFs (70/30) electrode in 6 M KOH aqueous electrolyte exhibited 64 F g-1 at current density of 400 mA g-1 and 50 F g-1 at 2000 mA g-1. The ECNFs (70/30) electrode also exhibited excellent cycling durability/stability, and the gravimetric capacitance merely reduced by ∼10% after 6000 cycles of charge/discharge.

  12. Electrochemical characteristics of vanadium redox reactions on porous carbon electrodes for microfluidic fuel cell applications

    International Nuclear Information System (INIS)

    Lee, Jin Wook; Hong, Jun Ki; Kjeang, Erik

    2012-01-01

    Microfluidic vanadium redox fuel cells are membraneless and catalyst-free fuel cells comprising a microfluidic channel network with two porous carbon electrodes. The anolyte and catholyte for fuel cell operation are V(II) and V(V) in sulfuric acid based aqueous solution. In the present work, the electrochemical characteristics of the vanadium redox reactions are investigated on commonly used porous carbon paper electrodes and compared to a standard solid graphite electrode as baseline. Half-cell electrochemical impedance spectroscopy is applied to measure the overall ohmic resistance and resistivity of the electrodes. Kinetic parameters for both V(II) and V(V) discharging reactions are extracted from Tafel plots and compared for the different electrodes. Cyclic voltammetry techniques reveal that the redox reactions are irreversible and that the magnitudes of peak current density vary significantly for each electrode. The obtained kinetic parameters for the carbon paper are implemented into a numerical simulation and the results show a good agreement with measured polarization curves from operation of a microfluidic vanadium redox fuel cell employing the same material as flow-through porous electrodes. Recommendations for microfluidic fuel cell design and operation are provided based on the measured trends.

  13. Carbon Dioxide Utilization by the Five-Membered Ring Products of Cyclometalation Reactions.

    Science.gov (United States)

    Omae, Iwao

    2016-04-01

    In carbon dioxide utilization by cyclometalated five-membered ring products, the following compounds are used in four types of applications: 1. 2-Phenylpyrazole iridium compounds, pincer phosphine iridium compounds and 2-phenylimidazoline iridium compounds are used as catalysts for both formic acid production from CO 2 and H 2 , and hydrogen production from the formic acid. This formic acid can be a useful agent for H 2 production and storage for fuel cell electric vehicles. 2. Other chemicals, e.g. , dimethyl carbonate, methane, methanol and CO, are produced with dimethylaminomethylphenyltin compounds, pincer phosphine iridium compounds, pincer phosphine nickel compound and ruthenium carbene compound or 2-phenylpyridine iridium compounds, and phenylbenzothiazole iridium compounds as the catalysts for the reactions with CO 2 . 3. The five-membered ring intermediates of cyclometalation reactions with the conventional substrates react with carbon dioxide to afford their many types of carboxylic acid derivatives. 4. Carbon dioxide is easily immobilized at room temperature with immobilizing agents such as pincer phosphine nickel compounds, pincer phosphine palladium compounds, pincer N , N -dimethylaminomethyltin compounds and tris(2-pyridylthio)methane zinc compounds.

  14. Carbon Dioxide Utilization by the Five-Membered Ring Products of Cyclometalation Reactions

    Science.gov (United States)

    Omae, Iwao

    2016-01-01

    In carbon dioxide utilization by cyclometalated five-membered ring products, the following compounds are used in four types of applications: 1. 2-Phenylpyrazole iridium compounds, pincer phosphine iridium compounds and 2-phenylimidazoline iridium compounds are used as catalysts for both formic acid production from CO2 and H2, and hydrogen production from the formic acid. This formic acid can be a useful agent for H2 production and storage for fuel cell electric vehicles. 2. Other chemicals, e.g., dimethyl carbonate, methane, methanol and CO, are produced with dimethylaminomethylphenyltin compounds, pincer phosphine iridium compounds, pincer phosphine nickel compound and ruthenium carbene compound or 2-phenylpyridine iridium compounds, and phenylbenzothiazole iridium compounds as the catalysts for the reactions with CO2. 3. The five-membered ring intermediates of cyclometalation reactions with the conventional substrates react with carbon dioxide to afford their many types of carboxylic acid derivatives. 4. Carbon dioxide is easily immobilized at room temperature with immobilizing agents such as pincer phosphine nickel compounds, pincer phosphine palladium compounds, pincer N,N-dimethylaminomethyltin compounds and tris(2-pyridylthio)methane zinc compounds. PMID:28503084

  15. Nuclear reaction rate uncertainties and astrophysical modeling: Carbon yields from low-mass giants

    International Nuclear Information System (INIS)

    Herwig, Falk; Austin, Sam M.; Lattanzio, John C.

    2006-01-01

    Calculations that demonstrate the influence of three key nuclear reaction rates on the evolution of asymptotic giant branch stars have been carried out. We study the case of a star with an initial mass of 2 M · and a metallicity of Z=0.01, somewhat less than the solar metallicity. The dredge-up of nuclear processed material from the interior of the star and the yield predictions for carbon are sensitive to the rate of the 14 N(p,γ) 15 O and triple-α reactions. These reactions dominate the H- and He-burning shells of stars in this late evolutionary phase. Published uncertainty estimates for each of these two rates propagated through stellar evolution calculations cause uncertainties in carbon enrichment and yield predictions of about a factor of 2. The other important He-burning reaction, 12 C(α,γ) 16 O, although associated with the largest uncertainty in our study, does not have a significant influence on the abundance evolution compared with other modeling uncertainties. This finding remains valid when the entire evolution from the main sequence to the tip of the asymptotic giant branch is considered. We discuss the experimental sources of the rate uncertainties addressed here and give some outlooks for future work

  16. Dissolution and secondary mineral precipitation in basalts due to reactions with carbonic acid

    Science.gov (United States)

    Kanakiya, Shreya; Adam, Ludmila; Esteban, Lionel; Rowe, Michael C.; Shane, Phil

    2017-06-01

    One of the leading hydrothermal alteration processes in volcanic environments is when rock-forming minerals with high concentrations of iron, magnesium, and calcium react with CO2 and water to form carbonate minerals. This is used to the advantage of geologic sequestration of anthropogenic CO2. Here we experimentally investigate how mineral carbonation processes alter the rock microstructure due to CO2-water-rock interactions. In order to characterize these changes, CO2-water-rock alteration in Auckland Volcanic Field young basalts (less than 0.3 Ma) is studied before and after a 140 day reaction period. We investigate how whole core basalts with similar geochemistry but different porosity, permeability, pore geometry, and volcanic glass content alter due to CO2-water-rock reactions. Ankerite and aluminosilicate minerals precipitate as secondary phases in the pore space. However, rock dissolution mechanisms are found to dominate this secondary mineral precipitation resulting in an increase in porosity and decrease in rigidity of all samples. The basalt with the highest initial porosity and volcanic glass volume shows the most secondary mineral precipitation. At the same time, this sample exhibits the greatest increase in porosity and permeability, and a decrease in rock rigidity post reaction. For the measured samples, we observe a correlation between volcanic glass volume and rock porosity increase due to rock-fluid reactions. We believe this study can help understand the dynamic rock-fluid interactions when monitoring field scale CO2 sequestration projects in basalts.

  17. Synthesis of propylene carbonate from urea and propylene glycol over zinc oxide: A homogeneous reaction

    Directory of Open Access Journals (Sweden)

    Dengfeng Wang

    2014-11-01

    Full Text Available In this work, several metal oxides and zinc salts were used to catalyze propylene carbonate (PC synthesis from urea and propylene glycol (PG. According to the results of catalytic test and characterization, the catalytic pattern of ZnO was different from that of other metal oxides such as CaO, MgO and La2O3, but similar to that of zinc salts. In fact, the leaching of Zn species took place during reaction for ZnO. And ZnO was found to be the precursor of homogenous catalyst for reaction of urea and PG. Thus, the relationship between the amount of dissolved zinc species and the catalytic performance of employed ZnO was revealed. In addition, a possible reaction mechanism over ZnO was discussed based on the catalytic runs and the characterization of XRD, FTIR, and element analysis.

  18. Métodos de evaluación de las reacciones álcali-sílice en hormigones con áridos reciclados Evaluation methods of alkali-silica reaction in concrete with recycled aggre-gates

    Directory of Open Access Journals (Sweden)

    Miguel Barreto Santos

    2009-08-01

    Full Text Available Las reacciones álcali-sílice son una de las causas químicas de la degradación de los hormigones con áridos pétreos (HAP que comprometen su durabilidad. La introducción de áridos reciclados (AR en los hormigones produce alteraciones en sus propiedades y diferencias en los resultados de los ensayos de evaluación de las RAS. Se encuentran en la bibliografía algunos cuidados en la evaluación de los AR y de los hormigones con áridos reciclados (HAR en cuanto a la RAS, así como propuestas de modificación de las metodologías de ensayo existentes. Existen propuestas de modificación del ensayo acelerado de mortero y hormigón con AR para acelerar las reacciones y recomendaciones para evitar alteraciones en las características del AR grueso, durante la preparación de probetas. Algunos artículos recomiendan la pre-saturación del AR, debido a su absorción de agua, para evitar variaciones en los resultados de expansión de probetas de hormigón a edades prematuras. El presente artículo pretende describir sucintamente las características de los HAR y de las RAS presentando observaciones de la bibliografía en cuanto a los métodos de evaluación de las RAS en HAR y en HAP.Alkali-silica reactions (ASR are one of the causes of chemical degradation of concrete with natural aggregates (CNA that compromise its durability. The introduction of recycled aggregates (RA in concrete creates changes in their properties and differences in the results of the evaluation tests of ASR. Existing bibliography emphasizes special care in the evaluation of RA and concrete with recycled aggregate (CRA for ASR and changes are proposed to the existing test methods. There are proposals to change the accelerated test of mortar and concrete with RA to accelerate the reactions and recommendations to prevent changes in the characteristics of the RA, during the preparation of samples. Some articles recommend the pre-saturation of the AR, due to its absorption of

  19. Thermodynamic Data for Geochemical Modeling of Carbonate Reactions Associated with CO2 Sequestration – Literature Review

    Energy Technology Data Exchange (ETDEWEB)

    Krupka, Kenneth M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Cantrell, Kirk J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); McGrail, B. Peter [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2010-09-01

    Permanent storage of anthropogenic CO2 in deep geologic formations is being considered as a means to reduce the concentration of atmospheric CO2 and thus its contribution to global climate change. To ensure safe and effective geologic sequestration, numerous studies have been completed of the extent to which the CO2 migrates within geologic formations and what physical and geochemical changes occur in these formations when CO2 is injected. Sophisticated, computerized reservoir simulations are used as part of field site and laboratory CO2 sequestration studies. These simulations use coupled multiphase flow-reactive chemical transport models and/or standalone (i.e., no coupled fluid transport) geochemical models to calculate gas solubility, aqueous complexation, reduction/oxidation (redox), and/or mineral solubility reactions related to CO2 injection and sequestration. Thermodynamic data are critical inputs to modeling geochemical processes. The adequacy of thermodynamic data for carbonate compounds has been identified as an important data requirement for the successful application of these geochemical reaction models to CO2 sequestration. A review of thermodynamic data for CO2 gas and carbonate aqueous species and minerals present in published data compilations and databases used in geochemical reaction models was therefore completed. Published studies that describe mineralogical analyses from CO2 sequestration field and natural analogue sites and laboratory studies were also reviewed to identify specific carbonate minerals that are important to CO2 sequestration reactions and therefore require thermodynamic data. The results of the literature review indicated that an extensive thermodynamic database exists for CO2 and CH4 gases, carbonate aqueous species, and carbonate minerals. Values of ΔfG298° and/or log Kr,298° are available for essentially all of these compounds. However, log Kr,T° or heat capacity values at temperatures above 298 K exist for less than

  20. Thermodynamic Data for Geochemical Modeling of Carbonate Reactions Associated with CO2 Sequestration - Literature Review

    International Nuclear Information System (INIS)

    Krupka, Kenneth M.; Cantrell, Kirk J.; McGrail, B. Peter

    2010-01-01

    Permanent storage of anthropogenic CO 2 in deep geologic formations is being considered as a means to reduce the concentration of atmospheric CO 2 and thus its contribution to global climate change. To ensure safe and effective geologic sequestration, numerous studies have been completed of the extent to which the CO 2 migrates within geologic formations and what physical and geochemical changes occur in these formations when CO 2 is injected. Sophisticated, computerized reservoir simulations are used as part of field site and laboratory CO 2 sequestration studies. These simulations use coupled multiphase flow-reactive chemical transport models and/or standalone (i.e., no coupled fluid transport) geochemical models to calculate gas solubility, aqueous complexation, reduction/oxidation (redox), and/or mineral solubility reactions related to CO 2 injection and sequestration. Thermodynamic data are critical inputs to modeling geochemical processes. The adequacy of thermodynamic data for carbonate compounds has been identified as an important data requirement for the successful application of these geochemical reaction models to CO 2 sequestration. A review of thermodynamic data for CO 2 gas and carbonate aqueous species and minerals present in published data compilations and databases used in geochemical reaction models was therefore completed. Published studies that describe mineralogical analyses from CO 2 sequestration field and natural analogue sites and laboratory studies were also reviewed to identify specific carbonate minerals that are important to CO 2 sequestration reactions and therefore require thermodynamic data. The results of the literature review indicated that an extensive thermodynamic database exists for CO 2 and CH 4 gases, carbonate aqueous species, and carbonate minerals. Values of Δ f G 298 o and/or log K r,298 o are available for essentially all of these compounds. However, log K r,T o or heat capacity values at temperatures above 298 K exist

  1. Reactions of Criegee Intermediates with Non-Water Greenhouse Gases: Implications for Metal Free Chemical Fixation of Carbon Dioxide.

    Science.gov (United States)

    Kumar, Manoj; Francisco, Joseph S

    2017-09-07

    High-level theoretical calculations suggest that a Criegee intermediate preferably interacts with carbon dioxide compared to two other greenhouse gases, nitrous oxide and methane. The results also suggest that the interaction between Criegee intermediates and carbon dioxide involves a cycloaddition reaction, which results in the formation of a cyclic carbonate-type adduct with a barrier of 6.0-14.0 kcal/mol. These results are in contrast to a previous assumption that the reaction occurs barrierlessly. The subsequent decomposition of the cyclic adduct into formic acid and carbon dioxide follows both concerted and stepwise mechanisms. The latter mechanism has been overlooked previously. Under formic acid catalysis, the concerted decomposition of the cyclic carbonate may be favored under tropospheric conditions. Considering that there is a strong nexus between carbon dioxide levels in the atmosphere and global warming, the high reactivity of Criegee intermediates could be utilized for designing efficient carbon capture technologies.

  2. Upgrading of petroleum oil feedstocks using alkali metals and hydrocarbons

    Science.gov (United States)

    Gordon, John Howard

    2014-09-09

    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.

  3. Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

    Science.gov (United States)

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1995-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  4. Modification of multi-walled carbon nanotubes by Diels-Alder and Sandmeyer reactions.

    Science.gov (United States)

    Gergely, A; Telegdi, J; Mészáros, E; Pászti, Z; Tárkanyi, G; Kármán, F H; Kálmán, E

    2007-08-01

    Random (L) and aligned (A) multi-walled carbon nanotubes (MWNTs) were modified by Diels-Alder (DA) [4+2] cycloaddition, Sandmeyer (SM) reaction and by catalytic oxidation (OX). The properties of modified carbon nanotubes were studied by dispersability tests, elemental analysis, thermogravimetry/mass spectrometry, X-ray photoelectron spectroscopy, and NMR spectroscopy. The cycloaddition reaction could only be successfully performed with the L-MWNTs in molten and in solution state by using an aluminum chloride homogeneous catalyst. The efficiency and thermal stability of the solution phase cycloaddition were much higher than in the case of modification in the molten phase. The functionalization of both types of MWNTs by Sandmeyer reaction was carried out by copper(I) and iron(ll) ions that helped in the radical decomposition of diazonium salts. Successful functionalization of nanotubes is achieved by a long decomposition time of the thermally activated diazonium salts. To the contrary, in the case of radical decomposition of diazonium salts, the time is not a decisive parameter. The dispersability tests have proved the changes in the physical features of modified carbon nanotubes depending on the hydrophobic and hydrophilic character of the solvents. The presence of the modifying groups and their fragments from the functionalized MWNTs has been demonstrated by thermogravimetry/mass spectrometry (TG/MS). Relatively high concentration of sulfur atoms was detected by X-ray photoelectron spectroscopy in nanotubes modified by sulfur substituent groups. In the case of catalytic oxidation, the X-ray photoelectron spectroscopic signal of oxygen bound to nanotubes showed considerable change as compared to pristine nanotubes. Due to the high thermal stability of modified multi-walled carbon nanotubes, the functionalized derivatives are applicable in several industrial fields.

  5. Electron transfer in reactions of ketones with organolithium reagents. A carbon-14 kinetic isotope effect probe

    International Nuclear Information System (INIS)

    Yamataka, H.; Fujimura, N.; Kawafuji, Y.; Hanafusa, T.

    1987-01-01

    Kinetic isotope effects have been determined for reactions of ketones labeled with carbon-14 at the carbonyl carbon with MeLi and Me 2 CuLi in diethyl ether at 0 0 C. Observed isotope effects were as follows: (C 6 H 5 ) 2 C double bonds O + MeLi, 12 k/ 14 k = 1.000 +/- 0.002; (C 6 H 5 ) 2 C double bonds O + Me 2 CuLi, 1.029 +/- 0.005; 2,4,6-Me 3 C 6 H 2 COC 6 H 5 + MeLi, 1.023 +/- 0.004. The relative reactivities of ortho-, meta-, and para-substituted benzophenones with these reagents were also determined by the competition experiments. These results are consistent with an electron-transfer step which is followed by a carbon-carbon bond-forming step that is or is not rate determining depending on the structure of ketones and reagents. The reaction of benzophenone with MeLi proceeds via rate-determining electron transfer; the change in nucleophile from MeLi to Me 2 CuLi shifts the rate-determining step from electron transfer to recombination; the change in ketone from benzophenone to 2,4,6-trimethylbenzophenone also shifts the rate-determining step from electron transfer to recombination because the latter step becomes slower for the more hindered ketone. The extent of the geometrical change of the substrate at the electron-transfer transition state of the reaction of benzophenone with MeLi was estimated to be small on the basis of the magnitude of the KIE and the rho value of the Hammett correlation

  6. Polyaniline-Derived Ordered Mesoporous Carbon as an Efficient Electrocatalyst for Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Kai Wan

    2015-06-01

    Full Text Available Nitrogen-doped ordered mesoporous carbon was synthesized by using polyaniline as the carbon source and SBA-15 as the template. The microstructure, composition and electrochemical behavior were extensively investigated by the nitrogen sorption isotherm, X-ray photoelectron spectroscopy, cyclic voltammetry and rotating ring-disk electrode. It is found that the pyrolysis temperature yielded a considerable effect on the pore structure, elemental composition and chemical configuration. The pyrolysis temperature from 800 to 1100 °C yielded a volcano-shape relationship with both the specific surface area and the content of the nitrogen-activated carbon. Electrochemical tests showed that the electrocatalytic activity followed a similar volcano-shape relationship, and the carbon catalyst synthesized at 1000 °C yielded the best performance. The post-treatment in NH3 was found to further increase the specific surface area and to enhance the nitrogen doping, especially the edge-type nitrogen, which favored the oxygen reduction reaction in both acid and alkaline media. The above findings shed light on electrocatalysis and offer more strategies for the controllable synthesis of the doped carbon catalyst.

  7. Sintering uranium oxide in the reaction product of hydrogen-carbon dioxide mixtures

    International Nuclear Information System (INIS)

    De Hollander, W.R.; Nivas, Y.

    1975-01-01

    Compacted pellets of uranium oxide alone or containing one or more additives such as plutonium dioxide, gadolinium oxide, titanium dioxide, silica, and alumina are heated to 900 to 1599 0 C in the presence of a mixture of hydrogen and carbon dioxide, either alone or with an inert carrier gas and held at the desired temperature in this atmosphere to sinter the pellets. The sintered pellets are then cooled in an atmosphere having an oxygen partial pressure of 10 -4 to 10 -18 atm of oxygen such as dry hydrogen, wet hydrogen, dry carbon monoxide, wet carbon monoxide, inert gases such as nitrogen, argon, helium, and neon and mixtures of ayny of the foregoing including a mixture of hydrogen and carbon dioxide. The ratio of hydrogen to carbon dioxide in the gas mixture fed to the furnace is controlled to give a ratio of oxygen to uranium atoms in the sintered particles within the range of 1.98:1 to about 2.10:1. The water vapor present in the reaction products in the furnace atmosphere acts as a hydrolysis agent to aid removal of fluoride should such impurity be present in the uranium oxide. (U.S.)

  8. Effect Of Reaction Environments On The Reactivity Of PCB (2-Chlorobiphenyl) Over Activated Carbon Impregnated With Palladized Iron

    Science.gov (United States)

    Reactive activated carbon (RAC) impregnated with palladized iron nanoparticles has been developed to treat polychlorinated biphenyls (PCBs). In this study, we evaluated the effects of various reaction environments on the adsorption-mediated dechlorination of 2-chlorobiphenyl (2-...

  9. Synergistically enhanced activity of nitrogen-doped carbon dots/graphene composites for oxygen reduction reaction

    Science.gov (United States)

    Liu, Hui; Zhao, Qingshan; Liu, Jingyan; Ma, Xiao; Rao, Yuan; Shao, Xiaodong; Li, Zhongtao; Wu, Wenting; Ning, Hui; Wu, Mingbo

    2017-11-01

    With rapid dissociative adsorption of oxygen, nitrogen-doped carbon nanomaterials have been demonstrated to be efficient alternative catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we developed a mild hydrothermal strategy to construct nitrogen-doped carbon dots/graphene (NCDs-NG) composites towards ORR. Carbon dots (CDs) were derived from petroleum coke via acid oxidation while graphene oxide (GO) was obtained from graphite by modified Hummer's method. Graphene was employed as a conductive substrate to disperse CDs during hydrothermal reducing reaction while ammonia was utilized as N source to dope both graphene and CDs. The synergistic effects, i.e. CDs as pillars for graphene and catalytic sites for ORR, the high conductivity of graphene, the quick O2 adsorption on doped pyridinic nitrogen endow the NCDs-NG composites with enhanced ORR catalytic performance in alkaline electrolyte. The onset potential of -95 mV and kinetic current density of 12.7 mA cm-2 at -0.7 V (vs. Ag/AgCl) can be compared to those of the commercial 20 wt% Pt/C catalyst. The electron transfer number is about 3.9, revealing a four-electron pathway for ORR. The optimal NCDs-NG catalyst shows superior durability and methanol tolerance than 20 wt% Pt/C. This work demonstrates a feasible and effective strategy to prepare metal-free efficient ORR electrocatalysts for fuel cell applications.

  10. Coupling Reactions of Carbon Dioxide with Epoxides Catalyzed by Vanadium Aminophenolate Complexes.

    Science.gov (United States)

    Elkurtehi, Ali I; Kerton, Francesca M

    2017-03-22

    A series of vanadium compounds supported by tetradentate aminobis(phenolate) ligands were screened for catalytic reactivity in the reaction of propylene oxide (PO) with CO 2 : [VO(OMe)(O 2 NO BuMeMeth )], [VO(OMe)(ON 2 O BuMe )], [VO(OMe)(O 2 NN BuBuPy )], and [VO(OMe)(O 2 NO BuBuFurf )]. They showed similar reactivities, but reaction rates were higher for [VO(OMe)(ON 2 O BuMe )], which was studied in more detail. Turnover frequencies for conversion of PO over 500 h -1 were observed. Activation energies were determined experimentally through in situ IR spectroscopy for propylene carbonate (48.2 kJ mol -1 ), styrene carbonate (45.6 kJ mol -1 ), and cyclohexene carbonate (54.7 kJ mol -1 ) formation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Chlor-alkali electrolysis

    International Nuclear Information System (INIS)

    Sammer, G.

    2001-01-01

    The chlor-alkali industry produces simultaneously chlorine (Cl 2 ) and caustic soda (NaOH) by decomposition of a salt solution in water. Additionally to the chlorine and caustic soda, hydrogen (H 2 ) is produced. The global production capacity of chlorine in 1995 was approximately 44 million tons. The development of the chlorine production capacity in Western Europe since 1960 is presented. The most important chlorine producer in Western Europe is Germany with 38 % of the annual chlorine capacity of Western Europe. The chlorine capacity in 1997 in different Western European countries and their share an the total capacity in Western Europe is also presented. World-wide several processes are available for the production of chlorine and caustic soda. The most important routes are the following: ion exchange membrane process; mercury cell process; diaphragm process. Several other processes are available but do not have a significant contribution to the total production. The geographical distribution of the processes differs widely. In Japan the membrane process is predominate with 73 %, in the United States the diaphragm process with 75 %, whereas in Western Europe the mercury cell process is the most important one (64 %) [EIPPCB, 2000]. Approximately 65 % of the global chlorine capacity is located in these three regions. A comparison of the relative contribution of different production technologies to the chlor-alkali capacity in these three regions and in the world in 1994 is given. The distribution of processes and capacities of chlor-alkali plants in some European countries is presented (October 1999). Note that any one plant can have more than one cell technology installed. (author)

  12. Bifunctional metal-free catalysis of mesoporous noble carbons for oxygen reduction and evolution reactions.

    Science.gov (United States)

    Sakaushi, Ken; Fellinger, Tim-Patrick; Antonietti, Markus

    2015-04-13

    Electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are key reactions in lithium-oxygen batteries (LOBs) being a promising candidate to store renewable energies due to their high specific energy. However current development on LOBs is suffering from unsuitable catalysts. In particular, carbon-based catalysts were found to perform poorly in this system. Here, we show that metal-free mesoporous nitrogen-doped carbons (meso-NdCs) offer highly promising performances in both ORR and OER; they act as bifunctional catalysts, and can be synthesized by a very simple method. The efficient electrocatalytic activity of ORR and OER was used in a LOB cell during discharge and charge, respectively, and the present system showed a lower overpotential comparable to metal-based catalysts in LOB system. Thus, we demonstrate that meso-NdCs act as a new and affordable candidate for the efficient bifunctional oxygen catalysis, therefore can be applied to many energy-related applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Heidelberg polarized alkali source

    International Nuclear Information System (INIS)

    Kraemer, D.; Steffens, E.; Jaensch, H.; Philipps Universitaet, Marburg, Germany)

    1984-01-01

    A new atomic beam type polarized alkali ion source has been installed at Heidelberg. In order to improve the beam polarization considerably optical pumping is applied in combination with an adiabatic medium field transition which results in beams in single hyperfine sublevels. The m state population is determined by laser-induced fluorescence spectroscopy. Highly polarized beams (P/sub s/ > 0.9, s = z, zz) with intensities of 30 to 130 μA can be extracted for Li + and Na + , respectively

  14. Influence of curing conditions on durability of alkali-resistant glass ...

    Indian Academy of Sciences (India)

    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 ...

  15. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

    Science.gov (United States)

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1995-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  16. Two dimensional N-containing carbon materials for oxygen reduction reaction

    Science.gov (United States)

    Feng, Yexin; Hu, Zhenpeng; Zhang, Lixin

    2013-03-01

    Seeking Pt replacement catalysts for cathode oxygen reduction reaction (ORR) is very important for the application of some new energy technologies like fuel cells and lithium-air batteries. N-doped graphene and carbon nitride sheets are two kinds of promising materials. For the N-doped graphene, it is found that nitrogen clusters other than isolated substitutionals are the active sites for oxygen reduction. Clusters with three or four N atoms are found to be the most active. Codoping boron (or Fe, Co) can effectively stabilize these high energy clusters while keep the cluster's high activity. For the carbon nitride sheets, in the C:N ratio range of 2.0-3.0, they are stable enough and can potentially catalyze the oxygen reduction as efficiently as Pt. It is revealed that the concentration of nitrogen can tune the Fermi level of the material and thus the catalytic property. The catalytic sites are located at those carbon atoms with special configurations rather than the nitrogen atoms. These results are helpful in designing N-containing carbon materials for ORR.

  17. Solvent-Free Henry and Michael Reactions with Nitroalkanes Promoted by Potassium Carbonate as a Versatile Heterogeneous Catalyst

    Directory of Open Access Journals (Sweden)

    Giovanna Bosica

    2017-01-01

    Full Text Available The use of a simple weak inorganic base such as potassium carbonate facilitated the formation of carbon-carbon bonds through both the Henry and the Michael reactions with nitrocompounds. The application of this catalyst under environmentally friendly solventless heterogeneous conditions gave satisfactory to good yields of β-nitroalcohols, involving aliphatic and aromatic starting materials, as well as high to excellent yields in the formation of Michael adducts using several different Michael acceptors and nitroalkanes.

  18. Palladium on Carbon-Catalyzed Suzuki-Miyaura Coupling Reaction Using an Efficient and Continuous Flow System

    Directory of Open Access Journals (Sweden)

    Tomohiro Hattori

    2015-01-01

    Full Text Available The continuous flow Suzuki-Miyaura reaction between various haloarenes and arylboronic acids was successfully achieved within only ca. 20 s during the single-pass through a cartridge filled with palladium on carbon (Pd/C. No palladium leaching was observed in the collected reaction solution by atomic absorption spectrometry (detection limit: 1 ppm.

  19. Cobalt-Bridged Ionic Liquid Polymer on a Carbon Nanotube for Enhanced Oxygen Evolution Reaction Activity.

    Science.gov (United States)

    Ding, Yuxiao; Klyushin, Alexander; Huang, Xing; Jones, Travis; Teschner, Detre; Girgsdies, Frank; Rodenas, Tania; Schlögl, Robert; Heumann, Saskia

    2018-03-19

    By taking inspiration from the catalytic properties of single-site catalysts and the enhancement of performance through ionic liquids on metal catalysts, we exploited a scalable way to place single cobalt ions on a carbon-nanotube surface bridged by polymerized ionic liquid. Single dispersed cobalt ions coordinated by ionic liquid are used as heterogeneous catalysts for the oxygen evolution reaction (OER). Performance data reveals high activity and stable operation without chemical instability. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  20. Numerical study for melting heat transfer and homogeneous-heterogeneous reactions in flow involving carbon nanotubes

    Science.gov (United States)

    Hayat, Tasawar; Muhammad, Khursheed; Alsaedi, Ahmed; Asghar, Saleem

    2018-03-01

    Present work concentrates on melting heat transfer in three-dimensional flow of nanofluid over an impermeable stretchable surface. Analysis is made in presence of porous medium and homogeneous-heterogeneous reactions. Single and multi-wall CNTs (carbon nanotubes) are considered. Water is chosen as basefluid. Adequate transformations yield the non-linear ordinary differential systems. Solution of emerging problems is obtained using shooting method. Impacts of influential variables on velocity and temperature are discussed graphically. Skin friction coefficient and Nusselt number are numerically discussed. The results for MWCNTs and SWCNTs are compared and examined.

  1. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    Science.gov (United States)

    Nandan, Ravi; Nanda, Karuna Kar

    2015-06-01

    We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min-1. The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

  2. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Nandan, Ravi, E-mail: aerawat27@gmail.com; Nanda, Karuna Kar [Materials Research Centre, Indian Institute of Science, Bangalore-560012 (India)

    2015-06-24

    We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min{sup −1}. The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

  3. Inverted supercritical carbon dioxide/aqueous biphasic media for rhodium-catalyzed hydrogenation reactions.

    Science.gov (United States)

    Burgemeister, Katja; Franciò, Giancarlo; Gego, Volker H; Greiner, Lasse; Hugl, Herbert; Leitner, Walter

    2007-01-01

    An inverted supercritical carbon dioxide (scCO(2))/aqueous biphasic system has been used as reaction media for Rh-catalysed hydrogenation of polar substrates. Chiral and achiral CO(2)-philic catalysts were efficiently immobilised in scCO(2) as the stationary phase, while the polar substrates and products were contained in water as the mobile phase. Notably, product separation and catalyst recycling were conducted without depressurisation of the autoclave. The catalyst phase was reused several times with high conversion and product recovery of more than 85 %. Loss of rhodium and phosphorus by leaching were found to be below the detection limit after the first two cycles in the majority of repetitive experiments. The reaction conditions were optimised with a minimum of experiments by using a simplex algorithm in a sequential optimisation. Total turnover numbers (TTNs) of up to 1600, turnover frequencies (TOFs) of up to 340 h(-1) and ee's up to 99 % were obtained in repetitive batch operations. The scope of the devised catalytic system has been investigated and a semicontinuous reaction setup has been implemented. The chiral ligand (R,S)-3-H(2)F(6)-BINAPHOS allowed highly enantioselective hydrogenation of itaconic acid and methyl-2-acetamidoacrylate combined with a considerable catalyst stability in these reaction media.

  4. An amorphous Co-carbonate-hydroxide nanowire array for efficient and durable oxygen evolution reaction in carbonate electrolytes.

    Science.gov (United States)

    Xie, Maowen; Yang, Lin; Ji, Yuyao; Wang, Ziqiang; Ren, Xiang; Liu, Zhiang; Asiri, Abdullah M; Xiong, Xiaoli; Sun, Xuping

    2017-11-09

    The development of earth-abundant catalysts toward high-efficient and durable oxygen evolution reaction (OER) electrocatalysis in the carbonate electrolyte is in great demand but remains a huge challenge. In this communication, we describe the development of a Co-carbonate-hydroxide nanowire array on nickel foam (CoCH/NF) via in situ electrochemical conversion of the Co(CO 3 ) 0.5 (OH)·0.11H 2 O nanowire array. When utilized as a 3D catalyst electrode for the OER in 1.0 M KHCO 3 (pH: 8.3), as-formed CoCH/NF demands overpotential of only 332 mV to drive a geometrical catalytic current density of 10 mA cm -2 , with its catalytic activity being maintained for at least 130 h. Impressively, it also demonstrates a high turnover frequency value of 0.22 mol O 2 s -1 at an overpotential of 500 mV.

  5. Efficient Construction of Energetic Materials via Nonmetallic Catalytic Carbon-Carbon Cleavage/Oxime-Release-Coupling Reactions.

    Science.gov (United States)

    Zhao, Gang; He, Chunlin; Yin, Ping; Imler, Gregory H; Parrish, Damon A; Shreeve, Jean'ne M

    2018-03-14

    The exploitation of C-C activation to facilitate chemical reactions is well-known in organic chemistry. Traditional strategies in homogeneous media rely upon catalyst-activated or metal-mediated C-C bonds leading to the design of new processes for applications in organic chemistry. However, activation of a C-C bond, compared with C-H bond activation, is a more challenging process and an underdeveloped area because thermodynamics does not favor insertion into a C-C bond in solution. Carbon-carbon bond cleavage through loss of an oxime moiety has not been reported. In this paper, a new observation of self-coupling via C-C bond cleavage with concomitant loss of oxime in the absence of metals (either metal-complex mediation or catalysis) results in dihydroxylammonium 5,5-bistetrazole-1,10-diolate (TKX-50) as well as N, N'-([3,3'-bi(1,2,4-oxadiazole)]-5,5'-diyl)dinitramine, a potential candidate for a new generation of energetic materials.

  6. Carbon Dioxide Promotes Dehydrogenation in the Equimolar C2H2-CO2Reaction to Synthesize Carbon Nanotubes.

    Science.gov (United States)

    Shi, Wenbo; Peng, Yue; Steiner, Stephen A; Li, Junhua; Plata, Desiree L

    2018-01-16

    The equimolar C 2 H 2 -CO 2 reaction has shown promise for carbon nanotube (CNT) production at low temperatures and on diverse functional substrate materials; however, the electron-pushing mechanism of this reaction is not well demonstrated. Here, the role of CO 2 is explored experimentally and theoretically. In particular, 13 C labeling of CO 2 demonstrates that CO 2 is not an important C source in CNT growth by thermal catalytic chemical vapor deposition. Consistent with this experimental finding, the adsorption behaviors of C 2 H 2 and CO 2 on a graphene-like lattice via density functional theory calculations reveal that the binding energies of C 2 H 2 are markedly higher than that of CO 2 , suggesting the former is more likely to incorporate into CNT structure. Further, H-abstraction by CO 2 from the active CNT growth edge would be favored, ultimately forming CO and H 2 O. These results support that the commonly observed, promoting role of CO 2 in CNT growth is due to a CO 2 -assisted dehydrogenation mechanism. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Investigation of catalytic oxidation of diamond by water vapor and carbon dioxide in the presence of alkali melts of some rare earth oxides

    International Nuclear Information System (INIS)

    Kulakova, I.I.; Rudenko, A.P.; Sulejmenova, A.S.; Tolstopyatova, A.A.

    1978-01-01

    The results of an investigation of the catalytic oxydation of diamond by carbon dioxide and water vapors at 906 deg C in the presence of melts of some rare earth oxides in potassium hydroxide are given. The ion La 3+ was shown to possess the most catalytic activity. The earlier proposed mechanisms of the diamond oxidation by CO 2 and H 2 O were corroborated. The ions of rare earth elements were found to accelerate the different stages of the process

  8. Alkali metal and alkali earth metal gadolinium halide scintillators

    Science.gov (United States)

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

    2016-08-02

    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.

  9. Coal chemistry. 8. Reactions of tetralin with coal and with some carbon-14-containing model compounds

    Energy Technology Data Exchange (ETDEWEB)

    Collins, C.J.; Raaen, V.F.; Benjamin, B.M.; Maupin, P.H.; Roark, W.H.

    1979-08-15

    When coal was treated with tetralin-l-/sup 14/C at 400/sup 0/C, small yields of ..cap alpha..- and ..beta..-methylnaphthalenes-/sup 14/C were observed. In order to determine the mechanism of the reaction, tetralin was heated with /sup 14/C-labeled 1,3-diphenylpropanes (1), with 1,3-diphenylpropene (2), and with /sup 14/C-labeled phenetoles (3). In each case methylnaphthalenes were observed, and the origins of the methyl groups were determined with carbon-14. In addition to the methylnaphthalenes, 1 and 2 also yielded toluene and ethylbenzene (after 19 h), whereas phenetole-..beta..-/sup 14/C (3-..beta..-/sup 14/C) yielded toluene (unlabeled) plus ethyl-/sup 14/C-benzene, benzene, phenol, and a mixture of ..cap alpha..- and ..beta..-ethyl-/sup 14/C-naphthalenes. Crossover experiments with labeled phenetole and unlabeled ethyl p-tolyl ether proved the intramolecularity of the reaction phenetole ..-->.. toluene + ethylbenzene, thus illustrating a 1,2-phenyl shift from oxygen to carbon.

  10. Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts

    Science.gov (United States)

    Senanayake, Sanjaya D.; Pappoe, Naa Adokaley; Nguyen-Phan, Thuy-Duong; Luo, Si; Li, Yuanyuan; Xu, Wenqian; Liu, Zongyuan; Mudiyanselage, Kumudu; Johnston-Peck, Aaron C.; Frenkel, Anatoly I.; Heckler, Ilana; Stacchiola, Dario; Rodriguez, José A.

    2016-10-01

    We have studied the catalytic carbon monoxide (CO) oxidation (CO + 0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5 wt.% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface states or intermediates of this reaction. With the aid of several ex situ characterization techniques including transmission electron microscopy (TEM), the local catalyst morphology and structure were also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggest that surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Both in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.

  11. Investigation of chemical and electrochemical reactions mechanisms in a direct carbon fuel cell using olive wood charcoal as sustainable fuel

    Science.gov (United States)

    Elleuch, Amal; Halouani, Kamel; Li, Yongdan

    2015-05-01

    Direct carbon fuel cell (DCFC) is a high temperature fuel cell using solid carbon as fuel. The use of environmentally friendly carbon material constitutes a promising option for the DCFC future. In this context, this paper focuses on the use of biomass-derived charcoal renewable fuel. A practical investigation of Tunisian olive wood charcoal (OW-C) in planar DCFCs is conducted and good power density (105 mW cm-2) and higher current density (550 mA cm-2) are obtained at 700 °C. Analytical and predictive techniques are performed to explore the relationships between fuel properties and DCFC chemical and electrochemical mechanisms. High carbon content, carbon-oxygen groups and disordered structure, are the key parameters allowing the achieved good performance. Relatively complex chain reactions are predicted to explain the gas evolution within the anode. CO, H2 and CH4 participation in the anodic reaction is proved.

  12. The effect of alkali on the product distribution from black liquor conversion under supercritical water.

    Science.gov (United States)

    Hawangchu, Y; Atong, D; Sricharoenchaikul, V

    2017-07-01

    Lignin in chemical pulping waste, or black liquor (BL), can be converted into various products via supercritical water gasification (SCWG). However, the inherited alkaline contents from the pulping chemicals may affect the product yields and properties. In this research, the influence of the residual alkali on the product distribution via SCWG of soda BL and kraft BL was evaluated. The SCWG was performed in a batch quartz reactor for 10 min at various temperatures (673, 773 and 873 K) and pressures (250, 300 and 400 bar). The highest hydrogen (H 2 ) production occurred at 873 K for the soda BL. The water-gas shift reaction with sodium ions played an important part in the H 2 production, while only small amounts of methane and carbon monoxide were detected. Hydrocarbons, carboxylic acids and esters were the dominant substrates in the liquid products, which denoted the potential of this method for bond cleaving of the lignin macromolecule. As a result, BL, which typically contains alkali salt, was an appropriate feedstock for the SCWG reaction to produce renewable fuel. This method not only has a positive influence on the generation of value added products from highly corrosive waste but also helps avoid some technical problems commonly encountered with direct firing in a recovery boiler.

  13. Performance of a biogas upgrading process based on alkali absorption with regeneration using air pollution control residues.

    Science.gov (United States)

    Baciocchi, Renato; Carnevale, Ennio; Costa, Giulia; Gavasci, Renato; Lombardi, Lidia; Olivieri, Tommaso; Zanchi, Laura; Zingaretti, Daniela

    2013-12-01

    This work analyzes the performance of an innovative biogas upgrading method, Alkali absorption with Regeneration (AwR) that employs industrial residues and allows to permanently store the separated CO2. This process consists in a first stage in which CO2 is removed from the biogas by means of chemical absorption with KOH or NaOH solutions followed by a second stage in which the spent absorption solution is contacted with waste incineration Air Pollution Control (APC) residues. The latter reaction leads to the regeneration of the alkali reagent in the solution and to the precipitation of calcium carbonate and hence allows to reuse the regenerated solution in the absorption process and to permanently store the separated CO2 in solid form. In addition, the final solid product is characterized by an improved environmental behavior compared to the untreated residues. In this paper the results obtained by AwR tests carried out in purposely designed demonstrative units installed in a landfill site are presented and discussed with the aim of verifying the feasibility of this process at pilot-scale and of identifying the conditions that allow to achieve all of the goals targeted by the proposed treatment. Specifically, the CO2 removal efficiency achieved in the absorption stage, the yield of alkali regeneration and CO2 uptake resulting for the regeneration stage, as well as the leaching behavior of the solid product are analyzed as a function of the type and concentration of the alkali reagent employed for the absorption reaction. Copyright © 2013 Elsevier Ltd. All rights reserved.

  14. N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells.

    Science.gov (United States)

    Shui, Jianglan; Wang, Min; Du, Feng; Dai, Liming

    2015-02-01

    The availability of low-cost, efficient, and durable catalysts for oxygen reduction reaction (ORR) is a prerequisite for commercialization of the fuel cell technology. Along with intensive research efforts of more than half a century in developing nonprecious metal catalysts (NPMCs) to replace the expensive and scarce platinum-based catalysts, a new class of carbon-based, low-cost, metal-free ORR catalysts was demonstrated to show superior ORR performance to commercial platinum catalysts, particularly in alkaline electrolytes. However, their large-scale practical application in more popular acidic polymer electrolyte membrane (PEM) fuel cells remained elusive because they are often found to be less effective in acidic electrolytes, and no attempt has been made for a single PEM cell test. We demonstrated that rationally designed, metal-free, nitrogen-doped carbon nanotubes and their graphene composites exhibited significantly better long-term operational stabilities and comparable gravimetric power densities with respect to the best NPMC in acidic PEM cells. This work represents a major breakthrough in removing the bottlenecks to translate low-cost, metal-free, carbon-based ORR catalysts to commercial reality, and opens avenues for clean energy generation from affordable and durable fuel cells.

  15. Effect of different chemical modification of carbon nanotubes for the oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Dumitru, Anca; Mamlouk, M.; Scott, K.

    2014-01-01

    The electrochemical reduction of oxygen on chemically modified multi-walled carbon nanotubes (CNTs) electrodes in 1 M KOH solution has been studied using the rotating ring disc electrode (RDE). The surface modification of CNTs has been estimated by XPS and Raman spectroscopy. The effect of different oxygen functionalities on the surface of carbon nanotube for the oxygen reduction reaction (ORR) is considered in terms of the number of electrons (n) involved. Electrochemical studies indicate that in the case of the modification of CNTs with citric acid and diazonium salts the n values were close to two in the measured potential range, and the electrochemical reduction is limited to the production of peroxide as the final product. In the case of the modification of carbon nanotubes with peroxymonosulphuric acid, in the measured potential range, the n value is close to 4 indicating the four-electron pathway for the ORR. By correlating ORR measurements with the XPS analysis, we propose that the increase in electrocatalytic activity towards the ORR, for CNT can be attributed to the increase in C-O groups on the surface of CNTs after modification with peroxymonosulphuric acid

  16. Ordered hierarchically porous carbon codoped with iron and nitrogen as electrocatalyst for the oxygen reduction reaction.

    Science.gov (United States)

    Deng, Chengwei; Zhong, Hexiang; Yao, Lan; Liu, Sisi; Xu, Zhuang; Zhang, Huamin

    2014-12-01

    N-doped carbon catalysts have attracted great attention as potential alternatives to expensive Pt-based catalysts used in fuel cells. Herein, an ordered hierarchically porous carbon codoped with N and Fe (Fe-NOHPC) is prepared by an evaporation-induced self-assembly process followed by carbonization under ammonia. The soft template and Fe species promote the formation of the porous structure and facilitate the oxygen reduction reaction (ORR).The catalyst possesses an ordered hierarchically porous structure with a large surface area (1172.5 m(2) g(-1) ) and pore volume of 1.03 cm(3) g(-1) . Compared to commercial 20% Pt/C, it exhibits better ORR catalytic activity and higher stability as well as higher methanol tolerance in an alkaline electrolyte, which demonstrates its potential use in fuel cells as a nonprecious cathode catalyst. The N configuration, Fe species, and pore structure of the catalysts are believed to correlate with its high catalytic activity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Nitrogen and Fluorine-Codoped Carbon Nanowire Aerogels as Metal-Free Electrocatalysts for Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Shaofang [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA; Zhu, Chengzhou [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA; Song, Junhua [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99352 USA; Xiao, Biwei [Energy and Environmental Directory, Pacific Northwest National Laboratory, Richland WA 99352 USA; Du, Dan [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA; Lin, Yuehe [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA

    2017-07-11

    The development of active, durable, and low-cost catalysts to replace noble metal-based materials is highly desirable to promote the sluggish oxygen reduction reaction in fuel cells. Herein, nitrogen and fluorine-codoped three-dimensional carbon nanowire aerogels, composed of interconnected carbon nanowires, were synthesized for the first time by a hydrothermal carbonization process. Owing to their porous nanostructures and heteroatom-doping, the as-prepared carbon nanowire aerogels, with optimized composition, present excellent electrocatalytic activity that is comparable to commercial Pt/C. Remarkably, the aerogels also exhibit superior stability and methanol tolerance. This synthesis procedure paves a new way to design novel heteroatomdoped catalysts.

  18. Acoustic emission monitoring of crack formation during alkali silica\

    Czech Academy of Sciences Publication Activity Database

    Lokajíček, Tomáš; Přikryl, R.; Šachlová, Š.; Kuchařová, A.

    2017-01-01

    Roč. 220, MAR 30 (2017), s. 175-182 ISSN 0013-7952 R&D Projects: GA ČR(CZ) GAP104/12/0915 Institutional support: RVO:67985831 Keywords : Alkali-silica reaction * accelerated expansion test * ultrasonic sounding * acoustic emission * backscattered electron imaging Subject RIV: JJ - Other Materials OBOR OECD: Materials engineering Impact factor: 2.569, year: 2016

  19. Effect of Reaction Temperature on Carbon Yield and Morphology of CNTs on Copper Loaded Nickel Nanoparticles

    Directory of Open Access Journals (Sweden)

    Hu Ming

    2016-01-01

    Full Text Available This investigation was attempted to introduce carbon nanotubes (CNTs onto surface of copper powders in order to improve heat transfer performance of copper matrix for engineering application of electrical packaging materials. The Ni/MgO catalyst was formed on the copper powders surface by means of codeposition method. CVD technique was executed to fabricate uniform CNTs on copper powders and effect of reaction temperature on the morphology of CNTs was surveyed. The results showed that CNTs products on the copper powder surface were distributed uniformly even if reaction temperature was different. The diameter dimension of CNTs was within the scope of 30~60 nm. Growth behaviors of CNTs by CVD method were considered to be “tip-growth” mechanism. Raman spectra of CNTs proved that intensity ratio of D-band to G-band (ID/IG increased as deposition reaction temperature increased, which implied that order degree of graphitic structure in synthesized CNTs improved.

  20. Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions

    Directory of Open Access Journals (Sweden)

    Matthieu Jouffroy

    2014-10-01

    Full Text Available The capacity of two cavity-shaped ligands, HUGPHOS-1 and HUGPHOS-2, to generate exclusively singly phosphorus-ligated complexes, in which the cyclodextrin cavity tightly wraps around the metal centre, was explored with a number of late transition metal cations. Both cyclodextrin-derived ligands were assessed in palladium-catalysed Mizoroki–Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine complexes under catalytic conditions was established by high-pressure NMR studies and shown to have a deep impact on the two carbon–carbon bond forming reactions both in terms of activity and selectivity. For example, when used as ligands in the rhodium-catalysed hydroformylation of styrene, they lead to both high isoselectivity and high enantioselectivity. In the study dealing with the Mizoroki–Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2.

  1. Revealing Brown Carbon Chromophores Produced in Reactions of Methylglyoxal with Ammonium Sulfate.

    Science.gov (United States)

    Lin, Peng; Laskin, Julia; Nizkorodov, Sergey A; Laskin, Alexander

    2015-12-15

    Atmospheric brown carbon (BrC) is an important contributor to light absorption and climate forcing by aerosols. Reactions between small water-soluble carbonyls and ammonia or amines have been identified as one of the potential pathways of BrC formation. However, detailed chemical characterization of BrC chromophores has been challenging and their formation mechanisms are still poorly understood. Understanding BrC formation is impeded by the lack of suitable methods which can unravel the variability and complexity of BrC mixtures. This study applies high performance liquid chromatography (HPLC) coupled to photodiode array (PDA) detector and high resolution mass spectrometry (HRMS) to investigate optical properties and chemical composition of individual BrC components produced through reactions of methylglyoxal (MG) and ammonium sulfate (AS), both of which are abundant in the atmospheric environment. A direct relationship between optical properties and chemical composition of 30 major BrC chromophores is established. Nearly all of these chromophores are nitrogen-containing compounds that account for >70% of the overall light absorption by the MG+AS system in the 300-500 nm range. These results suggest that reduced-nitrogen organic compounds formed in reactions between atmospheric carbonyls and ammonia/amines are important BrC chromophores. It is also demonstrated that improved separation of BrC chromophores by HPLC will significantly advance understanding of BrC chemistry.

  2. The influenced of reaction time on the degradation of palm oil empty fruit bunch (EFB) in hydrothermal carbonization

    Science.gov (United States)

    Sarwono, Rakhman; Kurniawan, Hendris Hendarsyah

    2017-11-01

    Hydrothermal carbonization (HTC) of empty fruit bunch (EFB) of palm oil in different reaction times were investigated. Experiments were carried out in an autoclave at different reaction time of 3,6,9, 15, 20, 25 and 40 hours. With a fixed solid/liquid ratio of 5 gram of EFB in 50 ml water as a solvent, and temperature reaction of 250 °C. Increase the reaction time the soluble products are also increased. The liquid products were analyzed using GCMS to determine the chemical composition. The chemical composition were greatly affected by the reaction time. The main component was glycolic acid, by increasing the reaction time made the varieties of chemical compositions in liquid products, especially for the glycolic acid component, it was decreased slightly. The higher heating value (HHV) also increase slighly by increasing the reaction time both solid and liquid products.

  3. Alkali injection system with controlled CO.sub.2 /O.sub.2 ratios for combustion of coal

    Science.gov (United States)

    Berry, Gregory F.

    1988-01-01

    A high temperature combustion process for an organic fuel containing sulfur n which the nitrogen of air is replaced by carbon dioxide for combination with oxygen with the ratio of CO.sub.2 /O.sub.2 being controlled to generate combustion temperatures above 2000 K. for a gas-gas reaction with SO.sub.2 and an alkali metal compound to produce a sulfate and in which a portion of the carbon-dioxide rich gas is recycled for mixing with oxygen and/or for injection as a cooling gas upstream from heating exchangers to limit fouling of the exchangers, with the remaining carbon-dioxide rich gas being available as a source of CO.sub.2 for oil recovery and other purposes.

  4. Monitoreo mediante EIS del acero embebido en un concreto de escoria activada alcalinamente expuesto a carbonatación EIS monitoring of embedded steel in alkali activated concrete exposed to carbonation

    Directory of Open Access Journals (Sweden)

    Willian Aperador

    2011-01-01

    Full Text Available En este trabajo se utilizó la técnica de espectroscopia de impedancia electroquímica (EIS para evaluar la acción del dióxido de carbono sobre la corrosión de un acero estructural ASTM A 706 embebido en un concreto de escoria activado alcalinamente (AAS, el concreto AAS es una mezcla de escoria molida granulada, agregados finos y gruesos y solución alcalina (silicato de sodio en la cantidad requerida para la mezcla de concreto. El estudio se realizó comparativamente con especímenes expuestos a condiciones naturales con una baja concentración de CO2 (0,03% CO2. La carbonatación del concreto se obtuvo de forma acelerada bajo condiciones controladas (3% CO2, 65% de humedad relativa y 20°C de temperatura. Los datos de Impedancia fueron adquiridos en un rango de 1mHz hasta 100kHz. A las frecuencias altas se encontró la respuesta de la interfase medio de exposición-concreto y a frecuencias bajas la respuesta de la interfase correspondiente al concreto - acero. Mediante EIS se estableció la capacidad de lograr la pasivación del acero embebido en concreto AAS, en condiciones ambientales naturales y aceleradas.In this work the technique of impedance spectroscopy electrochemistry (EIS was used to evaluate the effects of carbon dioxide on the corrosion of ASTM A 706 structural steel embedded in concrete with alkali activated slag (AAS, AAS concrete is a mixture of ground granulated slag, fine and coarse aggregates and alkaline solution (sodium silicate in the amount required for the concrete mix. The study was conducted in comparison with specimens exposed to natural conditions with a low concentration of CO2 (0.03% CO2. The carbonation of the concrete was obtained through accelerated carbonation under controlled conditions (3% CO2, 65% of relative humidity and 20°C of temperature. The data of Impedance in the middle frequency region 1mHz - 100KHz. A high frequency response was found using the interface-specific exposure and low frequency

  5. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama

    2013-07-02

    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  6. MOF-derived Cu/nanoporous carbon composite and its application for electro-catalysis of hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Raoof, Jahan-Bakhsh; Hosseini, Sayed Reza; Ojani, Reza; Mandegarzad, Sakineh

    2015-01-01

    In this work, metal-organic framework Cu 3 (BTC) 2 [BTC = 1,3,5-benzenetricarboxylate] (commonly known as MOF-199 or HKUST-1), is used as porous template for preparation of a Cu/nanoporous carbon composite. The MOF-derived Cu/nanoporous carbon composite (Cu/NPC composite) is synthesized by direct carbonization of the MOF-199 without any carbon precursor additive. The physical characterization of the solid catalyst is achieved by using a variety of different techniques, including XRD (X-ray powder diffraction), scanning electron microscopy, thermo-gravimetric analysis, and nitrogen physisorption measurements. The electrochemical results have shown that the Cu/NPC composite modified glassy carbon electrode (Cu/NPC/GCE) as a non-platinum electrocatalyst exhibited favorable catalytic activity for hydrogen evolution reaction, in spite of high resistance to faradic process. This behavior can be attributed to existence of Cu metal confirmed by XRD and/or high effective pore surface area (1025 m 2 g −1 ) in the Cu/NPC composite. The electron transfer coefficient and exchange current density for the Cu/NPC/GCE is calculated by Tafel plot at about 0.34 and 1.2 × 0 −3 mAcm −2 , respectively. - Graphical abstract: Metal organic framework-derived Cu/nanoporous carbon composite (Cu/NPC composite) was prepared by direct carbonization of MOF-199 without addition of any carbon source at 900 °C. The Cu/NPC/GCE demonstrated an excellent electrocatalytic activity towards hydrogen evolution reaction compared with bare GCE. - Highlights: • MDNPC (MOF-199 derived nanoporous carbon) is prepared by direct carbonization. • MOF-199 is utilized as a template without addition of carbon resource. • The MDNPC has a good electrocatalytic activity in hydrogen evolution reaction. • High BET surface area and hydrogen adsorption property improved catalyst activity.

  7. Differentiation of chemical reaction activity of various carbon nanotubes using redox potential: Classification by physical and chemical structures.

    Science.gov (United States)

    Tsuruoka, Shuji; Matsumoto, Hidetoshi; Castranova, Vincent; Porter, Dale W; Yanagisawa, Takashi; Saito, Naoto; Kobayashi, Shinsuke; Endo, Morinobu

    2015-12-01

    The present study systematically examined the kinetics of a hydroxyl radical scavenging reaction of various carbon nanotubes (CNTs) including double-walled and multi-walled carbon nanotubes (DWCNTs and MWCNTs), and carbon nano peapods (AuCl 3 @DWCNT). The theoretical model that we recently proposed based on the redox potential of CNTs was used to analyze the experimental results. The reaction kinetics for DWCNTs and thin MWCNTs agreed well with the theoretical model and was consistent with each other. On the other hand, thin and thick MWCNTs behaved differently, which was consistent with the theory. Additionally, surface morphology of CNTs substantially influenced the reaction kinetics, while the doped particles in the center hollow parts of CNTs (AuCl 3 @DWCNT) shifted the redox potential in a different direction. These findings make it possible to predict the chemical and biological reactivity of CNTs based on the structural and chemical nature and their influence on the redox potential.

  8. Improved Catalysis of Green-Synthesized Pd-Ag Alloy-Nanoparticles for Anodic Oxidation of Methanol in Alkali

    International Nuclear Information System (INIS)

    Roy Chowdhury, Sreya; Ghosh, Srabanti; Bhattachrya, Swapan Kumar

    2017-01-01

    Highlights: • Pd and Pd x Ag y nanoalloys are synthesised by simple green synthetic method without using any capping agent. • Increased electrochemical surface area and roughness factor in case of Pd x Ag y alloy generates enhanced catalytically active sites which help methanol oxidation reaction. • By analysing the products of MOR reaction by CV, FTIR and HPLC plausible mechanism of the reaction is proposed. • Among different compositions Pd 4 Ag and Pd are the best electrodes for oxidation of methanol and formate respectively in alkali. - Abstract: Monometallic Pd, Ag and bimetallic Pd x Ag y alloy nanoparticles were synthesized in a single pot using a green synthetic protocol in absence of any capping agent. X-ray, electron diffraction, microscopic and spectroscopic studies of synthesized material demonstrate the formation of nanoballs with radius of 10–20 nm of face centred cubic metals and alloys. The electrochemical studies of as-synthesized materials loaded on carbon support reveal that the Pd 4 Ag nanoparticles exhibit the best and synergistic electro-catalytic activity in reference to oxidation of methanol in alkali. The most active Pd 4 Ag nanoparticles show higher peak current (201 mA mg −1 ) in comparison to that (133 mA mg −1 ) of Pd in cyclic voltammetric study. The electrode shows the highest exchange current density (1.95 × 10 −2 mA mg −1 of Pd) for methanol oxidation reaction (MOR) and higher catalytic activity for oxidation of possible intermediates like formaldehyde and sodium formate of MOR. Ex-situ infrared spectrometry and chromatographic studies of reaction products reveal that Ag accelerates the formation of formate rather than carbonate elucidating the plausible mechanism of the reaction. These findings have important implications for further fine-tuning of the Pd nano alloys toward highly active and selective catalysts for alcohol fuel cells.

  9. Modern aspects of homogeneous-heterogeneous reactions and variable thickness in nanofluids through carbon nanotubes

    Science.gov (United States)

    Hayat, Tasawar; Ahmed, Sohail; Muhammad, Taseer; Alsaedi, Ahmed

    2017-10-01

    This article examines homogeneous-heterogeneous reactions and internal heat generation in Darcy-Forchheimer flow of nanofluids with different base fluids. Flow is generated due to a nonlinear stretchable surface of variable thickness. The characteristics of nanofluid are explored using CNTs (single and multi walled carbon nanotubes). Equal diffusion coefficients are considered for both reactants and auto catalyst. The conversion of partial differential equations (PDEs) to ordinary differential equations (ODEs) is done via appropriate transformations. Optimal homotopy approach is implemented for solutions development of governing problems. Averaged square residual errors are computed. The optimal solution expressions of velocity, temperature and concentration are explored through plots by using several values of physical parameters. Further the coefficient of skin friction and local Nusselt number are examined through graphs.

  10. Melting Heat in Radiative Flow of Carbon Nanotubes with Homogeneous-Heterogeneous Reactions

    Science.gov (United States)

    Hayat, Tasawar; Muhammad, Khursheed; Muhammad, Taseer; Alsaedi, Ahmed

    2018-04-01

    The present article provides mathematical modeling for melting heat and thermal radiation in stagnation-point flow of carbon nanotubes towards a nonlinear stretchable surface of variable thickness. The process of homogeneous-heterogeneous reactions is considered. Diffusion coefficients are considered equal for both reactant and autocatalyst. Water and gasoline oil are taken as base fluids. The conversion of partial differential system to ordinary differential system is done by suitable transformations. Optimal homotopy technique is employed for the solutions development of velocity, temperature, concentration, skin friction and local Nusselt number. Graphical results for various values of pertinent parameters are displayed and discussed. Our results indicate that the skin friction coefficient and local Nusselt number are enhanced for larger values of nanoparticles volume fraction.

  11. Effect of electron injection on defect reactions in irradiated silicon containing boron, carbon, and oxygen

    Science.gov (United States)

    Makarenko, L. F.; Lastovskii, S. B.; Yakushevich, H. S.; Moll, M.; Pintilie, I.

    2018-04-01

    Comparative studies employing Deep Level Transient Spectroscopy and C-V measurements have been performed on recombination-enhanced reactions between defects of interstitial type in boron doped silicon diodes irradiated with alpha-particles. It has been shown that self-interstitial related defects which are immobile even at room temperatures can be activated by very low forward currents at liquid nitrogen temperatures. Their activation is accompanied by the appearance of interstitial carbon atoms. It has been found that at rather high forward current densities which enhance BiOi complex disappearance, a retardation of Ci annealing takes place. Contrary to conventional thermal annealing of the interstitial boron-interstitial oxygen complex, the use of forward current injection helps to recover an essential part of charge carriers removed due to irradiation.

  12. The reduction of carbon dioxide in iron biocatalyst catalytic hydrogenation reaction: a theoretical study.

    Science.gov (United States)

    Yang, Longhua; Wang, Hongming; Zhang, Ning; Hong, Sanguo

    2013-08-21

    The reaction mechanism of CO₂ hydrogenation catalyzed by [FeH(PP₃)]BF₄ (PP₃ = P(CH₂CH₂PPh₂)₃) had been investigated by DFT calculations. Our calculations indicated that the reduction of carbon dioxide could be carried out via two spin states, the high-spin (HS) triplet state and the low-spin (LS) singlet state. The minimum energy crossing points (MECPs) on the seam of two intersecting PESs (potential energy surfaces) were searched out. Some interesting phenomena, such as the open-loop phenomenon, and the O-rebound process, were demonstrated to be the important causes of the spin crossover. All these calculations gave us insight into the essence of the related experiment from the macro point of view, and helped to verify which spin states the related complexes pertinent were in. All of these researches would help advance the development of efficient and structurally tailorable CO₂ hydrogenation catalysts.

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

    Directory of Open Access Journals (Sweden)

    al-Swaidani Aref M.

    2015-11-01

    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.

  14. Visible-Light-Irradiated Graphitic Carbon Nitride Photocatalyzed Diels-Alder Reactions with Dioxygen as Sustainable Mediator for Photoinduced Electrons.

    Science.gov (United States)

    Zhao, Yubao; Antonietti, Markus

    2017-08-01

    Photocatalytic Diels-Alder (D-A) reactions with electron rich olefins are realized by graphitic carbon nitride (g-C 3 N 4 ) under visible-light irradiation and aerobic conditions. This heterogeneous photoredox reaction system is highly efficient, and the apparent quantum yield reaches a remarkable value of 47 % for the model reaction. Dioxygen plays a critical role as electron mediator, which is distinct from the previous reports in the homogeneous Ru II complex photoredox system. Moreover, the reaction intermediate vinylcyclobutane is captured and monitored during the reaction, serving as a direct evidence for the proposed reaction mechanism. The cycloaddition process is thereby determined to be the combination of direct [4+2] cycloaddition and [2+2] cycloaddition followed by photocatalytic rearrangement of the vinylcyclobutane intermediate. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Utilization of Mineral Wools as Alkali-Activated Material Precursor

    Directory of Open Access Journals (Sweden)

    Juho Yliniemi

    2016-04-01

    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.

  16. Thermodynamic modelling of alkali-activated slag cements

    International Nuclear Information System (INIS)

    Myers, Rupert J.; Lothenbach, Barbara; Bernal, Susan A.; Provis, John L.

    2015-01-01

    Highlights: • A thermodynamic modelling analysis of alkali-activated slag cements is presented. • Thermodynamic database describes zeolites, alkali carbonates, C–(N–)A–S–H gel. • Updated thermodynamic model for Mg–Al layered double hydroxides. • Description of phase assemblages in Na 2 SiO 3 - and Na 2 CO 3 -activated slag cements. • Phase diagrams for NaOH-activated and Na 2 SiO 3 -activated slag cements are simulated. - Abstract: This paper presents a thermodynamic modelling analysis of alkali-activated slag-based cements, which are high performance and potentially low-CO 2 binders relative to Portland cement. The thermodynamic database used here contains a calcium (alkali) aluminosilicate hydrate ideal solid solution model (CNASH-ss), alkali carbonate and zeolite phases, and an ideal solid solution model for a hydrotalcite-like Mg–Al layered double hydroxide phase. Simulated phase diagrams for NaOH- and Na 2 SiO 3 -activated slag-based cements demonstrate the high stability of zeolites and other solid phases in these materials. Thermodynamic modelling provides a good description of the chemical compositions and types of phases formed in Na 2 SiO 3 -activated slag cements over the most relevant bulk chemical composition range for these cements, and the simulated volumetric properties of the cement paste are consistent with previously measured and estimated values. Experimentally determined and simulated solid phase assemblages for Na 2 CO 3 -activated slag cements were also found to be in good agreement. These results can be used to design the chemistry of alkali-activated slag-based cements, to further promote the uptake of this technology and valorisation of metallurgical slags

  17. Fluid phase equilibria of the reaction mixture during the selective hydrogenation of 2-butenal in dense carbon dioxide

    DEFF Research Database (Denmark)

    Musko, Nikolai; Jensen, Anker Degn; Baiker, Alfons

    2012-01-01

    Knowledge of the phase behaviour and composition is of paramount importance for understanding multiphase reactions. We have investigated the effect of the phase behaviour in the palladium-catalysed selective hydrogenation of 2-butenal to saturated butanal in dense carbon dioxide. The reactions were...... performed using a 5wt% Pd on activated carbon in custom-designed high pressure autoclaves at 323K. The Cubic-Plus-Association (CPA) equation of state was employed to model the phase behaviour of the experimentally studied systems. CPA binary interaction parameters were estimated based on the experimental...

  18. Ruthenium/Graphene-like Layered Carbon Composite as an Efficient Hydrogen Evolution Reaction Electrocatalyst.

    Science.gov (United States)

    Chen, Zhe; Lu, Jinfeng; Ai, Yuejie; Ji, Yongfei; Adschiri, Tadafumi; Wan, Lijun

    2016-12-28

    Efficient water splitting through electrocatalysis has been studied extensively in modern energy devices, while the development of catalysts with activity and stability comparable to those of Pt is still a great challenge. In this work, we successfully developed a facile route to synthesize graphene-like layered carbon (GLC) from a layered silicate template. The obtained GLC has layered structure similar to that of the template and can be used as support to load ultrasmall Ru nanoparticles on it in supercritical water. The specific structure and surface properties of GLC enable Ru nanoparticles to disperse highly uniformly on it even at a large loading amount (62 wt %). When the novel Ru/GLC was used as catalyst on a glass carbon electrode for hydrogen evolution reaction (HER) in a 0.5 M H 2 SO 4 solution, it exhibits an extremely low onset potential of only 3 mV and a small Tafel slope of 46 mV/decade. The outstanding performance proved that Ru/GLC is highly active catalyst for HER, comparable with transition-metal dichalcogenides or selenides. As the price of ruthenium is much lower than platinum, our study shows that Ru/GLC might be a promising candidate as an HER catalyst in future energy applications.

  19. Formation of tungsten carbide nanoparticles on graphitized carbon to facilitate the oxygen reduction reaction

    Science.gov (United States)

    Yan, Zaoxue; He, Guoqiang; Cai, Mei; Meng, Hui; Shen, Pei Kang

    2013-11-01

    Tungsten carbide nanoparticles with the average size less than 5 nm uniformly dispersed on the graphitized carbon matrix have been successfully synthesized by a one-step ion-exchange method. This route is to locally anchor the interested species based on an ionic level exchange process using ion-exchange resin. The advantage of this method is the size control of targeted nanomaterial as well as the graphitization of resin at low temperatures catalyzed by iron salt. The Pt nanoparticles coupled with tungsten carbide nanoparticles on graphitized carbon nanoarchitecture form a stable electrocatalyst (Pt/WC-GC). The typical Pt/WC-GC electrocatalyst gives a Pt-mass activity of 247.7 mA mgPt-1, which is much higher than that of commercial Pt/C electrocatalyst (107.1 mA mgPt-1) for oxygen reduction reaction due to the synergistic effect between Pt and WC. The presented method is simple and could be readily scaled up for mass production of the nanomaterials.

  20. Non-Noble Metal-based Carbon Composites in Hydrogen Evolution Reaction: Fundamentals to Applications.

    Science.gov (United States)

    Wang, Jing; Xu, Fan; Jin, Haiyan; Chen, Yiqing; Wang, Yong

    2017-04-01

    Hydrogen has been hailed as a clean and sustainable alternative to finite fossil fuels in many energy systems. Water splitting is an important method for hydrogen production in high purity and large quantities. To accelerate the hydrogen evolution reaction (HER) rate, it is highly necessary to develop high efficiency catalysts and to select a proper electrolyte. Herein, the performances of non-noble metal-based carbon composites under various pH values (acid, alkaline and neutral media) for HER in terms of catalyst synthesis, structure and molecular design are systematically discussed. A detailed analysis of the structure-activity-pH correlations in the HER process gives an insight on the origin of the pH-dependence for HER, and provide guidance for future HER mechanism studies on non-noble metal-based carbon composites. Furthermore, this Review gives a fresh impetus to rational design of high-performance noble-metal-free composites catalysts and guide researchers to employ the established electrocatalysts in proper water electrolysis technologies. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Toward Activity Origin of Electrocatalytic Hydrogen Evolution Reaction on Carbon-Rich Crystalline Coordination Polymers.

    Science.gov (United States)

    Wang, Lihuan; Tranca, Diana C; Zhang, Jian; Qi, Yanpeng; Sfaelou, Stavroula; Zhang, Tao; Dong, Renhao; Zhuang, Xiaodong; Zheng, Zhikun; Seifert, Gotthard

    2017-10-01

    The fundamental understanding of electrocatalytic active sites for hydrogen evolution reaction (HER) is significantly important for the development of metal complex involved carbon electrocatalysts with low kinetic barrier. Here, the MS x N y (M = Fe, Co, and Ni, x/y are 2/2, 0/4, and 4/0, respectively) active centers are immobilized into ladder-type, highly crystalline coordination polymers as model carbon-rich electrocatalysts for H 2 generation in acid solution. The electrocatalytic HER tests reveal that the coordination of metal, sulfur, and nitrogen synergistically facilitates the hydrogen ad-/desorption on MS x N y catalysts, leading to enhanced HER kinetics. Toward the activity origin of MS 2 N 2 , the experimental and theoretical results disclose that the metal atoms are preferentially protonated and then the production of H 2 is favored on the MN active sites after a heterocoupling step involving a N-bound proton and a metal-bound hydride. Moreover, the tuning of the metal centers in MS 2 N 2 leads to the HER performance in the order of FeS 2 N 2 > CoS 2 N 2 > NiS 2 N 2 . Thus, the understanding of the catalytic active sites provides strategies for the enhancement of the electrocatalytic activity by tailoring the ligands and metal centers to the desired function. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Carbon-Heteroatom Bond Formation by an Ultrasonic Chemical Reaction for Energy Storage Systems.

    Science.gov (United States)

    Kim, Hyun-Tak; Shin, HyeonOh; Jeon, In-Yup; Yousaf, Masood; Baik, Jaeyoon; Cheong, Hae-Won; Park, Noejung; Baek, Jong-Beom; Kwon, Tae-Hyuk

    2017-12-01

    The direct formation of CN and CO bonds from inert gases is essential for chemical/biological processes and energy storage systems. However, its application to carbon nanomaterials for improved energy storage remains technologically challenging. A simple and very fast method to form CN and CO bonds in reduced graphene oxide (RGO) and carbon nanotubes (CNTs) by an ultrasonic chemical reaction is described. Electrodes of nitrogen- or oxygen-doped RGO (N-RGO or O-RGO, respectively) are fabricated via the fixation between N 2 or O 2 carrier gas molecules and ultrasonically activated RGO. The materials exhibit much higher capacitance after doping (133, 284, and 74 F g -1 for O-RGO, N-RGO, and RGO, respectively). Furthermore, the doped 2D RGO and 1D CNT materials are prepared by layer-by-layer deposition using ultrasonic spray to form 3D porous electrodes. These electrodes demonstrate very high specific capacitances (62.8 mF cm -2 and 621 F g -1 at 10 mV s -1 for N-RGO/N-CNT at 1:1, v/v), high cycling stability, and structural flexibility. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Carbon-based Solid Acid Catalyzed One-pot Mannich Reaction: A Facile Synthesis of β-Amino Carbonyl Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Davoodnia, Abolghasem; Tavakoli-Nishaburi, Afsaneh; Tavakoli-Hoseini, Niloofar [Islamic Azad University, Mashhad (Iran, Islamic Republic of)

    2011-02-15

    A simple and efficient method for the synthesis of β-amino carbonyl compounds by one-pot three-component Mannich reaction of acetophenone, aromatic aldehydes and aromatic amines using a carbon-based solid acid (CBSA), as an effective and reusable catalyst, is described. The present methodology offers several advantages such as simple procedure with an easy work-up, shorter reaction times, and high yields.

  4. Heteropoly Acid/Nitrogen Functionalized Onion-like Carbon Hybrid Catalyst for Ester Hydrolysis Reactions.

    Science.gov (United States)

    Liu, Wei; Qi, Wei; Guo, Xiaoling; Su, Dangsheng

    2016-02-18

    A novel heteropoly acid (HPA)/nitrogen functionalized onion-like carbon (NOLC) hybrid catalyst was synthesized through supramolecular (electrostatic and hydrogen bond) interactions between the two components. The chemical structure and acid strength of the HPA/NOLC hybrid have been fully characterized by thermogravimetric analysis, IR spectroscopy, X-ray photoelectron spectroscopy, NH3 temperature-programmed desorption and acid-base titration measurements. The proposed method for the fabrication of the HPA/NOLC hybrid catalyst is a universal strategy for different types of HPAs to meet various requirements of acidic or redox catalysis. The hydrophobic environment of NOLC effectively prevents the deactivation of HPA in an aqueous system, and the combination of uniformly dispersed HPA clusters and the synergistic effect between NOLC and HPA significantly promotes its activity in ester hydrolysis reactions, which is higher than that of bare PWA as homogeneous catalyst. The kinetics of the hydrolysis reactions indicate that the aggregation status of the catalyst particles has great influence on the apparent activity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. KOH-activated multi-walled carbon nanotubes as platinum supports for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    He, Chaoxiong; Song, Shuqin; Liu, Jinchao [State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-sen University, Guangzhou 510275 (China); Maragou, Vasiliki; Tsiakaras, Panagiotis [Department of Mechanical Engineering, School of Engineering, University of Thessaly, Pedion Areos, 38834 Volos (Greece)

    2010-11-01

    In the present investigation, multi-walled carbon nanotubes (MWCNTs) thermally treated by KOH were adopted as the platinum supporting material for the oxygen reduction reaction electrocatalysts. FTIR and Raman spectra were used to investigate the surface state of MWCNTs treated by KOH at different temperatures (700, 800, and 900 C) and showed MWCNTs can be successfully functionalized. The structural properties of KOH-activated MWCNTs supported Pt were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their electrochemical performance was evaluated by the aid of cyclic voltammetry (CV) and rotating disk electrode (RDE) voltammetry. According to the experimental findings of the present work, the surrface of MWCNTs can be successfully functionalized with oxygen-containing groups after activation by KOH, favoring the good dispersion of Pt nanoparticles with narrow size distribution. The as-prepared Pt catalysts supported on KOH treated MWCNTs at higher temperature, possess higher electrochemical surface area and exhibit desirable activity towards oxygen reduction reaction (ORR). More precisely, it has been found that the electrochemical active area of Pt/MWCNTs-900 is approximately two times higher than that of Pt/MWCNTs. It can be concluded that KOH activation is an effective way to decorate MWCNTs' surface with oxygen-containing groups and bigger surface area, which makes them more suitable as electrocatalyst support materials. (author)

  6. Heavily Graphitic-Nitrogen Self-doped High-porosity Carbon for the Electrocatalysis of Oxygen Reduction Reaction

    Science.gov (United States)

    Feng, Tong; Liao, Wenli; Li, Zhongbin; Sun, Lingtao; Shi, Dongping; Guo, Chaozhong; Huang, Yu; Wang, Yi; Cheng, Jing; Li, Yanrong; Diao, Qizhi

    2017-11-01

    Large-scale production of active and stable porous carbon catalysts for oxygen reduction reaction (ORR) from protein-rich biomass became a hot topic in fuel cell technology. Here, we report a facile strategy for synthesis of nitrogen-doped porous nanocarbons by means of a simple two-step pyrolysis process combined with the activation of zinc chloride and acid-treatment process, in which kidney bean via low-temperature carbonization was preferentially adopted as the only carbon-nitrogen sources. The results show that this carbon material exhibits excellent ORR electrocatalytic activity, and higher durability and methanol-tolerant property compared to the state-of-the-art Pt/C catalyst for the ORR, which can be mainly attributed to high graphitic-nitrogen content, high specific surface area, and porous characteristics. Our results can encourage the synthesis of high-performance carbon-based ORR electrocatalysts derived from widely-existed natural biomass.

  7. Adding nickel formate in alkali lignin to increase contents of alkylphenols and aromatics during fast pyrolysis.

    Science.gov (United States)

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

    2017-03-01

    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. Copyright © 2016. Published by Elsevier Ltd.

  8. Are Neutral-Neutral Reactions Effective for the Carbon-Chain Growth of Cyanopolyynes and Polyacetylenes in Interstellar Space?

    International Nuclear Information System (INIS)

    Fukuzawa, K.; Osamura, Y.; Schaefer, H.F. III

    1998-01-01

    Ab initio molecular quantum-mechanical methods have been applied to explore the possibility of neutral-neutral reactions leading to the formation of cyanopolyynes and polyacetylenes in interstellar cloud. Potential energy surfaces for the reactions between the CN radical and polyacetylenes indicate that all reactions, C 2n H 2 + CN (n = 1 endash 4), which form HC 2n+1 N molecules, are exothermic and have no energy barriers. We have also examined the possibility of the various product channels from the reactions C 2n H 2 + CN based on the thermochemical relationships. The theoretical results show that none of the product channels is exothermic except the case which produces HC 2n+1 N, with the carbon chain being longer than the reactant polyacetylene. Similar results are obtained for the regioselectivity of the reactions, C 2n H 2 + C 2 H (n = 1 endash 4), to produce hydrocarbons. The only possible products from the latter reactions are shown to be HC 2n+2 H + H under the conditions of interstellar space. These results clearly demonstrate the importance of the neutral-neutral reactions on the carbon-chain growth of cyanopolyynes and polyacetylenes. copyright copyright 1998. The American Astronomical Society

  9. Cobalt-Embedded Nitrogen-Rich Carbon Nanotubes Efficiently Catalyze Hydrogen Evolution Reaction at All pH Values

    Czech Academy of Sciences Publication Activity Database

    Zou, X.; Huang, X.; Goswami, A.; Silva, R.; Sathe, B. R.; Mikmeková, Eliška; Asefa, T.

    2014-01-01

    Roč. 53, č. 17 (2014), s. 4372-4376 ISSN 1433-7851 R&D Projects: GA MŠk(CZ) LO1212 Institutional support: RVO:68081731 Keywords : carbon nanotubes * cobalt nanoparticles * electrocatalysis * hydrogen evolution reaction * water splitting Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 11.261, year: 2014

  10. Alkali-vapor laser-excimer pumped alkali laser

    International Nuclear Information System (INIS)

    Yue Desheng; Li Wenyu; Wang Hongyan; Yang Zining; Xu Xiaojun

    2012-01-01

    Based on the research internal and overseas, the principle of the excimer pumped alkali laser (XPAL) is explained, and the advantages and disadvantages of the XPAL are analyzed. Taking into consideration the difficulties that the diode pumped alkali laser (DPAL) meets on its development, the ability to solve or avoid these difficulties of XPAL is also analyzed. By summing up the achievements of the XPAL, the possible further prospect is proposed. The XPAL is of possibility to improve the performance of the DPAL. (authors)

  11. Role of alkalis of aggregate origin in the deterioration of CAC concrete

    International Nuclear Information System (INIS)

    Blanco-Varela, M.T.; Martinez-Ramirez, S.; Vazquez, T.; Sanchez-Moral, S.

    2005-01-01

    Both hexagonal and cubic calcium aluminate cement (CAC) hydrates react with atmospheric CO 2 , bringing about mineralogical changes in concrete, which may, on occasion, lead to loss of mechanical strength. Alkaline hydrolysis or carbonation in the presence of alkalis is a highly destructive process. The purpose of the study was to determine what caused CAC concrete deterioration in a prestressed beam that had suffered intense external damage and showed signs of alkaline hydrolysis or a reaction between the aggregate and the cement. Samples of the internal (sound) and external (damaged) parts of the concrete were studied using XRF, XRD, FTIR, OM, SEM/EDX, and BSE techniques, and mechanical strength was measured on microspecimens extracted from both zones. The conclusion drawn from these analyses was that alkaline hydrolysis took place on or near the surface of the concrete. The white deposits observed around the alkali-containing aggregate were found to consist primarily of bayerite whose very loose consistency undermined the aggregate-matrix bond, greatly weakening the material

  12. Characterisation of Dissolved Organic Carbon by Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry

    Science.gov (United States)

    Materić, Dušan; Peacock, Mike; Kent, Matthew; Cook, Sarah; Gauci, Vincent; Röckmann, Thomas; Holzinger, Rupert

    2017-04-01

    Dissolved organic carbon (DOC) is an integral component of the global carbon cycle. DOC represents an important terrestrial carbon loss as it is broken down both biologically and photochemically, resulting in the release of carbon dioxide (CO2) to the atmosphere. The magnitude of this carbon loss can be affected by land management (e.g. drainage). Furthermore, DOC affects autotrophic and heterotrophic processes in aquatic ecosystems, and, when chlorinated during water treatment, can lead to the release of harmful trihalomethanes. Numerous methods have been used to characterise DOC. The most accessible of these use absorbance and fluorescence properties to make inferences about chemical composition, whilst high-performance size exclusion chromatography can be used to determine apparent molecular weight. XAD fractionation has been extensively used to separate out hydrophilic and hydrophobic components. Thermochemolysis or pyrolysis Gas Chromatography - Mass Spectrometry (GC-MS) give information on molecular properties of DOC, and 13C NMR spectroscopy can provide an insight into the degree of aromaticity. Proton Transfer Reaction - Mass Spectrometry (PTR-MS) is a sensitive, soft ionisation method suitable for qualitative and quantitative analysis of volatile and semi-volatile organic vapours. So far, PTR-MS has been used in various environmental applications such as real-time monitoring of volatile organic compounds (VOCs) emitted from natural and anthropogenic sources, chemical composition measurements of aerosols etc. However, as the method is not compatible with water, it has not been used for analysis of organic traces present in natural water samples. The aim of this work was to develop a method based on thermal desorption PTR-MS to analyse water samples in order to characterise chemical composition of dissolved organic carbon. We developed a clean low-pressure evaporation/sublimation system to remove water from samples and thermal desorption system to introduce

  13. A review of the high temperature oxidation of uranium oxides in molten salts and in the solid state to form alkali metal uranates, and their composition and properties

    Science.gov (United States)

    Griffiths, Trevor R.; Volkovich, Vladimir A.

    An extensive review of the literature on the high temperature reactions (both in melts and in the solid state) of uranium oxides (UO 2, U 3O 8 and UO 3) resulting in the formation of insoluble alkali metal (Li to Cs) uranates is presented. Their uranate(VI) and uranate(V) compounds are examined, together with mixed and oxygen-deficient uranates. The reactions of uranium oxides with carbonates, oxides, per- and superoxides, chlorides, sulfates, nitrates and nitrites under both oxidising and non-oxidising conditions are critically examined and systematised, and the established compositions of a range of uranate(VI) and (V) compounds formed are discussed. Alkali metal uranates(VI) are examined in detail and their structural, physical, thermodynamic and spectroscopic properties considered. Chemical properties of alkali metal uranates(VI), including various methods for their reduction, are also reported. Errors in the current theoretical treatment of uranate(VI) spectra are identified and the need to develop routes for the preparation of single crystals is stressed.

  14. Reaction velocity of sodium hydration in humid air and sodium carbonation in humid carbon dioxide atmosphere. Fundamental study on sodium carbonate process in FBR bulk sodium coolant disposal technology

    International Nuclear Information System (INIS)

    Tadokoro, Yutaka; Yoshida, Eiichi

    1999-11-01

    A sodium carbonate processing method, which changes sodium to sodium carbonate and/or sodium bicarbonate by humid carbon dioxide, has been examined and about to be applied to large test loops dismantling. However, that the basic data regarding the progress of the reaction is insufficient on the other hand, is a present condition. The present report therefore aims at presenting basic data regarding the reaction velocity of sodium hydration in humid air and sodium carbonation in humid carbon dioxide atmosphere, and observing the reaction progress, for the application to large test loops dismantling. The test result is summarized as follows. (1) Although the reaction velocity of sodium varied with sodium specimen sizes and velocity measurement methods, the reaction velocity of sodium hydration was in about 0.16 ∼ 0.34 mmh -1 (0.016 ∼ 0.033g cm -2 h -1 , 6.8x10 -4 ∼ 1.4x10 -3 mol cm -2 h -1 ) and that of sodium carbonation was in about 0.16 ∼ 0.27mmh -1 (0.016 ∼ 0.023g cm -2 h -1 , 6.8x10 -4 ∼ 1.1x10 -3 mol cm -2 h -1 ) (26 ∼ 31degC, RH 100%). (2) The reaction velocity of sodium in carbon dioxide atmosphere was greatly affected by vapor partial pressure (absolutely humidity). And the velocity was estimated in 0.08 ∼ 0.12mmh -1 (0.008 ∼ 0.012g cm -2 h -1 , 3.4x10 -4 ∼ 5.2x10 -4 mol cm -2 h -1 ) in the carbon dioxide atmosphere, whose temperature of 20degC and relative humidity of 80% are assumed real sodium carbonate process condition. (3) By the X-ray diffraction method, NaOH was found in humid air reaction product. Na 2 CO 3 , NaHCO 3 were found in carbon dioxide atmosphere reaction product. It was considered that Sodium changes to NaOH, and subsequently to NaHCO 3 through Na 2 CO 3 . (4) For the application to large test loops dismantling, it is considered possible to change sodium to a target amount of sodium carbonate (or sodium bicarbonate) by setting up gas supply quantity and also processing time appropriately according to the surface area

  15. Reaction of atomic oxygen with alkanes. Regioselective alcohol formation on γ-radiolysis of liquid carbon dioxide solutions of alkanes

    International Nuclear Information System (INIS)

    Hori, A.; Takamuku, S.; Sakurai, H.

    1977-01-01

    Gamma-radiolysis of liquid carbon dioxide in the presence of cyclohexane, methylcyclohexane, and cis- or trans-decalin has been studied at 0 0 C. The main products were corresponding alcohols and carbonyl compounds. The oxidizing species from carbon dioxide apparently shows selective attack on C--H bonds of alkane in the order tertiary greater than secondary greater than primary. The observed tendency could be rationalized in terms of the reaction of ground state triplet oxygen atoms, O( 3 P), with alkane in liquid carbon dioxide. In the case of cis- and trans-decalin, highly configurational retention of decalol-9 was observed. The formation of a dimer of alkane was negligibly small. The rapid recombination of radical pairs initially formed by the reaction of O( 3 P) atoms with alkane in a solvent cage is proposed. In addition, the production of cyclohexanone from cyclohexanol is described

  16. Near-infrared light controlled photocatalytic activity of carbon quantum dots for highly selective oxidation reaction

    Science.gov (United States)

    Li, Haitao; Liu, Ruihua; Lian, Suoyuan; Liu, Yang; Huang, Hui; Kang, Zhenhui

    2013-03-01

    Selective oxidation of alcohols is a fundamental and significant transformation for the large-scale production of fine chemicals, UV and visible light driven photocatalytic systems for alcohol oxidation have been developed, however, the long wavelength near infrared (NIR) and infrared (IR) light have not yet fully utilized by the present photocatalytic systems. Herein, we reported carbon quantum dots (CQDs) can function as an effective near infrared (NIR) light driven photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde. Based on the NIR light driven photo-induced electron transfer property and its photocatalytic activity for H2O2 decomposition, this metal-free catalyst could realize the transformation from benzyl alcohol to benzaldehyde with high selectivity (100%) and conversion (92%) under NIR light irradiation. HO&z.rad; is the main active oxygen specie in benzyl alcohol selective oxidative reaction confirmed by terephthalic acid photoluminescence probing assay (TA-PL), selecting toluene as the substrate. Such metal-free photocatalytic system also selectively converts other alcohol substrates to their corresponding aldehydes with high conversion, demonstrating a potential application of accessing traditional alcohol oxidation chemistry.Selective oxidation of alcohols is a fundamental and significant transformation for the large-scale production of fine chemicals, UV and visible light driven photocatalytic systems for alcohol oxidation have been developed, however, the long wavelength near infrared (NIR) and infrared (IR) light have not yet fully utilized by the present photocatalytic systems. Herein, we reported carbon quantum dots (CQDs) can function as an effective near infrared (NIR) light driven photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde. Based on the NIR light driven photo-induced electron transfer property and its photocatalytic activity for H2O2 decomposition, this metal-free catalyst could realize

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

    NARCIS (Netherlands)

    Ma, Y.

    2013-01-01

    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

  18. An alkali ion source based on graphite intercalation compounds for ion mobility spectrometry

    International Nuclear Information System (INIS)

    Tabrizchi, Mahmoud; Hosseini, Zahra S

    2008-01-01

    A variety of alkali cation emitters were developed as the ion source for ion mobility spectrometry. The cation emitters were constructed based on alkali ion graphite intercalation compounds (GICs). The compounds were prepared by fusing alkali salts with ground graphite. In order to produce alkali ions, the compounds were loaded on a filament and heated to red. Reactant ions of the form alk + ions were observed for the alkali salts NaCl, KCl.LiCl, CsCl and SrCl. In addition to Na + ions, K + ions were observed at the beginning of thermionic emission from Na-GIC. This is due to the low ionization potential of potassium that exists in trace amounts in sodium salts. In addition to the potassium ion, Na + was observed in the case of LiCl salt. The Na + and K + peaks originating from impurities totally disappeared after about 40 min. However, the thermionic emission of the main ion of the corresponding salt lasted for several days. No negative ions were observed upon reversing the drift field. Selected organic compounds (methyl isobutyl ketone, dimethyl sulfoxide, acetone and tetrahydrofuran) were also ionized via alkali cation attachment reaction. Distinct ion mobility patterns were observed for different substances using one type of alkali reactant ion. However, the ion mobility pattern for a given substance changed when a different alkali reactant ion was used. Ammonia and amines were not ionized when this source was used

  19. Reaction Coordinate, Free Energy, and Rate of Intramolecular Proton Transfer in Human Carbonic Anhydrase II.

    Science.gov (United States)

    Paul, Sanjib; Paul, Tanmoy Kumar; Taraphder, Srabani

    2018-03-22

    The role of structure and dynamics of an enzyme has been investigated at three different stages of its function including the chemical event it catalyzes. A one-pot computational method has been designed for each of these stages on the basis of classical and/or quantum mechanical-molecular mechanical molecular dynamics and transition path sampling simulations. For a pair of initial and final states A and B separated by a high free-energy barrier, using a two-stage selection process, several collective variables (CVs) are identified that can delineate A and B. However, these CVs are found to exhibit strong cross-coupling over the transition paths. A set of mutually orthogonal order parameters is then derived from these CVs and an optimal reaction coordinate, r, determined applying half-trajectory likelihood maximization along with a Bayesian information criterion. The transition paths are also used to project the multidimensional free energy surface and barrier crossing dynamics along r. The proposed scheme has been applied to the rate-determining intramolecular proton transfer reaction of the well-known enzyme human carbonic anhydrase II. The potential of mean force, F( r), in the absence of the chemical step is found to reproduce earlier results on the equilibrium population of two side-chain orientations of key residue His-64. Estimation of rate constants, k, from mean first passage times for the three different stages of catalysis shows that the rate-determining step of intramolecular proton transfer occurs with k ≃ 1.0 × 10 6 s -1 , in close agreement with known experimental results.

  20. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

    Science.gov (United States)

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1993-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  1. Biogenic Methane Generation Potential in the Eastern Nankai Trough, Japan: Effect of Reaction Temperature and Total Organic Carbon

    Science.gov (United States)

    Aung, T. T.; Fujii, T.; Amo, M.; Suzuki, K.

    2017-12-01

    Understanding potential of methane flux from the Pleistocene fore-arc basin filled turbiditic sedimentary formation along the eastern Nankai Trough is important in the quantitative assessment of gas hydrate resources. We considered generated methane could exist in sedimentary basin in the forms of three major components, and those are methane in methane hydrate, free gas and methane dissolved in water. Generation of biomethane strongly depends on microbe activity and microbes in turn survive in diverse range of temperature, salinity and pH. This study aims to understand effect of reaction temperature and total organic carbon on generation of biomethane and its components. Biomarker analysis and cultural experiment results of the core samples from the eastern Nankai Trough reveal that methane generation rate gets peak at various temperature ranging12.5°to 35°. Simulation study of biomethane generation was made using commercial basin scale simulator, PetroMod, with different reaction temperature and total organic carbon to predict how these effect on generation of biomethane. Reaction model is set by Gaussian distribution with constant hydrogen index and standard deviation of 1. Series of simulation cases with peak reaction temperature ranging 12.5°to 35° and total organic carbon of 0.6% to 3% were conducted and analyzed. Simulation results show that linear decrease in generation potential while increasing reaction temperature. But decreasing amount becomes larger in the model with higher total organic carbon. At higher reaction temperatures, >30°, extremely low generation potential was found. This is due to the fact that the source formation modeled is less than 1 km in thickness and most of formation do not reach temperature more than 30°. In terms of the components, methane in methane hydrate and free methane increase with increasing TOC. Drastic increase in free methane was observed in the model with 3% of TOC. Methane amount dissolved in water shows almost

  2. Method of making alkali metal hydrides

    Science.gov (United States)

    Pecharsky, Vitalij K.; Gupta, Shalabh; Pruski, Marek; Hlova, Ihor; Castle, Andra

    2017-05-30

    A method is provided for making alkali metal hydrides by mechanochemically reacting alkali metal and hydrogen gas under mild temperature (e.g room temperature) and hydrogen pressure conditions without the need for catalyst, solvent, and intentional heating or cooling.

  3. Carbonates in leaching reactions in context of {sup 14}C dating

    Energy Technology Data Exchange (ETDEWEB)

    Michalska, Danuta, E-mail: danamich@amu.edu.pl [Institute of Geology, Faculty of Geographical and Geological Sciences, Adam Mickiewicz University, ul. Makow Polnych 16, 61-606 Poznan (Poland); Czernik, Justyna, E-mail: justyna.czernik@gmail.com [Poznań Radiocarbon Laboratory, ul. Rubież 46, 61-612 Poznań (Poland)

    2015-10-15

    Lime mortars as a mixture of binder and aggregate may contain carbon of various origins. If the mortars are made of totally burnt lime, radiocarbon dating of binder yields the real age of building construction. The presence of carbonaceous aggregate has a significant influence on the {sup 14}C measurements results and depending on the type of aggregate and fraction they may cause overaging. Another problem, especially in case of hydraulic mortars that continue to be chemically active for a very long time, is the recrystallization usually connected with rejuvenation of the results but also, depending on local geological structures, with so called reservoir effect yielding apparent ages. An attempt in separating the binder from other carbonaceous components successfully was made for samples from Israel by Nawrocka-Michalska et al. (2007). The same preparation procedure, after taking into account the petrographic composition, was used for samples coming from Poland, Nawrocka et al. (2009). To verify the procedure used previously for non-hydraulic samples determination an experimental tests on carbonaceous mortars with crushed bricks from Novae in Bulgaria were made. Additionally, to identify different carbonaceous structures and their morphology, a cathodoluminescence and scanning electron microscope with electron dispersive spectrometer were applied. The crushed bricks and brick dust used in mortars production process have been interpreted as an alternative use to other pozzolanic materials. The reaction between lime and pozzolanic additives take place easily and affects the rate and course of carbonates decomposition in orthophosphric acid, during the samples pretreatment for dating. The composition of the Bulgarian samples together with influence of climate conditions on mortar carbonates do not allow for making straightforward conclusions in chronology context, but gives some new guidelines in terms of hydraulic mortars application for dating. This work has mainly

  4. Mechanical filter for alkali atoms

    CERN Document Server

    Toporkov, D K

    2000-01-01

    A device for separating gases of different mass is discussed. Such a device could be used in a laser-driven spin exchange source of polarized hydrogen atoms to reduce the contamination of alkali atoms. A Monte Carlo simulation has shown that the suggested apparatus based on a commercial turbo pump could reduce by a factor of 10-15 the concentration of the alkali-metal atoms in the hydrogen flow from a laser driven polarized source. This would greatly enhance the effective polarization in hydrogen targets.

  5. Self-assembled dopamine nanolayers wrapped carbon nanotubes as carbon-carbon bi-functional nanocatalyst for highly efficient oxygen reduction reaction and antiviral drug monitoring

    Science.gov (United States)

    Khalafallah, Diab; Akhtar, Naeem; Alothman, Othman Y.; Fouad, H.; Abdelrazek khalil, Khalil

    2017-09-01

    Oxygen reduction reaction (ORR) catalysts are the heart of eco-friendly energy resources particularly low temperature fuel cells. Although valuable efforts have been devoted to synthesize high performance catalysts for ORR, considerable challenges are extremely desirable in the development of energy technologies. Herein, we report a simple self-polymerization method to build a thin film of dopamine along the tubular nanostructures of multi-walled carbon nanotubes (CNT) in a weak alkaline solution. The dopamine@CNT hybrid (denoted as DA@CNT) reveals an enhanced electrocatalytic activity towards ORR with highly positive onset potential and cathodic current as a result of their outstanding features of longitudinal mesoporous structure, high surface area, and ornamentation of DA layers with nitrogen moieties, which enable fast electron transport and fully exposed electroactive sites. Impressively, the as-obtained hybrid afford remarkable electrochemical durability for prolonged test time of 60,000 s compared to benchmark Pt/C (20 wt%) catalyst. Furthermore, the developed DA@CNT electrode was successfully applied to access the quality of antiviral drug named Valacyclovir (VCR). The DA@CNT electrode shows enhanced sensing performance in terms of large linear range (3-75 nM), low limit of detection (2.55 nM) than CNT based electrode, indicating the effectiveness of the DA coating. Interestingly, the synergetic effect of nanostructured DA and CNT can significantly boost the electronic configuration and exposure level of active species for ORR and biomolecule recognition. Therefore, the existing carbon-based porous electrocatalyst may find numerous translational applications as attractive alternative to noble metals in polymer electrolyte membrane fuel cells and quality control assessment of pharmaceutical and therapeutic drugs.

  6. Hydrothermal chemistry, structures, and luminescence studies of alkali hafnium fluorides.

    Science.gov (United States)

    Underwood, Christopher C; McMillen, Colin D; Chen, Hongyu; Anker, Jeffery N; Kolis, Joseph W

    2013-01-07

    This paper describes the hydrothermal chemistry of alkali hafnium fluorides, including the synthesis and structural characterization of five new alkali hafnium fluorides. Two ternary alkali hafnium fluorides are described: Li(2)HfF(6) in space group P31m with a = 4.9748(7) Å and c = 4.6449(9) Å and Na(5)Hf(2)F(13) in space group C2/m with a = 11.627(2) Å, b = 5.5159(11) Å, and c = 8.4317(17) Å. Three new alkali hafnium oxyfluorides are also described: two fluoroelpasolites, K(3)HfOF(5) and (NH(4))(3)HfOF(5), in space group Fm3m with a = 8.9766(10) and 9.4144(11) Å, respectively, and K(2)Hf(3)OF(12) in space group R3m with a = 7.6486(11) Å and c = 28.802(6) Å. Infrared (IR) spectra were obtained for the title solids to confirm the structure solutions. Comparison of these materials was made based on their structures and synthesis conditions. The formation of these species in hydrothermal fluids appears to be dependent upon both the concentration of the alkali fluoride mineralizer solution and the reaction temperature. Both X-ray and visible fluorescence studies were conducted on compounds synthesized in this study and showed that fluorescence was affected by a variety of factors, such as alkali metal size, the presence/absence of oxygen in the compound, and the coordination environment of Hf(4+).

  7. Alkali-resistant bacteria in root canal systems.

    Science.gov (United States)

    Nakajo, K; Nakazawa, F; Iwaku, M; Hoshino, E

    2004-12-01

    The aim of this study was to isolate and identify alkali-resistant bacteria from the dentin of infected root canals. Bacteria from homogenized dentin powder made up from infected root canal walls from human teeth were cultured on buffer-enriched Brain Heart Infusion agar supplemented with 4% sheep blood (BHI-blood agar), adjusted to pH 7.0, 9.0 or 10.0. Incubation took place for 7 days at 37 degrees C in an anaerobic glove box. Bacterial strains selected according to colony and morphology were subcultured in buffer-enriched BHI broth adjusted to pH 9.0, 10.0 or 11.0 to confirm their growth as alkali-resistant bacteria. Polymerase chain reaction amplification using specific primer sets and 16S rDNA sequence analysis was performed for identification of alkali-resistant isolates. In the present study, 37 teeth extracted from 37 patients were used for preparation of the dentin powder samples. Bacteria were detected in 25 samples when standard BHI-blood agars (pH 7.0) were used. Of these, 29 strains from 15 samples were alkali resistant, 25 strains growing at pH 9.0 and 4 at pH 10.0. The alkali-resistant strains included Enterococcus faecium (10 strains) and Enterococcus faecalis (2 strains), Enterobacter cancerogenus (1 strains), Fusobacterium nucleatum (1 strains), Klebsiella ornithinolytica (2 strains), Lactobacillus rhamnosus (2 strains), Streptococcus anginosus (2 strains), Streptococcus constellatus (3 strains), and Streptococcus mitis (2 strains). Three strains were also identified as bacteria of genus Firmicutes or Staphylococcus at the genus level. The present study showed that many bacterial species in infected root canal dentin were alkali-resistant at pH 9.0 and/or pH 10.0, and belonged mainly to the genus Enterococcus.

  8. Electric transport properties of alkali polymethacrylates in alkali bromide solutions

    NARCIS (Netherlands)

    Drift, W.P.J.T. van der; Overbeek, J.Th.G.

    Electric mobilities of polyions, bromide ions, and alkali ions have been determined in solutions of Li, Na, and K salts of polymethacrylic acid (PMA) in aqueous solutions of the corresponding bromide of concentrations varying from 0.001 to 0.1 M. The Hittorf method was used for the determination of

  9. ATOMIC-LEVEL MODELING OF CO2 DISPOSAL AS A CARBONATE MINERAL: A SYNERGETIC APPROACH TO OPTIMIZING REACTION PROCESS DESIGN

    Energy Technology Data Exchange (ETDEWEB)

    A.V.G. Chizmeshya; M.J. McKelvy; J.B. Adams

    2001-11-01

    Fossil fuels, especially coal, can support the energy demands of the world for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Permanent and safe methods for CO{sub 2} capture and disposal/storage need to be developed. Mineralization of stationary-source CO{sub 2} emissions as carbonates can provide such safe capture and long-term sequestration. Mg-rich lamellar hydroxide mineral carbonation is a leading process candidate, which generates the stable naturally occurring mineral magnesite (MgCO{sub 3}) and water. Key to process cost and viability are the carbonation reaction rate and its degree of completion. This process, which involves simultaneous dehydroxylation and carbonation is very promising, but far from optimized. In order to optimize the dehydroxylation/carbonation process, an atomic-level understanding of the mechanisms involved is needed. In this investigation Mg(OH){sub 2} was selected as a model Mg-rich lamellar hydrocide carbonation feedstock material due to its chemical and structural simplicity. Since Mg(OH){sub 2} dehydroxylation is intimately associated with the carbonation process, its mechanisms are also of direct interest in understanding and optimizing the process. The aim of the current innovative concepts project is to develop a specialized advanced computational methodology to complement the ongoing experimental inquiry of the atomic level processes involved in CO{sub 2} mineral sequestration. The ultimate goal is to integrate the insights provided by detailed predictive simulations with the data obtained from optical microscopy, FESEM, ion beam analysis, SIMS, TGA, Raman, XRD, and C and H elemental analysis. The modeling studies are specifically designed to enhance the synergism with, and complement the analysis of, existing mineral-CO{sub 2} reaction process studies being carried out under DOE UCR Grant DE-FG2698-FT40112. Direct contact between the simulations and the experimental

  10. Silver nanowire catalysts on carbon nanotubes-incorporated bacterial cellulose membrane electrodes for oxygen reduction reaction.

    Science.gov (United States)

    Kim, Bona; Choi, Youngeun; Cho, Se Youn; Yun, Young Soo; Jin, Hyoung-Joon

    2013-11-01

    Silver nanowires have unique electrical, thermal and optical properties, which support their potential application in numerous fields including catalysis, electronics, optoelectronics, sensing, and surface-enhanced spectroscopy. Especially, their application such as catalysts for alkaline fuel cells (AFCs) have attracted much interest because of their superior electrical conductivity over that of any metal and their lower cost compared to Pt. In this study, multiwalled carbon nanotubes (MWCNTs)-incorporated bacterial cellulose (BC) membrane electrode with silver nanowire catalyst was prepared. First, acid-treated MWCNTs were incorporated into BC membranes and then freeze-dried after solvent exchange to tert-butanol in order to maintain the 3D-network macroporous structure. Second, silver nanowires synthesized by polyol process were introduced onto the surface of the MWCNTs-incorporated BC membrane through easy vacuum filtration. Finally, thermal treatment was carried out to confirm the effect of the PVP on the silver nanowire catalysts toward oxygen reduction reaction. The electrode with thermally treated silver nanowire had great electrocatalytic activity compared with non-treated one. These results suggest that the MWCNTs-incorporated BC electrode with silver nanowire catalysts after thermal treatment could be potentially used in cathodes of AFCs.

  11. Edges of graphene and carbon nanotubes with high catalytic performance for the oxygen reduction reaction.

    Science.gov (United States)

    Xu, Zhanwei; Fan, Xiaoli; Li, Hejun; Fu, Hao; Lau, Woon Ming; Zhao, Xueni

    2017-08-09

    We invented a practical and simple wet-grinding method to break conventional graphene sheets and CNTs for the production of new graphene/CNTs with adequate edge density (about 25 000 atoms per graphene-fragment of about 1 μm 2 in size) and no detectable changes in intrinsic defects, extrinsic impurities, and even surface-area. Measurements using the standard cyclic voltammetry, rotating disk electrode and rotating ring-disk electrode techniques all confirm that such mildly fragmented graphene, as well as carbon-nanotubes treated similarly using this wet-grinding method, can facilitate the fast 4-electron oxygen reduction reaction (ORR) pathway. Our first-principles computational studies of the ORR on graphene, as well as the relevant known data in the literature, support an intriguing proposition that the ORR can be speeded up simply by increasing the edge-density of graphene. The adsorption of O 2 involving both oxygen atoms, which causes O-O elongation, is best facilitated at the edge of graphene, facilitating a multi-step 4-electron ORR process.

  12. Long term stabilization of reaction center protein photochemistry by carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Magyar, Melinda; Hajdu, Kata; Szabo, Tibor; Nagy, Laszlo [Department of Medical Physics and Informatics, University of Szeged, 6720 Szeged (Hungary); Hernadi, Klara [Department of Applied and Environmental Chemistry, University of Szeged, 6720 Szeged (Hungary); Dombi, Andras [Institute of Material Sciences and Engineering, University of Szeged, 6701 Szeged (Hungary); Horvath, Endre; Magrez, Arnaud; Forro, Laszlo [Institute of Physics of Complex Matter, Ecole Polytechnique Federale de Lausanne, 1015 Lausanne (Switzerland)

    2011-11-15

    The long term stability and the redox interaction between single walled carbon nanotubes (SWNTs) and photosynthetic reaction center proteins (RCs) purified from purple bacterium Rhodobacter sphaeroides R-26 in the SWNT/RC complex has been investigated. The binding of SWNT to RC results in an accumulation of positive (the oxidized primary electron donor, P{sup +}) and negative (semiquinone forms, Q{sup -}{sub A} and Q{sup -}{sub B}, the reduced primary and secondary quinones, respectively) charges followed by slow reorganization of the protein structure after excitation. The photochemical activity of the SWNT/RC complexes remains stable for several weeks even in dried form. In the absence of SWNT the secondary quinone activity decays quickly as a function of time after drying the RC onto a glass surface. Polarography measurements substantiate the idea that there is an electronic interaction between the RCs and SWNTs after light excitation, which was suggested earlier by optical measurements. The special electronic properties of the SWNT/protein complexes open the possibility for several applications, e.g., in microelectronics, analytics, or energy conversion and storage. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. High Oxygen Reduction Reaction Performances of Cathode Materials Combining Polyoxometalates, Coordination Complexes, and Carboneous Supports.

    Science.gov (United States)

    Zhang, Shuangshuang; Oms, Olivier; Hao, Long; Liu, Rongji; Wang, Meng; Zhang, Yaqin; He, Hong-Yan; Dolbecq, Anne; Marrot, Jérôme; Keita, Bineta; Zhi, Linjie; Mialane, Pierre; Li, Bin; Zhang, Guangjin

    2017-11-08

    A series of carbonaceous-supported precious-metal-free polyoxometalate (POM)-based composites which can be easily synthesized on a large scale was shown to act as efficient cathode materials for the oxygen reduction reaction (ORR) in neutral or basic media via a four-electron mechanism with high durability. Moreover, exploiting the versatility of the considered system, its activity was optimized by the judicious choice of the 3d metals incorporated in the {(PW 9 ) 2 M 7 } (M = Co, Ni) POM core, the POM counterions and the support (thermalized triazine-based frameworks (TTFs), fluorine-doped TTF (TTF-F), reduced graphene oxide, or carbon Vulcan XC-72. In particular, for {(PW 9 ) 2 Ni 7 }/{Cu(ethylenediamine) 2 }/TTF-F, the overpotential required to drive the ORR compared well with those of Pt/C. This outstanding ORR electrocatalytic activity is linked with two synergistic effects due to the binary combination of the Cu and Ni centers and the strong interaction between the POM molecules and the porous and highly conducting TTF-F framework. To our knowledge, {(PW 9 ) 2 Ni 7 }/{Cu(ethylenediamine) 2 }/TTF-F represents the first example of POM-based noble-metal-free ORR electrocatalyst possessing both comparable ORR electrocatalytic activity and much higher stability than that of Pt/C in neutral medium.

  14. Effect of one step KOH activation and CaO modified carbon in transesterification reaction

    Science.gov (United States)

    Yacob, Abd Rahim; Zaki, Muhammad Azam Muhammad

    2017-11-01

    In this work, one step activation was introduced using potassium hydroxide (KOH) and calcium oxide (CaO) modified palm kernel shells. Various concentration of calcium oxide was used as catalyst while maintaining the same concentration of potassium hydroxide to activate and impregnate the palm kernel shell before calcined at 500°C for 5 hours. All the prepared samples were characterized using Fourier Transform Infrared (FTIR) and Field Emission Scanning Electron Microscope (FESEM). FTIR analysis of raw palm kernel shell showed the presence of various functional groups. However, after activation, most of the functional groups were eliminated. The basic strength of the prepared samples were determined using back titration method. The samples were then used as base heterogeneous catalyst for the transesterification reaction of rice bran oil with methanol. Analysis of the products were performed using Gas Chromatography Flame Ionization Detector (GC-FID) to calculate the percentage conversion of the biodiesel products. This study shows, as the percentage of one step activation potassium and calcium oxide doped carbon increases thus, the basic strength also increases followed by the increase in biodiesel production. Optimization study shows that the optimum biodiesel production was at 8 wt% catalyst loading, 9:1 methanol: oil molar ratio at 65°C and 6 hours which gives a conversion up to 95%.

  15. Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

    Science.gov (United States)

    Joshi, Ashok V [Salt Lake City, UT; Balagopal, Shekar [Sandy, UT; Pendelton, Justin [Salt Lake City, UT

    2011-12-13

    Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

  16. Construction of thermionic alkali-ion sources

    International Nuclear Information System (INIS)

    Ul Haq, F.

    1986-01-01

    A simple technique is described by which singly charged alkali ions of K, Na, Li, Rb and Cs are produced by heating ultra-pure chemical salts of different alkali metals on tungsten filaments without employing a temperature measuring device. The character of alkali-ion currents at different heating powers and the remarkably constant ion emission current for prolonged periods are discussed. (author)

  17. Alkali binding in hydrated Portland cement paste

    NARCIS (Netherlands)

    Chen, Wei; Brouwers, Jos

    2010-01-01

    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. Structural evolution and reaction mechanism of lithium nickelate (LiNiO2 during the carbonation reaction

    Directory of Open Access Journals (Sweden)

    Daniela González-Varela

    2018-03-01

    Full Text Available Lithium nickelate (LiNiO2 was synthesized using the lithium excess method, and then characterized by X-ray diffraction, scanning electron microscopy and N2 adsorption-desorption. Finally, differential thermal and thermogravimetric analyses were performed in CO2 presence, at high temperatures. Results show that LiNiO2 is able to react with CO2 through a complex structural evolution process, where lithium atoms are released to produce Li2CO3, while some nickel atoms are rearranged on different Li1-xNi1+xO2 crystalline phases. LiNiO2-CO2 reaction kinetic parameters were determined assuming a first-order reaction, where kinetic constants tended to increase as a function of temperature. However, kinetic constant values did not follow a linear trend. This atypical behavior was attributed to LiNiO2 sintering and crystalline evolution performed as a function of temperature.

  19. Heavy ion irradiation of glasses: enhanced diffusion and preferential sputtering of alkali elements

    International Nuclear Information System (INIS)

    Battaglin, G.; Boscoletto, A.; Della Mea, G.; De Marchi, G.; Miotello, A.; Tiveron, B.

    1986-01-01

    Soda-lime glasses have been irradiated by using different ions (H,N,O,Ne,Ar,Kr) in 20-300 keV energy range. The observed modifications in the alkali depth distribution have been analyzed on the basis of a phenomenological model, which takes into account for an enhanced diffusion and a surface preferential sputtering. A correlation between the alkali sputtering cross-section and the electronic stopping power regimes of incident particles has been determined. The alkali profiles, before and after irradiation, have been determined by resonant nuclear reactions. (author)

  20. Accelerated carbonation using municipal solid waste incinerator bottom ash and cold-rolling wastewater: Performance evaluation and reaction kinetics.

    Science.gov (United States)

    Chang, E-E; Pan, Shu-Yuan; Yang, Liuhanzi; Chen, Yi-Hung; Kim, Hyunook; Chiang, Pen-Chi

    2015-09-01

    Accelerated carbonation of alkaline wastes including municipal solid waste incinerator bottom ash (MSWI-BA) and the cold-rolling wastewater (CRW) was investigated for carbon dioxide (CO2) fixation under different operating conditions, i.e., reaction time, CO2 concentration, liquid-to-solid ratio, particle size, and CO2 flow rate. The MSWI-BA before and after carbonation process were analyzed by the thermogravimetry and differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy. The MSWI-BA exhibits a high carbonation conversion of 90.7%, corresponding to a CO2 fixation capacity of 102g perkg of ash. Meanwhile, the carbonation kinetics was evaluated by the shrinking core model. In addition, the effect of different operating parameters on carbonation conversion of MSWI-BA was statistically evaluated by response surface methodology (RSM) using experimental data to predict the maximum carbonation conversion. Furthermore, the amount of CO2 reduction and energy consumption for operating the proposed process in refuse incinerator were estimated. Capsule abstract: CO2 fixation process by alkaline wastes including bottom ash and cold-rolling wastewater was developed, which should be a viable method due to high conversion. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. Exciton emissions in alkali cyanides

    International Nuclear Information System (INIS)

    Weid, J.P. von der.

    1979-10-01

    The emissions of Alkali Cyanides X irradiated at low temperature were measured. In addition to the molecular (Frenkel Type) exciton emissions, another emitting centre was found and tentatively assigned to a charge transfer self trapped exciton. The nature of the molecular exciton emitting state is discussed. (Author) [pt

  2. Highly Efficient Electrocatalysts for Oxygen Reduction Reaction Based on 1D Ternary Doped Porous Carbons Derived from Carbon Nanotube Directed Conjugated Microporous Polymers

    KAUST Repository

    He, Yafei

    2016-10-11

    © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.One-dimensional (1D) porous materials have shown great potential for gas storage and separation, sensing, energy storage, and conversion. However, the controlled approach for preparation of 1D porous materials, especially porous organic materials, still remains a great challenge due to the poor dispersibility and solution processability of the porous materials. Here, carbon nanotube (CNT) templated 1D conjugated microporous polymers (CMPs) are prepared using a layer-by-layer method. As-prepared CMPs possess high specific surface areas of up to 623 m2 g-1 and exhibit strong electronic interactions between p-type CMPs and n-type CNTs. The CMPs are used as precursors to produce heteroatom-doped 1D porous carbons through direct pyrolysis. As-produced ternary heteroatom-doped (B/N/S) 1D porous carbons possess high specific surface areas of up to 750 m2 g-1, hierarchical porous structures, and excellent electrochemical-catalytic performance for oxygen reduction reaction. Both of the diffusion-limited current density (4.4 mA cm-2) and electron transfer number (n = 3.8) for three-layered 1D porous carbons are superior to those for random 1D porous carbon. These results demonstrate that layered and core-shell type 1D CMPs and related heteroatom-doped 1D porous carbons can be rationally designed and controlled prepared for high performance energy-related applications.

  3. Grafting methyl acrylic onto carbon fiber via Diels-Alder reaction for excellent mechanical and tribological properties of phenolic composites

    Science.gov (United States)

    Fei, Jie; Duan, Xiao; Luo, Lan; Zhang, Chao; Qi, Ying; Li, Hejun; Feng, Yongqiang; Huang, Jianfeng

    2018-03-01

    Carbon fibers (CFs) were grafted with methyl acrylic via Diels-Alder reaction at the different oil bath temperature effectively creating a carboxyl functionalized surface. The effect of grafting temperature on the surface morphology and functional groups of carbon fibers were investigated by FTIR, Raman spectroscopy, XPS and SEM respectively. The results showed that the optimal grafting temperature was 80 °C, and the relative surface coverage by carboxylic acid groups increased from an initial 5.16% up to 19.30% significantly improved the chemical activity without damaging the skin and core region of the carbon fibers. Mechanical property tests indicated that the shear and tensile strength of the sample with the grafting temperature of 80 °C (CFRP-3) increased obviously by 90.3% and 78.7%, respectively, compared with the pristine carbon fibers reinforced composite. Further, the sample CFRP-3 exhibited higher and more stable friction coefficient and improved wear resistance, while the wear rate decreased 52.7%, from 10.8 × 10-6 to 5.1 × 10-6 mm3/N m. The present work shows that grafting methyl acrylic via Diels-Alder reaction could be a highly efficient and facile method to functionalize carbon fibers for advanced composites.

  4. Electrochemical investigations of Pu(IV)/Pu(III) redox reaction using graphene modified glassy carbon electrodes and a comparison to the performance of SWCNTs modified glassy carbon electrodes

    International Nuclear Information System (INIS)

    Gupta, Ruma; Gamare, Jayashree; Sharma, Manoj K.; Kamat, J.V.

    2016-01-01

    Highlights: • First report of aqueous electrochemistry of Plutonium on graphene modified electrode. • Graphene is best electrocatalytic material for Pu(IV)/Pu(III) redox couple among the reported modifiers viz. reduced graphene oxide (rGO) and SWCNT’s. • The electrochemical reversibility of Pu(IV)/Pu(III) redox couple improves significantly on graphene modified electrode compared to previously reported rGO & SWCNTs modified electrodes • Donnan interaction between plutonium species and graphene surface offers a possibility for designing a highly sensitive sensor for plutonium • Graphene modified electrode shows higher sensitivity for the determination of plutonium compared to glassy carbon and single walled carbon nanotube modified electrode - Abstract: The work reported in this paper demonstrates for the first time that graphene modified glassy carbon electrode (Gr/GC) show remarkable electrocatalysis towards Pu(IV)/Pu(III) redox reaction and the results were compared with that of single-walled carbon nanotubes modified GC (SWCNTs/GC) and glassy carbon (GC) electrodes. Graphene catalyzes the exchange of current of the Pu(IV)/Pu(III) couple by reducing both the anodic and cathodic overpotentials. The Gr/GC electrode shows higher peak currents (i p ) and smaller peak potential separation (ΔE p ) values than the SWCNTs/GC and GC electrodes. The heterogeneous electron transfer rate constants (k s ), charge transfer coefficients (α) and the diffusion coefficients (D) involved in the electrocatalytic redox reaction were determined. Our observations show that graphene is best electrocatalytic material among both the SWCNTs and GC to study Pu(IV)/Pu(III) redox reaction.

  5. Molecular-level Simulations of Chemical Reaction Equilibrium for Nitric Oxide Dimerization Reaction in Disordered Nanoporous Carbons

    Czech Academy of Sciences Publication Activity Database

    Lísal, Martin; Cosoli, P.; Smith, W. R.; Jain, S.K.; Gubbins, K.E.

    2008-01-01

    Roč. 272, 1-2 (2008), s. 18-31 ISSN 0378-3812 R&D Projects: GA ČR GA203/08/0094; GA AV ČR 1ET400720409; GA AV ČR 1ET400720507; GA AV ČR KAN400720701; GA AV ČR IAA400720710 Institutional research plan: CEZ:AV0Z40720504 Keywords : nanoporous carbon * adsorption model * remc Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.699, year: 2008

  6. Behaviour of gaseous alkali compounds in coal gasification; Kaasumaisten alkaliyhdisteiden kaeyttaeytyminen kivihiilien kaasutuksessa

    Energy Technology Data Exchange (ETDEWEB)

    Nykaenen, J. [Imatran Voima Oy, Vantaa (Finland)

    1997-10-01

    In this project the behaviour of alkali compounds emitting from CO{sub 2}/O{sub 2}- and airblown gasification are studied. This research project is closely connected to an EU-project coordinated by the Delft University of Technology (DUT). In that project alkali emissions from a 1.6 MW pilot plant will be measured. The results from those measurements will be compared with the calculations performed in this LIEKKI 2 project. The equilibrium calculations show that the major gaseous alkali compounds emitting from combustion and gasification are chlorides and hydroxides. This applies both to air- and CO{sub 2}/O{sub 2}-blown processes. In all the cases studied the concentration of gaseous alkali compounds is determined mainly by the amount of chlorides. The key parameters, with respect to alkali behaviour, are the temperature of the process and chlorine content of the coal. By cooling the gases down to 600 deg C prior to a ceramic filter the alkali concentration can be kept about at 100 ppbv. In combustion, the addition of calcium carbonate increases the amount of gaseous alkali compounds by decreasing the amount of alkali sulphates. In the case of gasification the importance of limestone is negligible. The difference between air- and CO{sub 2}/O{sub 2}-blown processes, in terms of gaseous alkali emissions, is small. This is because CO{sub 2} concentration of the gas does not have a strong impact on alkali chlorides. Furthermore, the effect of CO{sub 2}/O{sub 2}-ratio of the recirculation process is negligible. (orig.)

  7. Structure peculiarities of mixed alkali silicate glasses

    International Nuclear Information System (INIS)

    Bershtein, V.A.; Gorbachev, V.V.; Egorov, V.

    1980-01-01

    The thermal porperties and structure of alkali and mixed alkali (Li, Na, K) silicate glasses by means of differential scanning calorimetry (DSC), the positron annihilation method, X-ray fluorescence and infrared (300-30 cm -1 ) spectroscopy were studied. Introduction of different alkali cations in glass results in nonadditive change in their electron structure (bond covalence degree growth) and the thermal behaviour. The different manifestations of mixed alkali effect can be explained by the lessening of long distance Coulomb interactions and strengthening the short-range forces in the mixed alkali glasses. (orig.)

  8. Experimental and modeling study of high performance direct carbon solid oxide fuel cell with in situ catalytic steam-carbon gasification reaction

    Science.gov (United States)

    Xu, Haoran; Chen, Bin; Zhang, Houcheng; Tan, Peng; Yang, Guangming; Irvine, John T. S.; Ni, Meng

    2018-04-01

    In this paper, 2D models for direct carbon solid oxide fuel cells (DC-SOFCs) with in situ catalytic steam-carbon gasification reaction are developed. The simulation results are found to be in good agreement with experimental data. The performance of DC-SOFCs with and without catalyst are compared at different operating potential, anode inlet gas flow rate and operating temperature. It is found that adding suitable catalyst can significantly speed up the in situ steam-carbon gasification reaction and improve the performance of DC-SOFC with H2O as gasification agent. The potential of syngas and electricity co-generation from the fuel cell is also evaluated, where the composition of H2 and CO in syngas can be adjusted by controlling the anode inlet gas flow rate. In addition, the performance DC-SOFCs and the percentage of fuel in the outlet gas are both increased with increasing operating temperature. At a reduced temperature (below 800 °C), good performance of DC-SOFC can still be obtained with in-situ catalytic carbon gasification by steam. The results of this study form a solid foundation to understand the important effect of catalyst and related operating conditions on H2O-assisted DC-SOFCs.

  9. Magnetic Carbon Supported Palladium Nanoparticles: An Efficient and Sustainable Catalyst for Hydrogenation Reactions

    Science.gov (United States)

    Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; the catalyst can be used for the hydrogenation of alkenes and reduction of aryl nitro compounds.

  10. Enrichment of semiconducting single-walled carbon nanotubes by carbothermic reaction for use in all-nanotube field effect transistors.

    Science.gov (United States)

    Li, Shisheng; Liu, Chang; Hou, Peng-Xiang; Sun, Dong-Ming; Cheng, Hui-Ming

    2012-11-27

    Selective removal of metallic single-walled carbon nanotubes (SWCNTs) and consequent enrichment of semiconducting SWCNTs were achieved through an efficient carbothermic reaction with a NiO thin film at a relatively low temperature of 350 °C. All-SWCNT field effect transistors (FETs) were fabricated with the aid of a patterned NiO mask, in which the as-grown SWCNTs behaving as source/drain electrodes and the remaining semiconducting SWCNTs that survive in the carbothermic reaction as a channel material. The all-SWCNT FETs demonstrate improved current ON/OFF ratios of ∼10(3).

  11. Applications of the water--gas shift reaction. II. Catalytic exchange of deuterium for hydrogen at saturated carbon

    International Nuclear Information System (INIS)

    Laine, R.M.; Thomas, D.W.; Cary, L.W.; Buttrill, S.E.

    1978-01-01

    Previous studies on the homogeneous catalysis of the water-gas shift reaction by metal complexes of groups 6 and 8 had been carried out using aqueous alcoholic solutions of group 8 metal carbonyl complexes made basic with KOH. Substitution of triethylamine (Et 3 N) for KOH as base and alcohol for solvent led to the discovery that Et 3 N in the presence of D 2 O, CO, and Rh 6 (CO) 16 at 150 0 C undergoes an unusual catalytic exchange of deuterium for hydrogen. A suggested mechanism for this reaction is given and includes activation of hydrogen at a saturated carbon

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

    Directory of Open Access Journals (Sweden)

    Lukáš Kalina

    2016-05-01

    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.

  13. Accelerated carbonation for the treatment of MSWIr: Optimisation and reaction modelling.

    OpenAIRE

    Bertos, M. F.

    2005-01-01

    Moist calcium silicate minerals are known to readily react with carbon dioxide (CO2). The Accelerated Carbonation of hazardous wastes is a controlled accelerated version of the naturally occurring process. The solid mixture is carbonated under a gaseous, CO2 rich environment at slightly positive pressures (3 bar), which promotes rapid stiffening of the non-hydrated product into a structural medium within minutes. In addition, an increased binding of toxic metals occurs as the solid carbonates...

  14. Synthesis and characterization of tetravalent actinide orthophosphates with alkali metals

    International Nuclear Information System (INIS)

    Volkov, Yu.F.; Melkaya, R.F.; Spiryakov, V.I.; Timofeev, G.A.

    1995-01-01

    A series of double phosphates of formula AM 2 (PO 4 ) 3 , where A = Li, Na, K, Rb, Cs; M = U, Np, Pu, is prepared by solid-state reactions. Various polymorphic modifications of AM 2 (PO 4 ) 3 are identified by using X-ray diffraction and IR spectroscopic analyses of the products from stepwise annealing. The crystal structure type, thermal stability of the modifications, and nature of the polymorphic transformations depend on the nature of the actinide and alkali metal

  15. Carbonation of steel slag for CO2 sequestration: Leaching of products and reaction mechanisms

    NARCIS (Netherlands)

    Huijgen, W.J.J.; Comans, R.N.J.

    2006-01-01

    Carbonation of industrial alkaline residues can be used as a CO2 sequestration technology to reduce carbon dioxide emissions. In this study, steel slag samples were carbonated to a varying extent. Leaching experiments and geochemical modeling were used to identify solubility-controlling processes of

  16. Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

    Science.gov (United States)

    Patki, Gauri Dilip

    Hydrogen is a promising energy carrier, for use in fuel cells, engines, and turbines for transportation or mobile applications. Hydrogen is desirable as an energy carrier, because its oxidation by air releases substantial energy (thermally or electrochemically) and produces only water as a product. In contrast, hydrocarbon energy carriers inevitably produce CO2, contributing to global warming. While CO2 capture may prove feasible in large stationary applications, implementing it in transportation and mobile applications is a daunting challenge. Thus a zero-emission energy carrier like hydrogen is especially needed in these cases. Use of H2 as an energy carrier also brings new challenges such as safe handling of compressed hydrogen and implementation of new transport, storage, and delivery processes and infrastructure. With current storage technologies, hydrogen's energy per volume is very low compared to other automobile fuels. High density storage of compressed hydrogen requires combinations of high pressure and/or low temperature that are not very practical. An alternative for storage is use of solid light weight hydrogenous material systems which have long durability, good adsorption properties and high activity. Substantial research has been conducted on carbon materials like activated carbon, carbon nanofibers, and carbon nanotubes due to their high theoretical hydrogen capacities. However, the theoretical values have not been achieved, and hydrogen uptake capacities in these materials are below 10 wt. %. In this thesis we investigated the use of silicon for hydrogen generation. Hydrogen generation via water oxidation of silicon had been ignored due to slow reaction kinetics. We hypothesized that the hydrogen generation rate could be improved by using high surface area silicon nanoparticles. Our laser-pyrolysis-produced nanoparticles showed surprisingly rapid hydrogen generation and high hydrogen yield, exceeding the theoretical maximum of two moles of H2 per

  17. Boron Doped Multi-walled Carbon Nanotubes as Catalysts for Oxygen Reduction Reaction and Oxygen Evolution Reactionin in Alkaline Media

    International Nuclear Information System (INIS)

    Cheng, Yuanhang; Tian, Yayuan; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei

    2014-01-01

    The boron doped multi-walled carbon nanotubes (B-MWCNTs) were synthesized by thermal annealing multi-walled carbon nanotubes (MWCNTs) in the presence of boric acid. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) results revealed that the structure of MWCNTs does not be destroyed during the doping process, and X-ray photoelectron spectroscopy (XPS) analysis demonstrated the boron atoms were successfully doped in the structure of MWCNTs. The electrocatalytic properties of B-MWCNTs are characterized by rotating disk electrode (RDE) methods. The results demonstrated that the B-MWCNTs catalyzed oxygen reduction reaction (ORR) in alkaline media by a 2 + 2 electron pathway and it showed good catalytic activity for oxygen evolution reaction (OER) as well

  18. Femtosecond laser control of chemical reaction of carbon monoxide and hydrogen

    CSIR Research Space (South Africa)

    Du Plessis, A

    2010-09-01

    Full Text Available relative fragmentation ratios for unimolecular dissociation reactions – therefore selectively breaking bonds in a molecule. More interestingly, the same techniques can be used to provide control over chemical reactions involving two or more reactant...

  19. Synthesis of graphitic carbon nitride by reaction of melamine and uric acid

    Energy Technology Data Exchange (ETDEWEB)

    Dante, Roberto C., E-mail: rcdante@yahoo.com [Laboratorio de Tecnologias del Medio Ambiente, Departamento de Ingenieria Agricola y Forestal, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Martin-Ramos, Pablo, E-mail: pablomartinramos@gmail.com [Laboratorio de Tecnologias del Medio Ambiente, Departamento de Ingenieria Agricola y Forestal, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Correa-Guimaraes, Adriana, E-mail: acg@iaf.uva.es [Laboratorio de Tecnologias del Medio Ambiente, Departamento de Ingenieria Agricola y Forestal, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Martin-Gil, Jesus, E-mail: jesusmartingil@gmail.com [Laboratorio de Tecnologias del Medio Ambiente, Departamento de Ingenieria Agricola y Forestal, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain)

    2011-11-01

    Highlights: {yields} Graphitic carbon nitrides by CVD of melamine and uric acid on alumina. {yields} The building blocks of carbon nitrides are heptazine nuclei. {yields} Composite particles with alumina core and carbon nitride coating. - Abstract: Graphitic carbon nitrides were synthesized starting from melamine and uric acid. Uric acid was chosen because it thermally decomposes, and reacts with melamine by condensation at temperatures in the range of 400-600 deg. C. The reagents were mixed with alumina and subsequently the samples were treated in an oven under nitrogen flux. Alumina favored the deposition of the graphitic carbon nitrides layers on the exposed surface. This method can be assimilated to an in situ chemical vapor deposition (CVD). Infrared (IR) spectra, as well as X-ray diffraction (XRD) patterns, are in accordance with the formation of a graphitic carbon nitride with a structure based on heptazine blocks. These carbon nitrides exhibit poor crystallinity and a nanometric texture, as shown by transmission electron microscopy (TEM) analysis. The thermal degradation of the graphitic carbon nitride occurs through cyano group formation, and involves the bridging tertiary nitrogen and the bonded carbon, which belongs to the heptazine ring, causing the ring opening and the consequent network destruction as inferred by connecting the IR and X-ray photoelectron spectroscopy (XPS) results. This seems to be an easy and promising route to synthesize graphitic carbon nitrides. Our final material is a composite made of an alumina core covered by carbon nitride layers.

  20. Durability of carbon-supported manganese oxide nanoparticles for the oxygen reduction reaction (ORR) in alkaline medium

    Czech Academy of Sciences Publication Activity Database

    Roche, I.; Chainet, E.; Chatenet, M.; Vondrák, Jiří

    2008-01-01

    Roč. 38, č. 9 (2008), s. 1195-1201 ISSN 0021-891X R&D Projects: GA AV ČR KJB4813302; GA ČR GA104/02/0731 Grant - others:CNRS(FR) 18105 Institutional research plan: CEZ:AV0Z40320502 Keywords : oxygen reduction reaction * rotating ring-disc electrode * carbon-supported manganese oxide Subject RIV: CA - Inorganic Chemistry Impact factor: 1.540, year: 2008

  1. The Reduction Reaction of Dissolved Oxygen in Water by Hydrazine over Platinum Catalyst Supported on Activated Carbon Fiber

    Energy Technology Data Exchange (ETDEWEB)

    Park, K.K.; Moon, J.S. [Korea Electric Power Research Institute, Taejon (Korea)

    1999-07-01

    The reduction reaction of dissolved oxygen (DO) by hydrazine was investigated on activated carbon fiber (ACF) and Pt/ACF catalysts using a batch reactor with an external circulating loop. The ACF itself showed catalytic activity and this was further improved by supporting platinum on ACF. The catalytic role platinum is ascribed to its acceleration of hydrazine decomposition, based on electric potential and current measurements as well as the kinetic study. (author). 15 refs., 13 figs.

  2. Using response surface methodology in optimisation of biodiesel production via alkali catalysed transesterification of waste cooking oil

    CSIR Research Space (South Africa)

    Naidoo, R

    2016-03-01

    Full Text Available The report focuses on optimisation of alkali catalysis as a process for producing biodiesel from waste cooking oils. Biodiesel production parameters that were optimised were methanol to oil ratio, catalyst concentration, reaction temperature...

  3. Synthesis of heterobimetallic Ru-Mn complexes and the coupling reactions of epoxides with carbon dioxide catalyzed by these complexes.

    Science.gov (United States)

    Man, Man Lok; Lam, King Chung; Sit, Wing Nga; Ng, Siu Man; Zhou, Zhongyuan; Lin, Zhenyang; Lau, Chak Po

    2006-01-23

    The heterobimetallic complexes [(eta5-C5H5)Ru(CO)(mu-dppm)Mn(CO)4] and [(eta5-C5Me5)Ru(mu-dppm)(mu-CO)2Mn(CO)3] (dppm = bis-diphenylphosphinomethane) have been prepared by reacting the hydridic complexes [(eta5-C5H5)Ru(dppm)H] and [(eta5-C5Me5)Ru(dppm)H], respectively, with the protonic [HMn(CO)5] complex. The bimetallic complexes can also be synthesized through metathetical reactions between [(eta5-C5R5)Ru(dppm)Cl] (R = H or Me) and Li+[Mn(CO)5]-. Although the complexes fail to catalyze the hydrogenation of CO2 to formic acid, they catalyze the coupling reactions of epoxides with carbon dioxide to yield cyclic carbonates. Two possible reaction pathways for the coupling reactions have been proposed. Both routes begin with heterolytic cleavage of the RuMn bond and coordination of an epoxide molecule to the Lewis acidic ruthenium center. In Route I, the Lewis basic manganese center activates the CO2 by forming the metallocarboxylate anion which then ring-opens the epoxide; subsequent ring-closure gives the cyclic carbonate. In Route II, the nucleophilic manganese center ring-opens the ruthenium-attached epoxide to afford an alkoxide intermediate; CO2 insertion into the RuO bond followed by ring-closure yields the product. Density functional calculations at the B3LYP level of theory were carried out to understand the structural and energetic aspects of the two possible reaction pathways. The results of the calculations indicate that Route II is favored over Route I.

  4. Alkali (Li, K and Na) and alkali-earth (Be, Ca and Mg) adatoms on SiC single layer

    Science.gov (United States)

    Baierle, Rogério J.; Rupp, Caroline J.; Anversa, Jonas

    2018-03-01

    First-principles calculations within the density functional theory (DFT) have been addressed to study the energetic stability, and electronic properties of alkali and alkali-earth atoms adsorbed on a silicon carbide (SiC) single layer. We observe that all atoms are most stable (higher binding energy) on the top of a Si atom, which moves out of the plane (in the opposite direction to the adsorbed atom). Alkali atoms adsorbed give raise to two spin unpaired electronic levels inside the band gap leading the SiC single layer to exhibit n-type semiconductor properties. For alkaline atoms adsorbed there is a deep occupied spin paired electronic level inside the band gap. These finding suggest that the adsorption of alkaline and alkali-earth atoms on SiC layer is a powerful feature to functionalize two dimensional SiC structures, which can be used to produce new electronic, magnetic and optical devices as well for hydrogen and oxygen evolution reaction (HER and OER, respectively). Furthermore, we observe that the adsorption of H2 is ruled by dispersive forces (van der Waals interactions) while the O2 molecule is strongly adsorbed on the functionalized system.

  5. Generalized eczematous reaction after fractional carbon dioxide laser therapy for tattoo allergy.

    Science.gov (United States)

    Meesters, Arne A; De Rie, Menno A; Wolkerstorfer, Albert

    2016-12-01

    Allergic tattoo reactions form a therapeutically difficult entity. Treatment with conventional quality-switched lasers does not completely remove the allergenic particles and may lead to generalized hypersensitivity reactions. Recently, ablative fractional laser therapy was introduced as a treatment for allergic tattoo removal. We present two cases of allergic reactions to red tattoo ink treated with 10,600-nm fractional CO 2 laser. At the end of treatment, almost complete removal of red ink accompanied by a significant reduction of symptoms was observed in the first patient, whereas the second patient developed an acute generalized eczematous reaction after five treatments. These findings confirm that ablative fractional laser therapy is capable of significant removal of tattoo ink in an allergic tattoo reaction. However, it implies a risk of generalized hypersensitivity reactions. To our knowledge, this is the first case of a generalized hypersensitivity reaction following treatment of tattoo allergy with the fractional CO 2 laser.

  6. Graphene-oxide-supported CuAl and CoAl layered double hydroxides as enhanced catalysts for carbon-carbon coupling via Ullmann reaction

    Science.gov (United States)

    Ahmed, Nesreen S.; Menzel, Robert; Wang, Yifan; Garcia-Gallastegui, Ainara; Bawaked, Salem M.; Obaid, Abdullah Y.; Basahel, Sulaiman N.; Mokhtar, Mohamed

    2017-02-01

    Two efficient catalyst based on CuAl and CoAl layered double hydroxides (LDHs) supported on graphene oxide (GO) for the carbon-carbon coupling (Classic Ullmann Homocoupling Reaction) are reported. The pure and hybrid materials were synthesised by direct precipitation of the LDH nanoparticles onto GO, followed by a chemical, structural and physical characterisation by electron microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area measurements and X-ray photoelectron spectroscopy (XPS). The GO-supported and unsupported CuAl-LDH and CoAl-LDH hybrids were tested over the Classic Ullman Homocoupling Reaction of iodobenzene. In the current study CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary and two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH.

  7. Method and composition for testing for the presence of an alkali metal

    Science.gov (United States)

    Guon, Jerold

    1981-01-01

    A method and composition for detecting the presence of an alkali metal on the surface of a body such as a metal plate, tank, pipe or the like is provided. The method comprises contacting the surface with a thin film of a liquid composition comprising a light-colored pigment, an acid-base indicator, and a nonionic wetting agent dispersed in a liquid carrier comprising a minor amount of water and a major amount of an organic solvent selected from the group consisting of the lower aliphatic alcohols, ketones and ethers. Any alkali metal present on the surface in elemental form or as an alkali metal hydroxide or alkali metal carbonate will react with the acid-base indicator to produce a contrasting color change in the thin film, which is readily discernible by visual observation or automatic techniques.

  8. Method and composition for testing for the presence of an alkali metal

    International Nuclear Information System (INIS)

    Guon, J.

    1981-01-01

    A method and composition for detecting the presence of an alkali metal on the surface of a body such as a metal plate, tank, pipe or the like is provided. The method comprises contacting the surface with a thin film of a liquid composition comprising a light-colored pigment, an acid-base indicator, and a nonionic wetting agent dispersed in a liquid carrier comprising a minor amount of water and a major amount of an organic solvent selected from the group consisting of the lower aliphatic alcohols, ketones and ethers. Any alkali metal present on the surface in elemental form or as an alkali metal hydroxide or alkali metal carbonate will react with the acid-base indicator to produce a contrasting color change in the thin film, which is readily discernible by visual observation or automatic techniques

  9. The chemistry of subcritical water reactions of a hardwood derived lignin and lignin model compounds with nitrogen, hydrogen, carbon monoxide and carbon dioxide

    Science.gov (United States)

    Hill Bembenic, Meredith A.

    collected solids from the CO reactions appeared to be the most reacted (i.e., the most changed from the unreacted lignin) according to solid state 13C-NMR analysis, and the widest variety of products (methoxy-substituted phenolic compounds) were obtained when using CO according to GC/MS analysis. Therefore, reactions with CO were completed that varied the initial reaction pressure (300, 500 and 800 psi) in order to elucidate the effects of CO pressure. Similar conversion (≈54--58%) and DCM-soluble liquid product yields (≈53--62%) were obtained for the different pressure reactions, but the reactions with an initial pressure of 500 psi had the greatest change in aromaticity from the unreacted lignin. Additional reactions between Organosolv lignin and H2O with CO (initial pressure of 500 psi) were conducted where the reaction time was varied (15, 30 and 60 min.) to determine the effect of reaction time. Longer reaction time (60 min.) appeared to inhibit conversion to low molecular weight compounds (i.e., conversion and DCM-soluble yields were lower at ≈53% and ≈28%, respectively). Solid state 13C-NMR of collected residues also showed that there are losses in carbons representative of both guaiacyl and syringyl components as reaction time increases, which may indicate that methoxy groups are being cleaved or the products are reacting with each other (i.e., repolymerization) to form high molecular weight compounds as reaction time is increased. The role of H2O and the gases during the baseline reactions and the expanded CO reactions is not intuitive based on the results, so reactions with lignin model compounds (i.e., aromatic aldehydes represented by vanillin and syringaldehyde, aromatic ketones represented by acetovanillone and acetosyringone, and aromatic ethers represented by dibenzyl ether and 2-phenethyl phenyl ether) were completed to study this. From these results, the suggested reaction pathway of Organosolv lignin reactions in subcritical H2O with and without

  10. Alkali-activated blast furnace slag-zeolite cements and concretes

    International Nuclear Information System (INIS)

    Rakhimov, R.; Rakhimova, N.

    2012-01-01

    The aim of this work has been the study of alkali-activated slag-zeolite cements and concretes based on them. Various compositions have been tested and some characteristics such as the compressive strength have been measured versus zeolite additions. A table lists the specific surface area and particle size distributions of different cements. The conclusions of the study are the following. First, alkali-activated slag cements and concretes based on them are effective for immobilization of radioactive wastes and the production of building structures, designed for high radiation load. Secondly, zeolite-containing mineral additions are able to increase the immobilization capacity and radiation resistance of alkali-activated blast furnace slag cements and concretes. Thirdly, the efficiency of different zeolite-containing additions - 10% to increase alkali-activated blast furnace slag-zeolite cement strength was established. It is with alkaline components of water-glass, sodium carbonate, sodium sulphate. Fourth, the effective way of introducing zeolite additions in alkali-activated blast furnace slag-zeolite cement is inter-grinding of the slag and addition. Increase in strength of alkali-activated blast furnace slag-zeolite cement stone is 40% higher than that of the stone of a mixture of separately milled components. Fifth, Alkali-activated blast furnace slag-zeolite cements with zeolite-containing additions with a compressive strength of 10.1 to 140 MPa; alkali-activated blast furnace slag-zeolite cements mortars with compressive strength from 35.2 to 97.7 MPa; alkali-activated blast furnace slag-zeolite cements concretes with compressive strength up to 84.5 MPa and frost resistant up to 800 cycles were obtained

  11. Oxygen reduction activity of carbon fibers cathode, and application for current generation from the NAD+ and NADH recycling reaction

    Directory of Open Access Journals (Sweden)

    H. Maeda

    2012-03-01

    Full Text Available Carbon fibers treated at 700 oC for 10 min were found to have O2 reduction activity when being used as a cathode. The special type of partition combined with both cationic and anionic exchange membranes was applied between anode cell and cathode cell in order to use a highly acidic solution such as 0.5 M H2SO4 as an electrolyte of the cathode cell for increasing the efficiency of O2 reduction activity. The current generation from NAD+ and NADH recycling system combined with D-gluconolactone production from 500 mg of D-glucose was performed by applying only carbon fibers for both anode and cathode. The total current volume obtained was 81.4 mAh during the reaction for 10 h, and the current efficiency was 93%. One gram of carbon fibers was pressed with Nafion paste on a piece of carbon paper(area : 50 mm×50mm with heating to prepare the cathode, and this construct was combined with conventional fuel cell. The power density was 3.6 mW/cm2, and the total power volume was calculated to be 90 mW per 1 g of carbon fibers.

  12. Metal-Carbon Hybrid Electrocatalysts Derived from Ion-Exchange Resin Containing Heavy Metals for Efficient Hydrogen Evolution Reaction.

    Science.gov (United States)

    Zhou, Yucheng; Zhou, Weijia; Hou, Dongman; Li, Guoqiang; Wan, Jinquan; Feng, Chunhua; Tang, Zhenghua; Chen, Shaowei

    2016-05-01

    Transition metal-carbon hybrids have been proposed as efficient electrocatalysts for hydrogen evolution reaction (HER) in acidic media. Herein, effective HER electrocatalysts based on metal-carbon composites are prepared by controlled pyrolysis of resin containing a variety of heavy metals. For the first time, Cr2 O3 nanoparticles of 3-6 nm in diameter homogeneously dispersed in the resulting porous carbon framework (Cr-C hybrid) is synthesized as efficient HER electrocatalyst. Electrochemical measurements show that Cr-C hybrids display a high HER activity with an onset potential of -49 mV (vs reversible hydrogen electrode), a Tafel slope of 90 mV dec(-1) , a large catalytic current density of 10 mA cm(-2) at -123 mV, and the prominent electrochemical durability. X-ray photoelectron spectroscopic measurements confirm that electron transfer occurs from Cr2 O3 into carbon, which is consistent with the reported metal@carbon systems. The obtained correlation between metals and HER activities may be exploited as a rational guideline in the design and engineering of HER electrocatalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Highly efficient nonprecious metal catalysts towards oxygen reduction reaction based on three-dimensional porous carbon nanostructures.

    Science.gov (United States)

    Zhu, Chengzhou; Li, He; Fu, Shaofang; Du, Dan; Lin, Yuehe

    2016-02-07

    Developing a low cost, highly active, durable cathode towards an oxygen reduction reaction (ORR) is one of the high-priority research directions for commercialization of low-temperature polymer electrolyte membrane fuel cells (PEMFCs). However, the electrochemical performance of PEMFCs is still hindered by the high cost and insufficient durability of the traditional Pt-based cathode catalysts. Under these circumstances, the search for efficient alternatives to replace Pt for constructing highly efficient nonprecious metal catalysts (NPMCs) has been growing intensively and has received great interest. Combining with the compositional effects, the accurate design of NPMCs with 3D porous nanostructures plays a significant role in further enhancing ORR performance. These 3D porous architectures are able to provide higher specific surface areas and larger pore volumes, not only maximizing the availability of electron transfer within the nanosized electrocatalyst surface area but also providing better mass transport of reactants to the electrocatalyst. In this Tutorial Review, we focus on the rational design and synthesis of different 3D porous carbon-based nanomaterials, such as heteroatom-doped carbon, metal-nitrogen-carbon nanostructures and a series of carbon/nonprecious metal-based hybrids. More importantly, their enhanced ORR performances are also demonstrated by virtue of their favorably porous morphologies and compositional effects. Finally, the future trends and perspectives for the highly efficient porous NPMCs regarding the material design are discussed, with an emphasis on substantial development of advanced carbon-based NPMCs for ORR in the near future.

  14. Large-Scale Synthesis of Carbon-Shell-Coated FeP Nanoparticles for Robust Hydrogen Evolution Reaction Electrocatalyst.

    Science.gov (United States)

    Chung, Dong Young; Jun, Samuel Woojoo; Yoon, Gabin; Kim, Hyunjoong; Yoo, Ji Mun; Lee, Kug-Seung; Kim, Taehyun; Shin, Heejong; Sinha, Arun Kumar; Kwon, Soon Gu; Kang, Kisuk; Hyeon, Taeghwan; Sung, Yung-Eun

    2017-05-17

    A highly active and stable non-Pt electrocatalyst for hydrogen production has been pursued for a long time as an inexpensive alternative to Pt-based catalysts. Herein, we report a simple and effective approach to prepare high-performance iron phosphide (FeP) nanoparticle electrocatalysts using iron oxide nanoparticles as a precursor. A single-step heating procedure of polydopamine-coated iron oxide nanoparticles leads to both carbonization of polydopamine coating to the carbon shell and phosphidation of iron oxide to FeP, simultaneously. Carbon-shell-coated FeP nanoparticles show a low overpotential of 71 mV at 10 mA cm -2 , which is comparable to that of a commercial Pt catalyst, and remarkable long-term durability under acidic conditions for up to 10 000 cycles with negligible activity loss. The effect of carbon shell protection was investigated both theoretically and experimentally. A density functional theory reveals that deterioration of catalytic activity of FeP is caused by surface oxidation. Extended X-ray absorption fine structure analysis combined with electrochemical test shows that carbon shell coating prevents FeP nanoparticles from oxidation, making them highly stable under hydrogen evolution reaction operation conditions. Furthermore, we demonstrate that our synthetic method is suitable for mass production, which is highly desirable for large-scale hydrogen production.

  15. Syntheses, structural variants and characterization of AInM′S4 (A=alkali metals, Tl; M′ = Ge, Sn) compounds; facile ion-exchange reactions of layered NaInSnS4 and KInSnS4 compounds

    International Nuclear Information System (INIS)

    Yohannan, Jinu P.; Vidyasagar, Kanamaluru

    2016-01-01

    Ten AInM′S 4 (A=alkali metals, Tl; M′= Ge, Sn) compounds with diverse structure types have been synthesized and characterized by single crystal and powder X-ray diffraction and a variety of spectroscopic methods. They are wide band gap semiconductors. KInGeS 4 (1-β), RbInGeS 4 (2), CsInGeS 4 (3-β), TlInGeS 4 (4-β), RbInSnS 4 (8-β) and CsInSnS 4 (9) compounds with three-dimensional BaGa 2 S 4 structure and CsInGeS 4 (3-α) and TlInGeS 4 (4-α) compounds with a layered TlInSiS 4 structure have tetrahedral [InM′S 4 ] − frameworks. On the other hand, LiInSnS 4 (5) with spinel structure and NaInSnS 4 (6), KInSnS 4 (7), RbInSnS 4 (8-α) and TlInSnS 4 (10) compounds with layered structure have octahedral [InM′S 4 ] − frameworks. NaInSnS 4 (6) and KInSnS 4 (7) compounds undergo facile topotactic ion-exchange, at room temperature, with various mono-, di- and tri-valent cations in aqueous medium to give rise to metastable layered phases. - Graphical abstract: NaInSnS 4 and KInSnS 4 compounds undergo, in aqueous medium at room temperature, facile topotactic ion-exchange with mono, di and trivalent cations. Display Omitted - Highlights: • Ten AInM′S 4 compounds with diverse structure types were synthesized. • They are wide band gap semiconductors. • NaInSnS 4 and KInSnS 4 compounds undergo facile topotactic ion-exchange at room temperature.

  16. Alkali Release from Typical Danish Aggregates to Potential ASR Reactive Concrete

    DEFF Research Database (Denmark)

    Thomsen, Hans Christian Brolin; Grelk, Bent; Barbosa, Ricardo Antonio

    Alkali-silica reaction (ASR) in concrete is a well-known deterioration mechanism affecting the long term durability of Danish concrete structures. Deleterious ASR cracking can be significantly reduced or prevented by limiting the total alkali content of concrete under a certain threshold limit......, which in Denmark is recommended to 3 kg/m3 Na2Oeq.. However, this threshold limit does not account for the possible internal contribution of alkali to the concrete pore solution by release from aggregates or external contributions from varies sources. This study indicates that certain Danish aggregates...... are capable of releasing more than 0.46 kg/m3 Na2Oeq. at 13 weeks of exposure in laboratory test which may increase the risk for deleterious cracking due to an increase in alkali content in the concrete....

  17. Defluidization in fluidized bed gasifiers using high-alkali content fuels

    DEFF Research Database (Denmark)

    Narayan, Vikas; Jensen, Peter Arendt; Henriksen, Ulrik Birk

    2016-01-01

    samples,agglomeration could be attributed to viscous silicate melts formed from reaction of inorganic alkalineand alkali earth species with silica from the bed particles. A mathematical model that addresses the defluidization behavior of alkali-rich samples was developed based on the experiments performed...... and calcium, which may form viscous melts that adhere on the surface of the colliding bed particles and bind them to form agglomerates. In this paper, studies were made to understand the behavior of inorganic elements (mainly K, Si and Ca) on agglomeration and de-fluidization of alkali rich bed...... in the bench-scale fluidized bed reactor as well as on results from literature. The model was then used topredict the de-fluidization behavior of alkali-rich bed material in a large-scale LTCFB gasifier....

  18. Tailoring Synthesis Conditions of Carbon Xerogels towards Their Utilization as Pt-Catalyst Supports for Oxygen Reduction Reaction (ORR

    Directory of Open Access Journals (Sweden)

    María Jesús Lázaro

    2012-10-01

    Full Text Available Carbon xerogels characterized by different textural, structural and chemical properties were synthesized and used as supports for Pt catalysts for the application in polymer electrolyte fuel cells. Synthesis conditions were varied in order to synthesize carbon xerogels following the sol-gel method. These included the reactants ratio (precursor/formaldehyde, the catalyst concentration (precursor/catalyst ratio and type (basic and acid, the precursor type (resorcinol and pyrogallol and the solvent (aqueous or acetone based. Stoichiometric mixtures of resorcinol and formaldehyde yielded well polymerized gels and highly developed structures. Slow gelation, favored by the presence of acetone as solvent in the sol and low catalyst concentration, resulted in higher polymerization extent with a highly mesoporous or even macroporous texture and more ordered structure, as evidenced by XPS and Raman spectroscopy. Small Pt particles of ca. 3.5 nm were obtained by using carbon xerogels characterized by an ordered surface structure. The specific activity towards the oxygen reduction reaction, i.e., the limiting catalytic process in low temperature fuel cells, is significantly favored by highly ordered carbon xerogels due to a metal-support enhanced interaction. Nevertheless, surface defects favor the distribution of the metallic particles on the surface of carbon, which in the end influences the effectiveness of the catalyst. Accelerated degradation tests were conducted to evaluate catalyst stability under potential cycling conditions. The observed decay of performance was considerably lower for the catalysts based on ordered carbon xerogels stabilizing Pt particles in a higher extent than the other xerogels and the commercial carbon black support.

  19. Facile Precursor for Synthesis of Silver Nanoparticles Using Alkali Treated Maize Starch

    Science.gov (United States)

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

    2014-01-01

    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

  20. Iron (II) tetrakis(diaquaplatinum) octacarboxyphthalocyanine supported on multi-walled carbon nanotubes as effective electrocatalyst for oxygen reduction reaction in alkaline medium

    CSIR Research Space (South Africa)

    Mamuru, SA

    2010-11-01

    Full Text Available Oxygen reduction reaction (ORR) in alkaline medium at iron (II) tetrakis (diaquaplatinum) octacarboxyphthalocyanine (PtFeOCPc) catalyst supported on multi-walled carbon nanotubes (MWCNTs) has been described. The ORR followed the direct 4-electron...

  1. Studies on the heterogeneous electron transport and oxygen reduction reaction at metal (Co, Fe) octabutylsulphonylphthalocyanines supported on multi-walled carbon nanotube modified graphite electrode

    CSIR Research Space (South Africa)

    Mamuru, SA

    2010-09-01

    Full Text Available Heterogeneous electron transfer dynamics and oxygen reduction reaction (ORR) activities using octabutylsulphonylphthalocyanine complexes of iron (FeOBSPc) and cobalt (CoOBSPc) supported on multi-walled carbon nanotube (MWCNT) platforms have been...

  2. Process for carrying out a chemical reaction with ionic liquid and carbon dioxide under pressure

    NARCIS (Netherlands)

    Kroon, M.C.; Shariati, A.; Florusse, L.J.; Peters, C.J.; Van Spronsen, J.; Witkamp, G.J.; Sheldon, R.A.; Gutkowski, K.I.

    2006-01-01

    The invention is directed to a process for carrying out a chemical reaction in an ionic liquid as solvent and CO2 as cosolvent, in which process reactants are reacted in a homogeneous phase at selected pressure and temperature to generate a reaction product at least containing an end-product of the

  3. Reaction-driven cracking during hydration and carbonation of olivine: Implications for in situ CO2 capture and storage

    Science.gov (United States)

    Kelemen, P. B.; Hirth, G.

    2011-12-01

    Reactions forming serpentine and/or Mg-carbonates via reaction of fluid with olivine may increase the solid volume, due to increasing solid mass and decreasing solid density, provided that fluid is supplied in an open system, and that dissolution does not remove significant solid mass. Increasing solid volume can create deviatoric stress within a rock, potentially causing fracture. In turn, this can provide a positive feedback to the alteration process, maintaining or increasing permeability and reactive surface area. This could be important - or even essential - for proposed in situ mineral carbonation for CO2 storage, and potentially for geological CO2 capture from surface waters. We use several methods to estimate the 'force of crystallization' during hydration and carbonation of olivine. The free energy changes driving these processes can potentially generate overpressures of 100's to 1000's of MPa. These potential stresses are larger for a given temperature for carbonation compared to serpentinization. Thermodynamic upper bounds can be compared to estimates based on microstructure in natural samples. Evans (Int Geol Rev 2004) and Jamtveit et al. (EPSL 2008) provide microphotographs of igneous troctolites, with interstitial plagioclase surrounding rounded olivine grains. The olivine grains are partially serpentinized, and the plagioclase has closely spaced fractures interpreted as a result of expansion during serpentinization. Strain energy due to expansion should be greater than surface energy on new fractures. Spacing and length of fractures in plagioclase yields a minimum of about 260 MPa for the differential stress. Alternatively, if fractures did not form, elastic stress in the plagioclase resulting from expansion during serpentinization should be proportional to the strain. Because some strain could be accommodated by irreversible mechanisms, such as friction and dilation on cracks and/or viscous flow, this yields a maximum stress of 270 MPa. The close

  4. Stabilization of aqueous alkali metal aluminate solutions

    Energy Technology Data Exchange (ETDEWEB)

    Allenson, S.J.

    1988-03-29

    A method of stabilizing an aqueous solution of alkali metal aluminate is described comprising: admixing an aqueous solution of alkali metal aluminate having a pH of at least 10 with a sufficient amount of vinyl polymer having pendant carboxylate groups to form a solution containing from 0.1 to 2.0 weight percent of an anionic vinyl polymer based on alkali metal aluminate solids. The anionic vinyl polymer has an average molecular weight of at least 500,000.

  5. Improving the electrocatalytic performance of carbon nanotubes for VO2+/VO2+ redox reaction by KOH activation

    International Nuclear Information System (INIS)

    Dai, Lei; Jiang, Yingqiao; Meng, Wei; Zhou, Huizhu; Wang, Ling; He, Zhangxing

    2017-01-01

    Highlights: • KOH-activated carbon nanotubes (CNTs) was investigated as superior catalyst for VO 2+ /VO 2 + redox reaction for vanadium redox flow battery (VRFB) for the first time. • KOH activation for CNTs can result in the chemical etching of surface and improved wettability, accelerating the mass transfer of vanadium ions. • KOH activation can introduce many oxygen-containing groups as active sites on the surface of CNTs. • KOH-activated CNTs as positive catalyst could increase the comprehensive energy storage performance of VRFB. - Abstract: In this paper, carbon nanotubes (CNTs) was activated by KOH treatment at high temperature and investigated as catalyst for VO 2+ /VO 2 + redox reaction for vanadium redox flow battery (VRFB). X-ray photoelectron spectroscopy results suggest that the oxygen-containing groups can be introduced on CNTs by KOH activation. The mass transfer of vanadium ions can be accelerated by chemical etching by KOH activation and improved wettability due to the introduction of hydrophilic groups. The electrochemical properties of VO 2+ /VO 2 + redox reaction can be enhanced by introduced oxygen-containing groups as active sites. The sample treated at 900 °C with KOH/CNTs mass ratio of 3:1 (CNTs-3) exhibits the highest electrocatalytic activity for VO 2+ /VO 2 + redox reaction. The cell using CNTs-3 as positive catalyst demonstrates the smallest electrochemical polarization, the highest capacity and efficiency among the samples. Using KOH-activated CNTs-3 can increase the average energy efficiency of the cell by 4.4%. This work suggests that KOH-activated CNTs is a low-cost, efficient and promising catalyst for VO 2+ /VO 2 + redox reaction for VRFB system.

  6. Synthesis and structural characterization of alkali metal arsinoamides.

    Science.gov (United States)

    Chen, Xiao; Gamer, Michael T; Roesky, Peter W

    2017-12-20

    The aminoarsane Mes 2 AsN(H)Ph was prepared from Mes 2 AsCl and aniline in good yields. Deprotonation of Mes 2 AsN(H)Ph with suitable alkali metal bases resulted in the corresponding alkali metal derivatives. Thus, reaction of Mes 2 AsN(H)Ph with nBuLi, NaN(SiMe 3 ) 2 , or KH gave the metal complexes [(Mes 2 AsNPh){Li(OEt 2 ) 2 }], [(Mes 2 AsNPh){Na(OEt 2 )}] 2 , and [(Mes 2 AsNPh){K(THF)}] 2 . These are the first metal complexes ligated by an arsinoamide. All solid-state structures were established by single crystal X-ray diffraction. The lithium compounds form a monomer in the solid-state, whereas the sodium and the potassium derivatives are dimers. In the dimeric compounds intra- and intermolecular π-interaction of the aromatic rings with the metal atoms is observed.

  7. Global search for low-lying crystal structures using the artificial force induced reaction method: A case study on carbon

    Science.gov (United States)

    Takagi, Makito; Taketsugu, Tetsuya; Kino, Hiori; Tateyama, Yoshitaka; Terakura, Kiyoyuki; Maeda, Satoshi

    2017-05-01

    We propose an approach to perform the global search for low-lying crystal structures from first principles, by combining the artificial force induced reaction (AFIR) method and the periodic boundary conditions (PBCs). The AFIR method has been applied extensively to molecular systems to elucidate the mechanism of chemical reactions such as homogeneous catalysis. The present PBC/AFIR approach found 274 local minima for carbon crystals in the C8 unit cell described by the generalized gradient approximation-Perdew-Burke-Ernzerhof functional. Among many newly predicted structures, three low-lying structures, which exhibit somewhat higher energy compared with those previously predicted, such as Cco -C8 (Z -carbon) and M -carbon, are further discussed with calculations of phonon and band dispersion curves. Furthermore, approaches to systematically explore two- or one-dimensional periodic structures are proposed and applied to the C8 unit cell with the slab model. These results suggest that the present approach is highly promising for predicting crystal structures.

  8. Synthesis of Cobalt Sulfide/Sulfur Doped Carbon Nanocomposites with Efficient Catalytic Activity in the Oxygen Evolution Reaction.

    Science.gov (United States)

    Qian, Huayu; Tang, Jing; Wang, Zhongli; Kim, Jeonghun; Kim, Jung Ho; Alshehri, Saad M; Yanmaz, Ekrem; Wang, Xin; Yamauchi, Yusuke

    2016-12-12

    Cobalt sulfide/sulfur doped carbon composites (Co 9 S 8 /S-C) were synthesized by calcining a rationally designed sulfur-containing cobalt coordination complex in an inert atmosphere. From the detailed transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) analyses, the electrocatalytically active Co 9 S 8 nanoparticles were clearly obtained and combined with the thin sulfur doped carbon layers. Electrochemical data showed that Co 9 S 8 /S-C had a good activity and long-term stability in catalyzing oxygen evolution reaction in alkaline electrolyte, even better than the traditional RuO 2 electrocatalyst. The excellent electrocatalytic activity of Co 9 S 8 /S-C was mainly attributed to the synergistic effect between the Co 9 S 8 catalyst which contributed to the oxygen evolution reaction and the sulfur doped carbon layer which facilitated the adsorption of reactants, prevented the Co 9 S 8 particles from aggregating and served as the electrically conductive binder between each component. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Nitrogen-doped carbon-embedded TiO2 nanofibers as promising oxygen reduction reaction electrocatalysts

    Science.gov (United States)

    Hassen, D.; Shenashen, M. A.; El-Safty, S. A.; Selim, M. M.; Isago, H.; Elmarakbi, A.; El-Safty, A.; Yamaguchi, H.

    2016-10-01

    The development of inexpensive and effective electrocatalysts for oxygen reduction reaction (ORR) as a substitute for commercial Pt/C catalyst is an important issue in fuel cells. In this paper, we report on novel fabrication of self-supported nitrogen-doped carbon-supported titanium nanofibers (Nsbnd TiO2@C) and carbon-supported titanium (TiO2@C) electrocatalysts via a facile electrospinning route. The nitrogen atom integrates physically and homogenously into the entire carbon-titanium structure. We demonstrate the catalytic performance of Nsbnd TiO2@C and TiO2@C for ORR under alkaline conditions in comparison with Pt/C catalyst. The Nsbnd TiO2@C catalyst shows excellent ORR reactivity and durability. Interestingly, among all the catalysts used in this ORR, Nsbnd TiO2@C-0.75 exhibits remarkable competitive oxygen reduction activity in terms of current density and onset potential, as well as superior methanol tolerance. Such tolerance attributes to maximizing the diffusion of trigger pulse electrons during catalytic reactions because of enhanced electronic features. Results indicate that our fabrication strategy can provide an opportunity to produce a simple, efficient, cost-effective, and promising ORR electrocatalyst for practical applications in energy conversion and storage technologies.

  10. Alkali Metal Coolants. Proceedings of the Symposium on Alkali Metal Coolants - Corrosion Studies and System Operating Experience

    International Nuclear Information System (INIS)

    1967-01-01

    Proceedings of a Symposium organized by the IAEA and held in Vienna, 28 November - 2 December 1966. The meeting was attended by 107 participants from 16 countries and two international organizations. Contents: Review papers (2 papers); Corrosion of steels and metal alloys (6 papers); Mass transfer in alkali metal systems, behaviour of carbon (5 papers); Effects of sodium environment on mechanical properties of materials (3 papers); Effect of water leakage into sodium systems (2 papers); Design-and operation of testing apparatus (6 papers); Control, measurements and removal of impurities (13 papers); Corrosion by other alkali metals: NaK, K, Li, Cs (6 papers); Behaviour of fission products (3 papers). Each paper is in its original language (32 English, 6 French and 8 Russian) and is preceded by an abstract in English and one in the original language if this is not English. Discussions are in English. (author)

  11. Unsaturated thiolates and their analogs in cycloaddition reactions

    International Nuclear Information System (INIS)

    Lajshev, V.Z.; Petrov, M.L.; Petrov, A.A.

    1981-01-01

    Salts of 2-arylethinyltellurol are prepared by means of alkali metal arylacetylenides interaction with tellurium in the medium of dimethylsulfoxide. The treatment of the salts with ether solution of hydrogen chloride results in 2,4-di(n- R-benzyliden)-1,3-ditelluranes; in the case of water (or oxidation by iodine)-di(2-arylethinyl) tellurides. With carbon sulfide and dimethyl ether of acetylenedicarbonic acid 2-phenylethinyltellurolate of sodium inters in cyclization reaction. In this case, the products of nucleophylic addition are formed. Non-stable N, N-diethylamide of phenylthioacetic acid is the initial product of 2-phenylethinyltellurolate of sodium interaction with diethylamine [ru

  12. CARBON DIOXIDE CAPTURE FROM FLUE GAS USING DRY REGENERABLE SORBENTS

    International Nuclear Information System (INIS)

    David A. Green; Brian S. Turk; Raghubir P. Gupta; William J. McMichael; Douglas P. Harrison; Ya Liang

    2002-01-01

    The objective of this project is to develop a simple, inexpensive process to separate CO(sub 2) as an essentially pure stream from a fossil fuel combustion system using a regenerable, sodium-based sorbent. The sorbents being investigated in this project are primarily alkali carbonates, and particularly sodium carbonate and potassium carbonate, which are converted to bicarbonates, through reaction with carbon dioxide and water vapor. Bicarbonates are regenerated to carbonates when heated, producing a nearly pure CO(sub 2) stream after condensation of water vapor. This quarter, electrobalance tests conducted at LSU indicated that exposure of sorbent to water vapor prior to contact with carbonation gas does not significantly increase the reaction rate. Calcined fine mesh trona has a greater initial carbonation rate than calcined sodium bicarbonate, but appears to be more susceptible to loss of reactivity under severe calcination conditions. The Davison attrition indices for Grade 5 sodium bicarbonate, commercial grade sodium carbonate and extra fine granular potassium carbonate were, as tested, outside of the range suitable for entrained bed reactor testing. Fluidized bed testing at RTI indicated that in the initial stages of reaction potassium carbonate removed 35% of the carbon dioxide in simulated flue gas, and is reactive at higher temperatures than sodium carbonate. Removals declined to 6% when 54% of the capacity of the sorbent was exhausted. Carbonation data from electrobalance testing was correlated using a shrinking core reaction model. The activation energy of the reaction of sodium carbonate with carbon dioxide and water vapor was determined from nonisothermal thermogravimetry

  13. Functionalization of Carbon Nanotubes via Electrophilic Substitution Reaction in Polyphosphoric Acid

    National Research Council Canada - National Science Library

    Baek, Jong-Beom

    2006-01-01

    .... Furthermore, on the basis of all supportive evidences, this work provides one of the most efficient methods to directly and uniformly grafting the surfaces of carbon nanotubes (CNT) and nanofibers (CNF...

  14. Graphene-oxide-supported CuAl and CoAl layered double hydroxides as enhanced catalysts for carbon-carbon coupling via Ullmann reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, Nesreen S. [Department of Chemistry, Faculty of Science, King Abdulaziz University (Saudi Arabia); Surface Chemistry and Catalytic Studies Group, King Abdulaziz University (Saudi Arabia); Menzel, Robert [Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Bio Nano Consulting, The Gridiron Building, One Pancras Square, London N1C 4AG (United Kingdom); Wang, Yifan [Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Garcia-Gallastegui, Ainara [Bio Nano Consulting, The Gridiron Building, One Pancras Square, London N1C 4AG (United Kingdom); Bawaked, Salem M.; Obaid, Abdullah Y.; Basahel, Sulaiman N. [Department of Chemistry, Faculty of Science, King Abdulaziz University (Saudi Arabia); Surface Chemistry and Catalytic Studies Group, King Abdulaziz University (Saudi Arabia); Mokhtar, Mohamed, E-mail: mmokhtar2000@yahoo.com [Department of Chemistry, Faculty of Science, King Abdulaziz University (Saudi Arabia); Surface Chemistry and Catalytic Studies Group, King Abdulaziz University (Saudi Arabia)

    2017-02-15

    Two efficient catalyst based on CuAl and CoAl layered double hydroxides (LDHs) supported on graphene oxide (GO) for the carbon-carbon coupling (Classic Ullmann Homocoupling Reaction) are reported. The pure and hybrid materials were synthesised by direct precipitation of the LDH nanoparticles onto GO, followed by a chemical, structural and physical characterisation by electron microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area measurements and X-ray photoelectron spectroscopy (XPS). The GO-supported and unsupported CuAl-LDH and CoAl-LDH hybrids were tested over the Classic Ullman Homocoupling Reaction of iodobenzene. In the current study CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary and two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH. - Graphical abstract: CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary, two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. - Highlights: • CuAl LDH/GO and CoAl LDH/GO hybrid materials with different LDH compositions were prepared. • Hybrids were fully characterised and their catalytic efficiency over the Classic Ullman Reaction was studied. • CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) in 25 min reaction times. • GO provides a light-weight, charge complementary, two-dimensional material that interacts effectively with the 2D LDHs. • After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH.

  15. Paragenesis of Palladium-Cobalt Nanoparticle in Nitrogen-Rich Carbon Nanotubes as a Bifunctional Electrocatalyst for Hydrogen-Evolution Reaction and Oxygen-Reduction Reaction.

    Science.gov (United States)

    Huang, Binbin; Chen, Liyu; Wang, Yan; Ouyang, Liuzhang; Ye, Jianshan

    2017-06-07

    The hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR) play important roles in many energy conversion and storage systems. To accelerate the reaction processes, there is a constant need for efficient new catalysts. In the present work, we have developed a facile pyrolysis-based process for the co-synthesis of palladium-cobalt nanoparticles supported on carbon nanotubes (Pd-CoCNTs), which exhibit superior catalytic activity for the HER and enhanced ORR performance. Non-agglomerated Pd nanoparticles of diameters 2-4 nm are uniformly distributed on the surface of CoCNTs, while the inner Co particles are an essential element in forming the framework of the CoCNTs. Compared to the Pd-free N-rich CoCNTs, Pd-CoCNTs have a more defective surface with a larger electrochemically active surface area (ECSA), and show enhanced ORR activity, outstanding methanol tolerance, and long-term stability in alkaline solution. At a low Pd loading of 0.0292 mg cm -2 , the Pd-CoCNTs require overpotentials of 0.024 V and 0.215 V to catalyze the HER and to drive a current density of 50 mA cm -2 in acidic solution, respectively. The palladium nanoparticles on the surface of the CoCNTs are considered to be highly active sites for HER, based on the results of control experiments, and it is easy to adjust the catalytic activity of the Pd-CoCNTs by changing the concentration of Pd therein. The proposed method provides a means of fabricating efficient bifunctional catalysts with controllable low contents of precious metals. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Review of alkali metal and refractory alloy compatibility for Rankine cycle applications

    International Nuclear Information System (INIS)

    DiStefano, J.R.

    1989-01-01

    The principal corrosion mechanisms in refractory metal-alkali systems are dissolution, mass transfer, and impurity reactions. In general, niobium, tantalum, molybdenum, and tungsten have low solubilities in the alkali metals, even to very high temperatures, and static corrosion studies have verified that the systems are basically compatible. Loop studies with niobium and tantalum based alloys do not indicate any serious problems due to temperature gradient mass transfer. Above 1000 K, dissimilar metal mass transfer is noted between the refractory metals and iron or nickel based alloys. The most serious corrosion problems encountered are related to impurity reactions associated with oxygen

  17. A novel electrocatalyst for oxygen evolution reaction based on rational anchoring of cobalt carbonate hydroxide hydrate on multiwall carbon nanotubes

    Science.gov (United States)

    Zhang, Yuxia; Xiao, Qingqing; Guo, Xin; Zhang, Xiaoxue; Xue, Yifei; Jing, Lin; Zhai, Xue; Yan, Yi-Ming; Sun, Kening

    2015-03-01

    Cobalt carbonate hydroxide hydrate (CCHH) nanosheets have been densely and strongly anchored onto mildly oxidized multiwalled carbon nanotubes with the assistance of diethylenetriamine (DETA). The resulted hybrid (CCHH/MWCNT) is used as high efficient electrocatalyst for water oxidation with an extremely low onset potential of ∼1.47 V vs. RHE and an overpotential of 285 mV to achieve a current density of 10 mA cm-2 in 1.0 mol L-1 KOH. The CCHH/MWCNT electrode affords a Tafel slope of 51 mV/decade and an exchange current density of 2.5 × 10-7 A cm-2. Moreover, the CCHH/MWCNT catalyst delivers a high faradic efficiency of 95% and possesses remarkable stability for long-term electrolysis of water. By contrast, neither MWCNT nor CCHH exhibits apparent catalytical activity towards water oxidation. Importantly, we demonstrate that DETA plays crucial role in determining the morphology, structure of the CCHH/MWCNT, therefore resulting in an enhanced performance for water oxidation. This work not only provides a novel cobalt-based electrocatalyst for oxygen evolution, but also offers a useful and viable approach to deliberately synthesize functional nanocomposites for applications in energy conversion and storage.

  18. Multiwalled carbon nanotubes@octavinyl polyhedral oligomeric silsesquioxanes nanocomposite preparation via cross-linking reaction in acidic media

    Energy Technology Data Exchange (ETDEWEB)

    Somasekharan, Lakshmipriya; Thomas, Sabu [Mahatma Gandhi University, International and Interuniversity Centre for Nanoscience and Nanotechnology (India); Comoy, Corinne [Université de Lorraine, SRSMC, UMR 7565 (France); Sivasankarapillai, Anilkumar [NSS Hindu College (India); Kalarikkal, Nandakumar [Mahatma Gandhi University, International and Interuniversity Centre for Nanoscience and Nanotechnology (India); Lamouroux, Emmanuel, E-mail: Emmanuel.Lamouroux@univ-lorraine.fr [Université de Lorraine, SRSMC, UMR 7565 (France)

    2016-11-15

    Multiwalled carbon nanotubes have unique properties allowing their use in a wide range of applications—from microelectronics to biomedical and polymer fields. Nevertheless, a crucial aspect for their use resides in the ease of handling them during the process. Here, we report a facile route to prepare multiwalled carbon nanotubes@octavinyl polyhedral oligomeric silsesquioxanes (MWCNT@POSS) nanocomposite. The method involves the formation of a covalent bond between carboxylated MWCNTs and OV-POSS using acid-catalyzed electrophilic addition reaction. The resulting nanocomposite have been characterized by Fourier transform infrared spectroscopy (FTIR), powder X-Ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The results confirmed that the formation of MWCNT@POSS nanocomposite did not deteriorate MWCNT structure or morphology. Here, we used a 1:1 ratio of carboxylated MWCNTs and OV-POSS and the POSS content in the nanocomposite was 39.5 wt%.

  19. Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells

    Science.gov (United States)

    Sawant, Sandesh Y.; Han, Thi Hiep; Cho, Moo Hwan

    2016-01-01

    Microbial fuel cells (MFCs) are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR). Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored. PMID:28029116

  20. Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells

    Directory of Open Access Journals (Sweden)

    Sandesh Y. Sawant

    2016-12-01

    Full Text Available Microbial fuel cells (MFCs are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR. Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored.

  1. Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells.

    Science.gov (United States)

    Sawant, Sandesh Y; Han, Thi Hiep; Cho, Moo Hwan

    2016-12-24

    Microbial fuel cells (MFCs) are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR). Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored.

  2. A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals

    KAUST Repository

    Khaled, Fathi

    2017-02-08

    The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt\\'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning\\'s augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

  3. Synthesis and Characterization of Graphene and Graphene Oxide Based Palladium Nanocomposites and Their Catalytic Applications in Carbon-Carbon Cross-Coupling Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Minjae [Kunsan National Univ., Gunsan (Korea, Republic of); Kim, Bohyun; Lee, Yuna; Kim, Beomtae; Park, Joon B. [Chonbuk National Univ., Jeonju (Korea, Republic of)

    2014-07-15

    We have developed an efficient method to generate highly active Pd and PdO nanoparticles (NPs) dispersed on graphene and graphene oxide (GO) by an impregnation method combined with thermal treatments in H{sub 2} and O{sub 2} gas flows, respectively. The Pd NPs supported on graphene (Pd/G) and the PdO NPs supported on GO (PdO/GO) demonstrated excellent carbon-carbon cross-coupling reactions under a solvent-free, environmentally-friendly condition. The morphological and chemical structures of PdO/GO and Pd/G were fully characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). We found that the remarkable reactivity of the Pd/G and PdO/GO catalysts toward the cross-coupling reaction is attributed to the high degree of dispersion of the Pd and PdO NPs while the oxidative states of Pd and the oxygen functionalities of graphene oxide are not critical for their catalytic performance.

  4. Synthesis and Characterization of Graphene and Graphene Oxide Based Palladium Nanocomposites and Their Catalytic Applications in Carbon-Carbon Cross-Coupling Reactions

    International Nuclear Information System (INIS)

    Lee, Minjae; Kim, Bohyun; Lee, Yuna; Kim, Beomtae; Park, Joon B.

    2014-01-01

    We have developed an efficient method to generate highly active Pd and PdO nanoparticles (NPs) dispersed on graphene and graphene oxide (GO) by an impregnation method combined with thermal treatments in H 2 and O 2 gas flows, respectively. The Pd NPs supported on graphene (Pd/G) and the PdO NPs supported on GO (PdO/GO) demonstrated excellent carbon-carbon cross-coupling reactions under a solvent-free, environmentally-friendly condition. The morphological and chemical structures of PdO/GO and Pd/G were fully characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). We found that the remarkable reactivity of the Pd/G and PdO/GO catalysts toward the cross-coupling reaction is attributed to the high degree of dispersion of the Pd and PdO NPs while the oxidative states of Pd and the oxygen functionalities of graphene oxide are not critical for their catalytic performance

  5. The NO-carbon reaction: the influence of potassium and CO on reactivity and populations of oxygen surface complexes

    Energy Technology Data Exchange (ETDEWEB)

    Diana Lopez; Joseph Calo [Brown University, Providence, RI (United States). Division of Engineering

    2007-08-15

    Results on the effects of a metal catalyst and the role of CO as a reducing agent are reported for a resin char and a Wyodak coal char, as well as demineralized samples of the latter. The effect of an active metal catalyst, such as potassium in the current work, is to significantly increase the reactivity both by increasing the number of reaction sites via the catalyst dispersion and reducing the activation energy and by increasing CO{sub 2} production. The latter is a beneficial result because it means that less carbon is consumed per molecule of NO reduced. Additional CO in the gas phase 'catalyzes' NO reduction via the creation of more labile surface complexes and facilitation of desorption of other oxygen complexes. This effect decreases with an increasing temperature and disappears by about 1123 K. The activation energy of this reaction is comparable to that induced by the metal catalyst. 21 refs., 9 figs., 2 tabs.

  6. Formation of Gas-Phase Formate in Thermal Reactions of Carbon Dioxide with Diatomic Iron Hydride Anions.

    Science.gov (United States)

    Jiang, Li-Xue; Zhao, Chongyang; Li, Xiao-Na; Chen, Hui; He, Sheng-Gui

    2017-04-03

    The hydrogenation of carbon dioxide involves the activation of the thermodynamically very stable molecule CO 2 and formation of a C-H bond. Herein, we report that HCO 2 - and CO can be formed in the thermal reaction of CO 2 with a diatomic metal hydride species, FeH - . The FeH - anions were produced by laser ablation, and the reaction with CO 2 was analyzed by mass spectrometry and quantum-chemical calculations. Gas-phase HCO 2 - was observed directly as a product, and its formation was predicted to proceed by facile hydride transfer. The mechanism of CO 2 hydrogenation in this gas-phase study parallels similar behavior of a condensed-phase iron catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Synthesis of biodiesel from a model waste oil feedstock using a carbon-based solid acid catalyst: reaction and separation.

    Science.gov (United States)

    Shu, Qing; Nawaz, Zeeshan; Gao, Jixian; Liao, Yuhui; Zhang, Qiang; Wang, Dezheng; Wang, Jinfu

    2010-07-01

    A solid acid catalyst that can keep high activity and stability is necessary when low cost feedstocks are utilized for biodiesel synthesis because the reaction medium contains a large amount of water. Three solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt. The structure of these catalysts was characterized by a variety of techniques. A new process that used the coupling of the reaction and separation was employed, which greatly improved the conversion of cottonseed oil (triglyceride) and free fatty acids (FFA) when a model waste oil feedstock was used. The vegetable oil asphalt-based catalyst showed the highest catalytic activity. This was due to the high density and stability of its acid sites, its loose irregular network, its hydrophobicity that prevented the hydration of -OH species, and large pores that provided more acid sites for the reactants. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  8. Cerium carbide embedded in nitrogen-doped carbon as a highly active electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Wang, Wei; Xue, Shouyuan; Li, Jinmei; Wang, Fengxia; Kang, Yumao; Lei, Ziqiang

    2017-08-01

    In this study, cerium carbide embedded in nitrogen-doped carbon (CeCx-NC) has been prepared by a facile pyrolysis of melamine formaldehyde resin containing rare-earth element. The as-prepared CeCx-NC catalyst shows high electrocatalytic activity towards oxygen reduction reaction (ORR) in alkaline electrolyte, with the half wave potential being almost equal to commercial Pt/C, nearly four electron transfer number, good toxicity tolerance durability and cycle stability. This rare-earth metal carbide opens a novel avenue for advanced electrocatalyst.

  9. Sensitivity of chemical reaction networks: a structural approach. 1. Examples and the carbon metabolic network.

    Science.gov (United States)

    Mochizuki, Atsushi; Fiedler, Bernold

    2015-02-21

    In biological cells, chemical reaction pathways lead to complex network systems like metabolic networks. One experimental approach to the dynamics of such systems examines their "sensitivity": each enzyme mediating a reaction in the system is increased/decreased or knocked out separately, and the responses in the concentrations of chemicals or their fluxes are observed. In this study, we present a mathematical method, named structural sensitivity analysis, to determine the sensitivity of reaction systems from information on the network alone. We investigate how the sensitivity responses of chemicals in a reaction network depend on the structure of the network, and on the position of the perturbed reaction in the network. We establish and prove some general rules which relate the sensitivity response to the structure of the underlying network. We describe a hierarchical pattern in the flux response which is governed by branchings in the network. We apply our method to several hypothetical and real life chemical reaction networks, including the metabolic network of the Escherichia coli TCA cycle. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. Up-Scaling Geochemical Reaction Rates for Carbon Dioxide (CO2) in Deep Saline Aquifers

    Energy Technology Data Exchange (ETDEWEB)

    Lindquist, W Brent

    2009-03-03

    The overall goal of the project was to bridge the gap between our knowledge of small-scale geochemical reaction rates and reaction rates meaningful for modeling transport at core scales. The working hypothesis was that reaction rates, determined from laboratory measurements based upon reactions typically conducted in well mixed batch reactors using pulverized reactive media may be significantly changed in in situ porous media flow due to rock microstructure heterogeneity. Specifically we hypothesized that, generally, reactive mineral surfaces are not uniformly accessible to reactive fluids due to the random deposition of mineral grains and to the variation in flow rates within a pore network. Expected bulk reaction rates would therefore have to be correctly up-scaled to reflect such heterogeneity. The specific objective was to develop a computational tool that integrates existing measurement capabilities with pore-scale network models of fluid flow and reactive transport. The existing measurement capabilities to be integrated consisted of (a) pore space morphology, (b) rock mineralogy, and (c) geochemical reaction rates. The objective was accomplished by: (1) characterizing sedimentary sandstone rock morphology using X-ray computed microtomography, (2) mapping rock mineralogy using back-scattered electron microscopy (BSE), X-ray dispersive spectroscopy (EDX) and CMT, (3) characterizing pore-accessible reactive mineral surface area, and (4) creating network models to model acidic CO{sub 2} saturated brine injection into the sandstone rock samples.

  11. Combined steam and carbon dioxide reforming of methane and side reactions: Thermodynamic equilibrium analysis and experimental application

    International Nuclear Information System (INIS)

    Jang, Won-Jun; Jeong, Dae-Woon; Shim, Jae-Oh; Kim, Hak-Min; Roh, Hyun-Seog; Son, In Hyuk; Lee, Seung Jae

    2016-01-01

    Highlights: • Selected variables have a significant influence on yields of synthesis gas. • (CO 2 + H 2 O)/CH 4 affects the temperature which can achieve the maximum conversion. • Coke is formed at low temperatures even with excess oxidizing agent. • The occurrence of RWGS becomes critical in real chemical reactions. • Equilibrium conversions are maintained for 500 h without detectable deactivation. - Abstract: Thermodynamic equilibrium analysis of the combined steam and carbon dioxide reforming of methane (CSCRM) and side reactions was performed using total Gibbs free energy minimization. The effects of (CO 2 + H 2 O)/CH 4 ratio (0.9–2.9), CO 2 :H 2 O ratio (3:1–1:3), and temperature (500–1000 °C) on the equilibrium conversions, yields, coke yield, and H 2 /CO ratio were investigated. A (CO 2 + H 2 O)/CH 4 ratio greater than 1.2, a CO 2 :H 2 O ratio of 1:2.1, and a temperature of at least 850 °C are preferable reaction conditions for the synthesis gas preparation in the gas to liquid process. Simulated conditions were applied to the CSCRM reaction and the experimental data were compared with the thermodynamic equilibrium results. The thermodynamic equilibrium results were mostly consistent with the experimental data, but the reverse water gas shift reaction rapidly occurred in the real chemical reaction and under excess oxidizing agent conditions. In addition, a long-term stability test (under simulated conditions) showed that the equilibrium conversion was maintained for 500 h and that the coke formation on the used catalyst was not observed.

  12. Centrality in Hadron-Carbon, Hadron-Lead, and Lead-Lead Reactions at 158 GeV/c

    International Nuclear Information System (INIS)

    Rybicki, A.

    2006-08-01

    A study of centrality in p + C, π + C, p + Pb, π + Pb, and Pb + Pb reactions is made. The analysis is performed by means of a simple geometrical model. The mean number of elementary collisions, , is estimated in minimum bias p + C reactions. For the specific case of the carbon nucleus, estimates on appear to depend strongly on assumed nuclear densities. Most realistic of the presented assumptions result in a value of 1.71 ± 0.05. Additional quantities, like predictions for the total inelastic cross-section in p + C reactions, or the number of participants in minimum bias C + C collisions, are given. The analysis is subsequently extended to minimum bias π + C, π + Pb, and p + Pb reactions. Estimates are given for the mean number of elementary collisions as well as for the contribution of single collisions P(1). A comparison with experimental data is made. Finally, the impact parameter dependence of p + Pb and Pb + Pb collisions is discussed. In view of future studies, various aspects of the analysis are discussed in detail; a bibliography of used references is included. (author)

  13. Chemical behaviour of plutonium in natural, aquatic systems: Hydrolysis, carbonate complexation and redox reactions

    International Nuclear Information System (INIS)

    Lierse, C.

    1985-01-01

    In order to clear up the geochemical behaviour of plutonium and its migration mechanisms in groundwater, hydrolysis, redox behaviour, compound formation in carbonate solutions and colloid formation were examined in groundwater conditions, i.e. at pH values between 5 and 8 and at redox potentials of between -300 and +700 mV. Solubility measurements, spectroscopic processes (UV, VIS, IR spectroscopy and laser induced photoacoustic spectroscopy) and electrochemical processes (cyclic voltammetry, differential pulse polarography) are used as methods of investigation. The hydrolysis constants of Pu IV and Pu VI and the solubility product of Pu (OH) 4 were determined and hydrolysis products of divalent and trivalent type are described. From solubility experiments, the stability constants for Pu (IV) carbonate compounds and the solubility product for the carbonate system of stable bodies of Pu (OH) 2 CO 3 were calculated. Using absorption spectroscopy, the disproportionate kinetics of Pu (V) in carbonate was determined at various pH values. A slow, but continuous, reduction in Pu (VI) was found in carbonate solution, which was derived from radiolytic effects. The speed of this auto-reduction was determined, depending on various experimental parameters. (orig./RB) [de

  14. Project Work Plan Carbon Tetrachloride and Chloroform Attenuation Parameter Studies: Heterogeneous Hydrolytic Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Amonette, James E.; Truex, Michael J.; Fruchter, Jonathan S.

    2006-06-01

    Between 1955 and 1973, an estimated 750,000 kg of carbon tetrachloride were discharged to the soil in the 200 West Area of the Hanford Site as part of the plutonium production process. Of this amount, some carbon tetrachloride reached the groundwater more than 70 m below the ground surface and formed a plume of 10 km2. Recent information has shown that the carbon tetrachloride plume extends to a depth of at least 60 m below the water table. Some carbon tetrachloride has been degraded either by the original process or subsequent transformations in the subsurface to form a co-existing chloroform plume. Although current characterization efforts are improving the conceptual model of the source area, more information is needed to effectively assess the fate and transport of carbon tetrachloride and chloroform to support upcoming remediation decisions for the plume. As noted in a simulation study by Truex et al. (2001), parameters describing porosity, sorption, and abiotic degradation have the largest influence on predicted plume behavior. The work proposed herein will improve the ability to predict future plume movement by better quantifying abiotic degradation mechanisms and rates. This effort will help define how much active remediation may be needed and estimate where the plume will eventually stabilize – key factors in determining the most appropriate remedy for the plume.

  15. DETERMINATION OF CRITICAL VALUE OF pH OF GEL FORMATION IN SILICATE-ALKALI MIXTURES OF VARIOUS COMPOSITION

    Directory of Open Access Journals (Sweden)

    Оlga Titova

    2017-07-01

    Full Text Available Purpose: The aim of this study is the research of a possibility of a direct and reverse titration usage for the critical pH determination. pH value change of the silicate-alkali mixture was analyzed while addition of alkalis, salt water and sodium hydrogen carbonate solutions. Methods: Methods of direct and reverse titration were used for the determination of various additives influence on results of pH measuring of sodium silicate mixtures. Results: Additives method or reverse titration of the alkali solution are the most appropriate methods for the determination of free alkali content in silicate solutions. Dilution of silicate-alkali solutions by salt water or its model leads to the faster decrease of pH value, than in case of water without any salts of hardness. Hydrogen carbonates influence should be accounted when execution of accurate calculations used in the development of silicate-alkali mixtures usage technology. Discussion: Alkali-silicate mixtures would be solutions for a long time when filtration proceeds in the porous medium at рН > рНcrit. The time of such solutions existence must be characterized by a before inductive period. When reaching the critical pH value, a gel is formed during an inductive period or the time of gel formation. As a rule, the before inductive period is in ten times or even more greater than the time of gel formation.

  16. γ'-Selective Functionalization of Cyclic Enones: Construction of a Chiral Quaternary Carbon Center by [4+2] Cycloaddition/Retro-Mannich Reaction with 3-Substituted Maleimides.

    Science.gov (United States)

    Zou, Chuncheng; Zeng, Chuikun; Liu, Zhen; Lu, Min; Sun, Xiaohua; Ye, Jinxing

    2016-11-07

    The first example of organocatalyzed γ'-selective functionalization of cyclic enones with 3-substituted maleimides results in the stereoselective construction quaternary carbon center is presented. The reactions provided γ'-functionalized cyclic enones and β-functionalized cyclopentenones in good to excellent yields with excellent diastereo- and enantioselectivities. DFT calculations indicated that the reaction might proceed as a [4+2] cycloaddition/retro-Mannich reaction which could explain the unexpected product with a chiral quaternary carbon center and the excellent stereoselectivity. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. The alkali metals: 200 years of surprises.

    Science.gov (United States)

    Dye, James L

    2015-03-13

    Alkali metal compounds have been known since antiquity. In 1807, Sir Humphry Davy surprised everyone by electrolytically preparing (and naming) potassium and sodium metals. In 1808, he noted their interaction with ammonia, which, 100 years later, was attributed to solvated electrons. After 1960, pulse radiolysis of nearly any solvent produced solvated electrons, which became one of the most studied species in chemistry. In 1968, alkali metal solutions in amines and ethers were shown to contain alkali metal anions in addition to solvated electrons. The advent of crown ethers and cryptands as complexants for alkali cations greatly enhanced alkali metal solubilities. This permitted us to prepare a crystalline salt of Na(-) in 1974, followed by 30 other alkalides with Na(-), K(-), Rb(-) and Cs(-) anions. This firmly established the -1 oxidation state of alkali metals. The synthesis of alkalides led to the crystallization of electrides, with trapped electrons as the anions. Electrides have a variety of electronic and magnetic properties, depending on the geometries and connectivities of the trapping sites. In 2009, the final surprise was the experimental demonstration that alkali metals under high pressure lose their metallic character as the electrons are localized in voids between the alkali cations to become high-pressure electrides! © 2015 The Author(s) Published by the Royal Society. All rights reserved.

  18. luminescence in coloured alkali halide crystals

    Indian Academy of Sciences (India)

    irradiated alkali halide crystals are similar to the luminescence excited by high energy radiation. Ueta et al [11] ... emission, a correlation between the deformation bleaching and mechanoluminescence of coloured alkali ..... [32] V P Zakrevskii, T S Orlova and A V Shuldiner, J. Solid State 37, 675 (1995). [33] C D Clark and ...

  19. Application of carbon dioxide towards the development of smart materials, green reaction schemes and metallic nanoparticle synthesis

    Science.gov (United States)

    Mohammed, Fiaz S.

    Global carbon dioxide (CO2) emissions have steadily risen over the last 50 years, with 34 billion tons of CO2 released in 2009 alone. Its potential as a greenhouse gas has negatively affected of our lives and environment by the resulting ocean acidification and climate change. To mitigate atmospheric CO2, various strategies have been implemented for CO2 separation, capture, storage and use as a chemical feedstock. The use of CO2 in various chemical industries is attractive as its non-flammable, non-toxic, and relatively inert properties have made it an inherently safer alternative to traditional organic solvents, as well as, a greener carbon feedstock. Also, the accessible critical properties, appreciable critical density, high diffusivity and tunable thermophysical properties make liquid and supercritical CO2 an attractive solvent for industrial applications. In recent years, significant progress has been made in the field of tunable solvent media by employing the reversible reaction of CO2 with amines to produce carbamates. This class of compounds possesses ionic properties that are significantly different from their amines resulting in a non-ionic to ionic switching mechanism that provides for switchable solvent properties, reversible surfactants, low molecular weight organogelators and stimuli responsive materials. The focus of this dissertation is therefore the implementation of the reversible CO2—amine reaction for the formation of smart surfaces, greener amine protection mechanisms, and cationic metallic nanoparticle synthesis. Chapter 2 of this dissertation demonstrates the reversible reaction of CO2 with amine-containing self-assembled monolayers to yield "smart" surfaces that undergo a reversible change in structure, charge, and wettability upon reaction with CO2. The formation carbamate esters are also a widely implemented mechanism for amine protection during organic synthesis. However, traditional methods of protection incur increased solvent use and

  20. Redox Reactions of Metalloporphyrins and their Role in Catalyzed Reduction of Carbon Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Neta, P.

    2002-09-01

    Pulse radiolysis and laser photolysis are used to study redox processes of metalloporphyrins and related complexes in order to evaluate these light absorbing molecules as sensitizers and intermediates in solar energy conversion schemes. The main thrust of the current studies is to investigate the role of reduced metalloporphyrins as intermediates in the catalyzed reduction of carbon dioxide. Studies involve cobalt and iron porphyrins, phthalocyanines, corroles, and corrins as homogeneous catalysts for reduction of carbon dioxide in solution. The main aim is to understand the mechanisms of these photochemical schemes in order to facilitate their potential utilization.

  1. Cesium Carbonate as a Heterogeneous Base Catalyst for Synthesis of 2-Aminothiophenes via Gewald Reaction

    International Nuclear Information System (INIS)

    Moeinpour, Farid; Omidinia, Raheleh; Dorostkar-Ahmadi, Nadieh; Khoshdeli, Bentalhoda

    2011-01-01

    We have reported a new simple catalytic method for the synthesis of 2-aminothiophenes via Gewald reaction using Cs 2 CO 3 as an efficient, reusable and green heterogeneous catalyst under heating conditions in refluxing ethanol. The catalyst could be recycled after a simple workup and reused at least three runs without appreciable reduction in its catalytic activity. Low catalyst loading, clean reaction profiles, simple experimental and workup procedures and high yields are some advantages of this protocol. The synthesis of substituted 2-aminothiophenes is attractive to chemical researchers as they are important intermediates in organic synthesis and frequently used as the scaffold motif of a variety of agrochemicals, dyes, and biologically active products. Thus, because of their wide utility, researchers have synthesized the substituted 2-aminothiophenes via efficient and convenient methods. The one-pot cyclocondensation of ketones with an activated α-hydrogen, a cyanomethylene containing an electron-withdrawing group such as cyanoacetate and elemental sulfur in the presence of organic base, for example, morpholine, diethylamine, etc, known as the Gewald reaction, has been one of the most well-studied multicomponent reactions in recent years. To extend the scope of the reaction, many alterations have been made to the original Gewald's base-catalyzed, two-component combination of α-mercapto ketones with cyanoacetate by varying the components and the conditions

  2. Cesium Carbonate as a Heterogeneous Base Catalyst for Synthesis of 2-Aminothiophenes via Gewald Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Moeinpour, Farid [Islamic Azad University, Bandar Abbas Branch, Abbas (Iran, Islamic Republic of); Omidinia, Raheleh; Dorostkar-Ahmadi, Nadieh; Khoshdeli, Bentalhoda [Islamic Azad University, Mashhad Branch, Mashhad (Iran, Islamic Republic of)

    2011-06-15

    We have reported a new simple catalytic method for the synthesis of 2-aminothiophenes via Gewald reaction using Cs{sub 2}CO{sub 3} as an efficient, reusable and green heterogeneous catalyst under heating conditions in refluxing ethanol. The catalyst could be recycled after a simple workup and reused at least three runs without appreciable reduction in its catalytic activity. Low catalyst loading, clean reaction profiles, simple experimental and workup procedures and high yields are some advantages of this protocol. The synthesis of substituted 2-aminothiophenes is attractive to chemical researchers as they are important intermediates in organic synthesis and frequently used as the scaffold motif of a variety of agrochemicals, dyes, and biologically active products. Thus, because of their wide utility, researchers have synthesized the substituted 2-aminothiophenes via efficient and convenient methods. The one-pot cyclocondensation of ketones with an activated α-hydrogen, a cyanomethylene containing an electron-withdrawing group such as cyanoacetate and elemental sulfur in the presence of organic base, for example, morpholine, diethylamine, etc, known as the Gewald reaction, has been one of the most well-studied multicomponent reactions in recent years. To extend the scope of the reaction, many alterations have been made to the original Gewald's base-catalyzed, two-component combination of α-mercapto ketones with cyanoacetate by varying the components and the conditions.

  3. Interplay between Reaction and Phase Behaviour in Carbon Dioxide Hydrogenation to Methanol.

    Science.gov (United States)

    Reymond, Helena; Amado-Blanco, Victor; Lauper, Andreas; Rudolf von Rohr, Philipp

    2017-03-22

    Condensation promotes CO 2 hydrogenation to CH 3 OH beyond equilibrium through in situ product separation. Although primordial for catalyst and reactor design, triggering conditions as well as the impact on sub-equilibrium reaction behaviour remain unclear. Herein we used an in-house designed micro-view-cell to gain chemical and physical insights into reaction and phase behaviour under high-pressure conditions over a commercial Cu/ZnO/Al 2 O 3 catalyst. Raman microscopy and video monitoring, combined with online gas chromatography analysis, allowed the complete characterisation of the reaction bulk up to 450 bar (1 bar=0.1 MPa) and 350 °C. Dew points of typical effluent streams related to a parametric study suggest that the improving reaction performance and reverting selectivities observed from 230 °C strongly correlate with (i) a regime transition from kinetic to thermodynamic, and (ii) a phase transition from a single supercritical to a biphasic reaction mixture. Our results advance a rationale behind transitioning CH 3 OH selectivities for an improved understanding of CO 2 hydrogenation under high pressure. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Milk alkali syndrome in an infant with chronic kidney disease

    Directory of Open Access Journals (Sweden)

    Kari JA

    2012-06-01

    Full Text Available Jameela A Kari, Sherif M El DesokyDepartment of Pediatrics and Pediatric Nephrology Unit, King Abdulaziz University, Jeddah, Kingdom of Saudi ArabiaAbstract: We report a case of milk alkali syndrome in a 15-month-old infant who had chronic kidney disease. His kidney function worsened, with creatinine raised from 1.11 mg/dL (98 µmol/L to 3.98 mg/dL (350.3 µmol/L, normal 0.4–1.0 mg/dL (35–91 µmol. He had hypercalcemia, serum calcium level 3.11 (normal 2.1–2.6 mmol/L, and metabolic alkalosis, HCO3 48.7 (normal 21–26 mmol/L. His kidney function returned to its base level and his calcium and bicarbonate levels normalized with adjustment of calcium carbonate and sodium bicarbonate doses. We report this case to highlight an unusual complication and to review the literature on milk alkali syndrome which is rare in children.Keywords: milk alkali syndrome, infants, chronic kidney disease

  5. Corrosion resistance of metals and alloys in molten alkalies

    International Nuclear Information System (INIS)

    Zarubitskij, O.G.; Dmitruk, B.F.; Minets, L.A.

    1979-01-01

    Literature data on the corrosion of non-ferrous and noble metals, iron and steels in the molten alkalis and mixtures of their base are presented. It is shown that zirconium, niobium and tantalum are characterized by high corrosion stability in the molten NaOH. Additions of NaOH and KOH to the alkali chloride melts result in a 1000 time decrease of zirconium corrosion rate at 850 deg. The data testify to the characteristic passivating properties of OH - ions; Mo and W do not possess an ability to selfpassivation in hydroxide melts. Corrosion resistance of carbon and chromium-nickel steels in hydroxide melts depends considerably on the temperature, electrolyte composition and atmosphere over them. At the temperatures up to 600 deg C chromium-nickel steel is corrosion resistant in the molten alkali only in the inert atmosphere. Corrosion rate of chromium-nickel alloy is the lower the less chromium and the more nickel it contains. For the small installations the 4Kh18N25S2 and Kh23N28M3D3T steels can be recommended

  6. Mechanism of the alkali degradation of (6-4) photoproduct-containing DNA.

    Science.gov (United States)

    Arichi, Norihito; Inase, Aki; Eto, Sachise; Mizukoshi, Toshimi; Yamamoto, Junpei; Iwai, Shigenori

    2012-03-21

    The (6-4) photoproduct is one of the major damaged bases produced by ultraviolet light in DNA. This lesion is known to be alkali-labile, and strand breaks occur at its sites when UV-irradiated DNA is treated with hot alkali. We have analyzed the product obtained by the alkali treatment of a dinucleoside monophosphate containing the (6-4) photoproduct, by HPLC, NMR spectroscopy, and mass spectrometry. We previously found that the N3-C4 bond of the 5' component was hydrolyzed by a mild alkali treatment, and the present study revealed that the following reaction was the hydrolysis of the glycosidic bond at the 3' component. The sugar moiety of this component was lost, even when a 3'-flanking nucleotide was not present. Glycosidic bond hydrolysis was also observed for a dimer and a trimer containing 5-methyl-2-pyrimidinone, which was used as an analog of the 3' component of the (6-4) photoproduct, and its mechanism was elucidated. Finally, the alkali treatment of a tetramer, d(GT(6-4)TC), yielded 2'-deoxycytidine 5'-monophosphate, while 2'-deoxyguanosine 3'-monophosphate was not detected. This result demonstrated the hydrolysis of the glycosidic bond at the 3' component of the (6-4) photoproduct and the subsequent strand break by β-elimination. It was also shown that the glycosidic bond at the 3' component of the Dewar valence isomer was more alkali-labile than that of the (6-4) photoproduct.

  7. Mesoporous N-doped carbons prepared with thermally removable nanoparticle templates: an efficient electrocatalyst for oxygen reduction reaction.

    Science.gov (United States)

    Niu, Wenhan; Li, Ligui; Liu, Xiaojun; Wang, Nan; Liu, Ji; Zhou, Weijia; Tang, Zhenghua; Chen, Shaowei

    2015-04-29

    Thermally removable nanoparticle templates were used for the fabrication of self-supported N-doped mesoporous carbons with a trace amount of Fe (Fe-N/C). Experimentally Fe-N/C was prepared by pyrolysis of poly(2-fluoroaniline) (P2FANI) containing a number of FeO(OH) nanorods that were prepared by a one-pot hydrothermal synthesis and homogeneously distributed within the polymer matrix. The FeO(OH) nanocrystals acted as rigid templates to prevent the collapse of P2FANI during the carbonization process, where a mesoporous skeleton was formed with a medium surface area of about 400 m(2)/g. Subsequent thermal treatments at elevated temperatures led to the decomposition and evaporation of the FeO(OH) nanocrystals and the formation of mesoporous carbons with the surface area markedly enhanced to 934.8 m(2)/g. Electrochemical measurements revealed that the resulting mesoporous carbons exhibited apparent electrocatalytic activity for oxygen reduction reactions (ORR), and the one prepared at 800 °C (Fe-N/C-800) was the best among the series, with a more positive onset potential (+0.98 V vs RHE), higher diffusion-limited current, higher selectivity (number of electron transfer n > 3.95 at +0.75 V vs RHE), much higher stability, and stronger tolerance against methanol crossover than commercial Pt/C catalysts in a 0.1 M KOH solution. The remarkable ORR performance was attributed to the high surface area and sufficient exposure of electrocatalytically active sites that arose primarily from N-doped carbons with minor contributions from Fe-containing species.

  8. Reaction induced nucleation and growth v. grain coarsening in contact metamorphic, impure carbonates

    DEFF Research Database (Denmark)

    Berger, Alfons; Brodhag, Sabine; Herwegh, Marco

    2010-01-01

    evolution of these samples are combined with the quantification of the microstructures, i.e. mean grain sizes and crystal size distributions. Growth of the matrix phase and second phases strongly depends on each other owing to coupled grain coarsening. The matrix phase is controlled by the interparticle...... distances between the second phases, while the second phases need the matrix grain boundary network for mass transfer processes during both grain coarsening and mineral reactions. Interestingly, similar final mean grain sizes of primary second phase and second phases newly formed by nucleation are observed...... of grain growth during reactions are orders of magnitudes larger compared to surface energy, allowing new reaction products subjected to fast growth rates to attain similar grain sizes as phases which underwent long-term grain coarsening. In contrast, observed variations in grain size of the same mineral...

  9. Method of handling radioactive alkali metal waste

    Science.gov (United States)

    Wolson, R.D.; McPheeters, C.C.

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

  10. Method of handling radioactive alkali metal waste

    International Nuclear Information System (INIS)

    Mcpheeters, C.C.; Wolson, R.D.

    1980-01-01

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1

  11. Supercritical carbon dioxide as an innovative reaction medium for selective oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Loeker, F.; Leitner, W. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    1998-12-31

    Although the catalytic efficiency of all catalytic oxidation processes studied in scCO{sub 2} up to now is far from being satisfactory, the principle possibility to carry out such reactions in this medium is clearly evident. Future research in our group will be directed towards the development of homogeneous and heterogeneous catalysts that are adopted to the special requirements of both the oxidation process and the supercritical reaction medium. Preliminary results from these studies regarding the epoxidation of olefins with molecular oxygen as oxidant will be presented on the conference poster. (orig.)

  12. Interfacial Reaction During High Energy Ball Milling Dispersion of Carbon Nanotubes into Ti6Al4V

    Science.gov (United States)

    Adegbenjo, A. O.; Olubambi, P. A.; Potgieter, J. H.; Nsiah-Baafi, E.; Shongwe, M. B.

    2017-12-01

    The unique thermal and mechanical properties of carbon nanotubes (CNTs) have made them choice reinforcements for metal matrix composites (MMCs). However, there still remains a critical challenge in achieving homogeneous dispersion of CNTs in metallic matrices. Although high energy ball milling (HEBM) has been reported as an effective method of dispersing CNTs into metal matrices, a careful selection of the milling parameters is important not to compromise the structural integrity of CNTs which may cause interfacial reactions with the matrix. In this study, multi-walled carbon nanotubes (MWCNTs) were purified by annealing in argon and vacuum atmospheres at 1000 and 1800 °C, respectively, for 5 h to remove possible metallic catalyst impurities. Subsequently, 1, 2 and 3 wt.% MWCNTs were dispersed by adapted HEBM into Ti6Al4V alloy metal matrix. Raman spectroscopy (RS), x-ray diffraction, scanning electron microscopy, energy-dispersive x-ray spectrometry and transmission electron microscopy techniques were used to characterize the as-received and annealed MWCNTs, as well as the admixed MWCNT/Ti6Al4V nanocomposite powders. The experimental results showed that vacuum annealing successfully eliminated retained nickel (Ni) catalysts from MWCNTs, while the adapted HEBM method achieved a relative homogeneous dispersion of MWCNTs into the Ti6Al4V matrix and helped to control interfacial reactions between defective MWCNTs and the metal matrix.

  13. Recent Advances in Carbon Supported Metal Nanoparticles Preparation for Oxygen Reduction Reaction in Low Temperature Fuel Cells

    Directory of Open Access Journals (Sweden)

    Yaovi Holade

    2015-03-01

    Full Text Available The oxygen reduction reaction (ORR is the oldest studied and most challenging of the electrochemical reactions. Due to its sluggish kinetics, ORR became the major contemporary technological hurdle for electrochemists, as it hampers the commercialization of fuel cell (FC technologies. Downsizing the metal particles to nanoscale introduces unexpected fundamental modifications compared to the corresponding bulk state. To address these fundamental issues, various synthetic routes have been developed in order to provide more versatile carbon-supported low platinum catalysts. Consequently, the approach of using nanocatalysts may overcome the drawbacks encountered in massive materials for energy conversion. This review paper aims at summarizing the recent important advances in carbon-supported metal nanoparticles preparation from colloidal methods (microemulsion, polyol, impregnation, Bromide Anion Exchange… as cathode material in low temperature FCs. Special attention is devoted to the correlation of the structure of the nanoparticles and their catalytic properties. The influence of the synthesis method on the electrochemical properties of the resulting catalysts is also discussed. Emphasis on analyzing data from theoretical models to address the intrinsic and specific electrocatalytic properties, depending on the synthetic method, is incorporated throughout. The synthesis process-nanomaterials structure-catalytic activity relationships highlighted herein, provide ample new rational, convenient and straightforward strategies and guidelines toward more effective nanomaterials design for energy conversion.

  14. Creation of Ge-Nx-Cy Configures in Carbon Nanotubes: Origin of Enhanced Electrocatalytic Performance for Oxygen Reduction Reaction.

    Science.gov (United States)

    She, Xilin; Li, Qianqian; Ma, Na; Sun, Jin; Jing, Dengwei; Chen, Chengmeng; Yang, Lijun; Yang, Dongjiang

    2016-04-27

    High-performance nitrogen and germanium codoped carbon nanotubes (N-Ge-CNTs) were synthesized as oxygen reduction reaction (ORR) catalysts by one-step sintering of carboxyethyl germanium sesquioxide and multiwalled CNTs in NH3 atmosphere. The ORR electrocatalytic activity evaluation was performed by using limited current density, selective reaction pathway, onset potential, H2O2 yields, and kinetic current density. In comparison with Ge or N solely doped CNTs, the codoped samples display more excellent ORR catalytic performance. It was observed that the codoped GeN3C, GeN4, and GeN4 + NC3 microstructures in N-Ge-CNTs are crucial to improving ORR catalytic performance, such as ideal 4 electron pathway (3.95) and positive onset potential (-0.08 V). The high ORR performance is attributed to the synergistic effect of N and Ge doping, which is capable of activating the π electrons of sp(2) hybridized orbital around carbon nantotubes. The ORR catalytic synergistic effect has also been verified by calculating the work function on the basis of density functional theory (DFT).

  15. Fabrication of calcite blocks from gypsum blocks by compositional transformation based on dissolution-precipitation reactions in sodium carbonate solution.

    Science.gov (United States)

    Ishikawa, Kunio; Kawachi, Giichiro; Tsuru, Kanji; Yoshimoto, Ayami

    2017-03-01

    Calcium carbonate (CaCO 3 ) has been used as a bone substitute, and is a precursor for carbonate apatite, which is also a promising bone substitute. However, limited studies have been reported on the fabrication of artificial calcite blocks. In the present study, cylindrical calcite blocks (ϕ6×3mm) were fabricated by compositional transformation based on dissolution-precipitation reactions using different calcium sulfate blocks as a precursor. In the dissolution-precipitation reactions, both CaSO 4 ·2H 2 O and CaSO 4 transformed into calcite, a polymorph of CaCO 3 , while maintaining their macroscopic structure when immersed in 1mol/L Na 2 CO 3 solution at 80°C for 1week. The diametral tensile strengths of the calcite blocks formed using CaSO 4 ·2H 2 O and CaSO 4 were 1.0±0.3 and 2.3±0.7MPa, respectively. The fabrication of calcite blocks using CaSO 4 ·2H 2 O and CaSO 4 proposed in this investigation may be a useful method to produce calcite blocks because of the self-setting ability and high temperature stability of gypsum precursors. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Determination of the percentage of quitine desacetilation reaction by solid state carbon-13 NMR

    International Nuclear Information System (INIS)

    Ferracin, Ricardo J.; Cass, Quezia B.; Bassi, Ana L.

    1997-01-01

    Quitine is a bi-polymer largely found in invertebrates. As most compounds of this class are insoluble in common organic solvents, the des-acetylation percentile was obtained by carbon-13 solid state nuclear magnetic resonance. The methodology is presented. Results are presented

  17. Analysis of unburned carbon in industrial ashes from biomass combustion by thermogravimetric method using Boudouard reaction

    Czech Academy of Sciences Publication Activity Database

    Straka, Pavel; Náhunková, Jana; Žaloudková, Margit

    2014-01-01

    Roč. 575, JAN (2014), s. 188-194 ISSN 0040-6031 R&D Projects: GA MZe QI102A207 Institutional support: RVO:67985891 Keywords : unburned carbon * biomass * ash * thermogravimetry Subject RIV: GD - Fertilization, Irrigation, Soil Processing Impact factor: 2.184, year: 2014 http://www.sciencedirect.com/science/article/pii/S0040603113005455

  18. Miniaturized reaction chamber for optimized laser-assisted carbon nanotube growth

    NARCIS (Netherlands)

    Burgt, Y. van de; Loon, W. van; Mandamparambil, R.; Bellouard, Y.

    2014-01-01

    The localized growth of carbon nanotube structures has potential in many applications such as interconnects, field emitters and sensors. Using a laser to locally heat the substrate offers a highly versatile process compatible with a broad range of substrates and devices. However, for laser-assisted

  19. Sustainable Ways of Combining Reactions and Separations Using Ionic Liquids and Carbon Dioxide

    NARCIS (Netherlands)

    Kazemi, S.

    2013-01-01

    Traditional chemical processes show shortcomings caused by using volatile organic compounds as solvents during reactions and separations. Therefore, it is necessary to address this issue by moving toward more environmentally friendly processes. This is possible by using less toxic and hazardous

  20. Ruthenium supported on nitrogen-doped carbon nanotubes for the oxygen reduction reaction in alkaline

    CSIR Research Space (South Africa)

    Mabena, LF

    2012-10-01

    Full Text Available between 0 and 10 wt.%. The activity of the prepared nanocatalysts toward the oxygen reduction reaction (ORR) was characterized using the rotating disk electrode and voltammetry techniques. The ORR activity was higher at lower concentrations of Ru on N...