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Sample records for ni-based organometallic compounds

  1. Organometallic compounds in cancer therapy: past lessons and future directions.

    Science.gov (United States)

    Martins, Pedro; Marques, Mara; Coito, Lidia; Pombeiro, Armando J L; Baptista, Pedro Viana; Fernandes, Alexandra R

    2014-01-01

    Over the past few years, modern medicinal chemistry has evolved towards providing us new and alternative chemotherapeutic compounds with high cytotoxicity towards tumor cells, alongside with reduced side effects in cancer patients. Organometallic compounds and their unique physic-chemical properties typically used in homogenous catalysis are now being translated as potential candidates for medical purposes. Their structural diversity, ligand exchange, redox and catalytic properties make them promising drug candidates for cancer therapy. Over the last decade this area has witnessed a steady growth and a few organometallic compounds have in fact already entered clinical trials, emphasizing its increasing importance and clinical relevance. Here we intend to stress out the different applications of organometallic compounds in medicine with emphasis on cancer therapy, as well as address setbacks regarding formulation issues, systemic toxicity and off-target effects. Advantages over classical coordination metal complexes, their nanovectorisation and specific molecular targets are also discussed.

  2. Research Progress on Ni-Based Antiperovskite Compounds

    Directory of Open Access Journals (Sweden)

    P. Tong

    2012-01-01

    Full Text Available The superconductivity in antiperovskite compound MgCNi3 was discovered in 2001 following the discovery of the superconducting MgB2. In spite of its lower superconducting transition temperature (8 K than MgB2 (39 K, MgCNi3 has attracted considerable attention due to its high content of magnetic element Ni and the cubic structure analogous to the perovskite cuprates. After years of extensive investigations both theoretically and experimentally, however, it is still not clear whether the mechanism for superconductivity is conventional or not. The central issue is if and how the ferromagnetic spin fluctuations contribute to the cooper paring. Recently, the experimental results on the single crystals firstly reported in 2007 trend to indicate a conventional s-wave mechanism. Meanwhile many compounds neighboring to MgCNi3 were synthesized and the physical properties were investigated, which enriches the physics of the Ni-based antiperovskite compounds and help understand the superconductivity in MgCNi3. In this paper, we summarize the research progress in these two aspects. Moreover, a universal phase diagram of these compounds is presented, which suggests a phonon-mediated mechanism for the superconductivity, as well as a clue for searching new superconductors with the antiperovskite structure. Finally, a few possible scopes for future research are proposed.

  3. Molecular switches in carbon-rich organometallic compounds: Theoretical aspects

    Energy Technology Data Exchange (ETDEWEB)

    Costuas, Karine, E-mail: kcostuas@univ-rennes1.fr [Sciences chimiques de Rennes, UMR 6226 CNRS - Université de Rennes 1, Avenue du Général Leclerc F-35042 Rennes (France)

    2015-01-22

    Organometallic complexes associated with an appropriate choice of ancillary ligands reveal to have a wide range of physical properties leading to promising applications when incorporated in nano-size devices. The challenge is to design innovative multifunctional compounds based on redox active carbon-rich organometallics associated with spin carriers and/or photochromic units. A multidisciplinary approach in this area has proved to be efficient in a series a systems combining carbon-rich bridging ligands and redox metallic moieties. In this domain, the role of theoretical investigations based on quantum mechanics tools have a crucial role in rationalizing and in helping designing systems possessing target properties.

  4. Progress towards bioorthogonal catalysis with organometallic compounds.

    Science.gov (United States)

    Völker, Timo; Dempwolff, Felix; Graumann, Peter L; Meggers, Eric

    2014-09-22

    The catalysis of bioorthogonal transformations inside living organisms is a formidable challenge--yet bears great potential for future applications in chemical biology and medicinal chemistry. We herein disclose highly active organometallic ruthenium complexes for bioorthogonal catalysis under biologically relevant conditions and inside living cells. The catalysts uncage allyl carbamate protected amines with unprecedented high turnover numbers of up to 270 cycles in the presence of water, air, and millimolar concentrations of thiols. By live-cell imaging of HeLa cells and with the aid of a caged fluorescent probe we could reveal a rapid development of intense fluorescence within the cellular cytoplasm and therefore support the proposed bioorthogonality of the catalysts. In addition, to illustrate the manifold applications of bioorthogonal catalysis, we developed a method for catalytic in-cell activation of a caged anticancer drug, which efficiently induced apoptosis in HeLa cells.

  5. Structural Representation of Organometallics and Coordination Compounds and a Recommended Representation by Use of Dashed Lines

    Directory of Open Access Journals (Sweden)

    Shu-Kun Lin

    2002-12-01

    Full Text Available By using broken lines to represent coordination interactions in organometallic and other coordinated compounds, we can draw structures satisfying the valencies of the atoms present. These broken lines should be used to replace many false single covalent bonds now used to depict organometallic and coordinated compounds. Chemical drawing software should not recognize such broken lines as single covalent bonds and they should be ignored. An example of confusing and erroneous structural representation of organometallics and coordination compounds is discussed.

  6. Complexation of DNA with ruthenium organometallic compounds: the high complexation ratio limit.

    Science.gov (United States)

    Despax, Stéphane; Jia, Fuchao; Pfeffer, Michel; Hébraud, Pascal

    2014-06-14

    Interactions between DNA and ruthenium organometallic compounds are studied by using visible light absorption and circular dichroism measurements. A titration technique allowing for the absolute determination of the advancement degree of the complexation, without any assumption about the number of complexation modes is developed. When DNA is in excess, complexation involves intercalation of one of the organometallic compound ligands between DNA base pairs. But, in the high complexation ratio limit, where organometallic compounds are in excess relative to the DNA base pairs, a new mode of interaction is observed, in which the organometallic compound interacts weakly with DNA. The weak interaction mode, moreover, develops when all the DNA intercalation sites are occupied. A regime is reached in which one DNA base pair is linked to more than one organometallic compound.

  7. Separation of metal chelates and organometallic compounds by SFC and SFE/GC.

    Science.gov (United States)

    Wai, C M; Wang, S

    2000-07-05

    Supercritical fluid chromatography (SFC) combines the high diffusion coefficients of gas chromatography (GC) and the solubility properties of liquid chromatography (LC). SFC generally requires lower temperatures for chromatographic separations and thus is more suitable for analyzing thermally labile compounds including a number of metal chelates and organometallic compounds. SFC also allows interfacing between supercritical fluid extraction (SFE) and chromatographic analysis of metal-containing compounds. A large number of metal chelates and organometallic compounds can be separated by SFC. This article summarizes SFC separation of various chelates of transition metals, heavy metals, lanthanides and actinides as well as organometallic compounds of lead, mercury, and tin reported in the recent literature. This article also discusses SFC detection systems and the determination of solubility of organometallic compounds by SFC.

  8. A Review of the Tissue Residue Approach for Organic and Organometallic Compounds in Aquatic Organisms

    Science.gov (United States)

    This paper reviews the tissue residue approach (TRA) for toxicity assessment as it applies to organic chemicals and some organometallic compounds (tin, mercury, and lead). Specific emphasis was placed on evaluating key factors that influence interpretation of critical body resid...

  9. Group 9 organometallic compounds for therapeutic and bioanalytical applications.

    Science.gov (United States)

    Ma, Dik-Lung; Chan, Daniel Shiu-Hin; Leung, Chung-Hang

    2014-12-16

    CONSPECTUS: Compared with organic small molecules, metal complexes offer several distinct advantages as therapeutic agents or biomolecular probes. Carbon atoms are typically limited to linear, trigonal planar, or tetrahedral geometries, with a maximum of two enantiomers being formed if four different substituents are attached to a single carbon. In contrast, an octahedral metal center with six different substituents can display up to 30 different stereoisomers. While platinum- and ruthenium-based anticancer agents have attracted significant attention in the realm of inorganic medicinal chemistry over the past few decades, group 9 complexes (i.e., iridium and rhodium) have garnered increased attention in therapeutic and bioanalytical applications due to their adjustable reactivity (from kinetically liable to substitutionally inert), high water solubility, stability to air and moisture, and relative ease of synthesis. In this Account, we describe our efforts in the development of group 9 organometallic compounds of general form [M(C(∧)N)2(N(∧)N)] (where M = Ir, Rh) as therapeutic agents against distinct biomolecular targets and as luminescent probes for the construction of oligonucleotide-based assays for a diverse range of analytes. Earlier studies by researchers had focused on organometallic iridium(III) and rhodium(III) half-sandwich complexes that show promising anticancer activity, although their precise mechanisms of action still remain unknown. More recently, kinetically-inert group 9 complexes have arisen as fascinating alternatives to organic small molecules for the specific targeting of enzyme activity. Research in our laboratory has shown that cyclometalated octahedral rhodium(III) complexes were active against Janus kinase 2 (JAK2) or NEDD8-activating enzyme (NAE) activity, or against NO production leading to antivasculogenic activity in cellulo. At the same time, recent interest in the development of small molecules as modulators of protein

  10. A golden future in medicinal inorganic chemistry: the promise of anticancer gold organometallic compounds.

    Science.gov (United States)

    Bertrand, Benoît; Casini, Angela

    2014-03-21

    From wedding rings on fingers to stained glass windows, by way of Olympic medals, gold has been highly prized for millennia. Nowadays, organometallic gold compounds occupy an important place in the field of medicinal inorganic chemistry due to their unique chemical properties with respect to gold coordination compounds. In fact, several studies have proved that they can be used to develop highly efficient metal-based drugs with possible applications in the treatment of cancer. This Perspective summarizes the results obtained for different families of bioactive organometallic gold compounds including cyclometallated gold(iii) complexes with C,N-donor ligands, gold(I) and gold(I/III) N-heterocyclic (NHC) carbene complexes, as well as gold(I) alkynyl complexes, with promising anticancer effects. Most importantly, we will focus on recent developments in the field and discuss the potential of this class of organometallic compounds in relation to their versatile chemistry and innovative mechanisms of action.

  11. Nitrogen Doped Carbon Nanotubes from Organometallic Compounds: A Review

    Directory of Open Access Journals (Sweden)

    Neil J. Coville

    2010-03-01

    Full Text Available Nitrogen doped carbon nanotubes (N-CNTs have become a topic of increased importance in the study of carbonaceous materials. This arises from the physical and chemical properties that are created when N is embedded in a CNT. These properties include modified chemical reactivity and modified conductivity and mechanical properties. A range of methodologies have been devised to synthesize N-CNTs. One of the procedures uses a floating catalyst in which an organometallic complex is decomposed in the gas phase in the presence of a nitrogen containing reactant to give N-CNTs. Most studies have been limited to ferrocene, ring substituted ferrocene and Fe(CO5. This review covers the synthesis (and properties of N-CNTs and other shaped carbon nanomaterials (SCNMs produced using organometallic complexes. It summarizes the effects that physical parameters such as temperature, pressure, gas flow rates, type and concentration of N source etc. have on the N-CNT type, size and yields as well as the nitrogen content incorporated into the tubes that are produced from organometallic complexes. Proposed growth models for N-CNT synthesis are also reported.

  12. A golden future in medicinal inorganic chemistry : The promise of anticancer gold organometallic compounds

    NARCIS (Netherlands)

    Bertrand, B.; Casini, A.

    2014-01-01

    From wedding rings on fingers to stained glass windows, by way of Olympic medals, gold has been highly prized for millennia. Nowadays, organometallic gold compounds occupy an important place in the field of medicinal inorganic chemistry due to their unique chemical properties with respect to gold co

  13. A golden future in medicinal inorganic chemistry : The promise of anticancer gold organometallic compounds

    NARCIS (Netherlands)

    Bertrand, B.; Casini, A.

    2014-01-01

    From wedding rings on fingers to stained glass windows, by way of Olympic medals, gold has been highly prized for millennia. Nowadays, organometallic gold compounds occupy an important place in the field of medicinal inorganic chemistry due to their unique chemical properties with respect to gold co

  14. Using Molecular Modeling in Teaching Group Theory Analysis of the Infrared Spectra of Organometallic Compounds

    Science.gov (United States)

    Wang, Lihua

    2012-01-01

    A new method is introduced for teaching group theory analysis of the infrared spectra of organometallic compounds using molecular modeling. The main focus of this method is to enhance student understanding of the symmetry properties of vibrational modes and of the group theory analysis of infrared (IR) spectra by using visual aids provided by…

  15. Homogeneous photocatalytic reactions with organometallic and coordination compounds--perspectives for sustainable chemistry.

    Science.gov (United States)

    Hoffmann, Norbert

    2012-02-13

    Since the time of Giacomo Ciamician at the beginning of the 20th century, photochemical transformations have been recognized as contributing to sustainable chemistry. Electronic excitation significantly changes the reactivity of chemical compounds. Thus, the application of activation reagents is frequently avoided and transformations can be performed under mild conditions. Catalysis plays a central role in sustainable chemistry. Stoichiometric amounts of activation reagents are often avoided. This fact and the milder catalytic reaction conditions diminish the formation of byproducts. In the case of homogeneous catalysis, organometallic compounds are often applied. The combination of both techniques develops synergistic effects in the sense of "Green Chemistry". Herein, metal carbonyl-mediated reactions are reported. These transformations are of considerable interest for the synthesis of complex polyfunctionalized compounds. Copper(I)-catalyzed [2+2] photocycloaddition gives access to a large variety of cyclobutane derivatives. Currently, a large number of publications deal with photochemical electron-transfer-induced reactions with organometallic and coordination compounds, particularly with ruthenium complexes. Several photochemically induced oxidations can easily be performed with air or molecular oxygen when they are catalyzed with organometallic complexes. Photochemical reaction conditions also play a certain role in C-H activation with organometallic catalysts, for instance, with alkanes, although such transformations are conveniently performed with a variety of other photochemical reactions.

  16. Assessing protein-ligand docking for the binding of organometallic compounds to proteins.

    Science.gov (United States)

    Ortega-Carrasco, Elisabeth; Lledós, Agusti; Maréchal, Jean-Didier

    2014-01-30

    Organometallic compounds are increasingly used as molecular scaffolds in drug development projects; their structural and electronic properties offering novel opportunities in protein-ligand complementarities. Interestingly, while protein-ligand dockings have long become a spearhead in computer assisted drug design, no benchmarking nor optimization have been done for their use with organometallic compounds. Pursuing our efforts to model metal mediated recognition processes, we herein present a systematic study of the capabilities of the program GOLD to predict the interactions of protein with organometallic compounds. The study focuses on inert systems for which no alteration of the first coordination sphere of the metal occurs upon binding. Several scaffolds are used as test systems with different docking schemes and scoring functions. We conclude that ChemScore is the most robust scoring function with ASP and ChemPLP providing with good results too and GoldScore slightly underperforming. This study shows that current state-of-the-art protein-ligand docking techniques are reliable for the docking of inert organometallic compounds binding to protein.

  17. Using Molecular Modeling in Teaching Group Theory Analysis of the Infrared Spectra of Organometallic Compounds

    Science.gov (United States)

    Wang, Lihua

    2012-01-01

    A new method is introduced for teaching group theory analysis of the infrared spectra of organometallic compounds using molecular modeling. The main focus of this method is to enhance student understanding of the symmetry properties of vibrational modes and of the group theory analysis of infrared (IR) spectra by using visual aids provided by…

  18. Hydrogenation of ethyl acetate to ethanol over Ni-based catalysts obtained from Ni/Al hydrotalcite-like compounds.

    Science.gov (United States)

    Zhang, Beixiao; Lin, Lu; Zhuang, Junping; Liu, Ying; Peng, Lincai; Jiang, Longfei

    2010-07-29

    A series of Ni-based catalysts were prepared using hydrogen reduction of Ni/Al hydrotalcite-like compounds (Ni/Al HTlcs) synthesized by coprecipitation. The physico-chemical properties of Ni/Al hydrotalcite-like compounds and the corresponding Ni-based catalysts were characterized using inductively coupled plasma (ICP), BET surface areas, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) techniques. The results indicated that Ni/Al HTlcs with layered structures could be successfully prepared by the coprecipitation method, and the characteristic HTlcs reflections were also observed in the XRD analysis. The NiO and Ni0 phases were identified in all Ni-based catalysts, which displayed randomly interconnected pores and no layer structures. In addition, the studies also found the Ni/Al HTlcs and Ni-based catalysts had high specific surface areas, low pore volumes and low pore diameters. The catalytic hydrogenation of ethyl acetate to ethanol with Ni-based catalysts was also investigated. Among the studied catalysts, RE1NASH-110-3 showed the highest selectivity and yield of ethyl acetate to ethanol, which were 68.2% and 61.7%, respectively. At the same time, a major by-product, butyl acetate, was formed due to an ester-exchange reaction. A proposed hydrogenation pathway for ethyl acetate over Ni-based catalysts was suggested.

  19. Hydrogenation of Ethyl Acetate to Ethanol over Ni-Based Catalysts Obtained from Ni/Al Hydrotalcite-Like Compounds

    Directory of Open Access Journals (Sweden)

    Longfei Jiang

    2010-07-01

    Full Text Available A series of Ni-based catalysts were prepared using hydrogen reduction of Ni/Al hydrotalcite-like compounds (Ni/Al HTlcs synthesized by coprecipitation. The physico-chemical properties of Ni/Al hydrotalcite-like compounds and the corresponding Ni-based catalysts were characterized using inductively coupled plasma (ICP, BET surface areas, X-ray diffraction (XRD, Fourier transform infrared (FTIR spectroscopy and scanning electron microscopy (SEM techniques. The results indicated that Ni/Al HTlcs with layered structures could be successfully prepared by the coprecipitation method, and the characteristic HTlcs reflections were also observed in the XRD analysis. The NiO and Ni0 phases were identified in all Ni-based catalysts, which displayed randomly interconnected pores and no layer structures. In addition, the studies also found the Ni/Al HTlcs and Ni-based catalysts had high specific surface areas, low pore volumes and low pore diameters. The catalytic hydrogenation of ethyl acetate to ethanol with Ni-based catalysts was also investigated. Among the studied catalysts, RE1NASH-110-3 showed the highest selectivity and yield of ethyl acetate to ethanol, which were 68.2% and 61.7%, respectively. At the same time, a major by-product, butyl acetate, was formed due to an ester-exchange reaction. A proposed hydrogenation pathway for ethyl acetate over Ni-based catalysts was suggested.

  20. Systems and methods for solar energy storage, transportation, and conversion utilizing photochemically active organometallic isomeric compounds and solid-state catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Vollhardt, K. Peter C.; Segalman, Rachel A; Majumdar, Arunava; Meier, Steven

    2015-02-10

    A system for converting solar energy to chemical energy, and, subsequently, to thermal energy includes a light-harvesting station, a storage station, and a thermal energy release station. The system may include additional stations for converting the released thermal energy to other energy forms, e.g., to electrical energy and mechanical work. At the light-harvesting station, a photochemically active first organometallic compound, e.g., a fulvalenyl diruthenium complex, is exposed to light and is photochemically converted to a second, higher-energy organometallic compound, which is then transported to a storage station. At the storage station, the high-energy organometallic compound is stored for a desired time and/or is transported to a desired location for thermal energy release. At the thermal energy release station, the high-energy organometallic compound is catalytically converted back to the photochemically active organometallic compound by an exothermic process, while the released thermal energy is captured for subsequent use.

  1. Metal-rich organometallics.

    Science.gov (United States)

    Krüger, Robin A; Baumgartner, Thomas

    2010-07-07

    The scope of organometallics has recently been expanded considerably, when researchers have started to employ these compounds in the context of materials chemistry. Traditionally, organometallic complexes have been and continue to be important tools for many (catalytic) chemical transformations. This perspective highlights how metal-rich organometallics, that is compounds with more than one type of metal, can play an important role in the advancement of new value-added functional materials.

  2. Cyclopentadienyl-ruthenium(II) and iron(II) organometallic compounds with carbohydrate derivative ligands as good colorectal anticancer agents.

    Science.gov (United States)

    Florindo, Pedro R; Pereira, Diane M; Borralho, Pedro M; Rodrigues, Cecília M P; Piedade, M F M; Fernandes, Ana C

    2015-05-28

    New ruthenium(II) and iron(II) organometallic compounds of general formula [(η(5)-C5H5)M(PP)Lc][PF6], bearing carbohydrate derivative ligands (Lc), were prepared and fully characterized and the crystal structures of five of those compounds were determined by X-ray diffraction studies. Cell viability of colon cancer HCT116 cell line was determined for a total of 23 organometallic compounds and SAR's data analysis within this library showed an interesting dependency of the cytotoxic activity on the carbohydrate moiety, linker, phosphane coligands, and metal center. More importantly, two compounds, 14Ru and 18Ru, matched oxaliplatin IC50 (0.45 μM), the standard metallodrug used in CC chemotherapeutics, and our leading compound 14Ru was shown to be significantly more cytotoxic than oxaliplatin to HCT116 cells, triggering higher levels of caspase-3 and -7 activity and apoptosis in a dose-dependent manner.

  3. NATO Advanced Research Workshop on the Mechanisms of Reactions of Organometallic Compounds with Surfaces

    CERN Document Server

    Williams, J

    1989-01-01

    A NATO Advanced Research Workshop on the "Mechanisms of Reactions of Organometallic Compounds with Surfaces" was held in St. Andrews, Scotland in June 1988. Many of the leading international researchers in this area were present at the workshop and all made oral presentations of their results. In addition, significant amounts of time were set aside for Round Table discussions, in which smaller groups considered the current status of mechanistic knowledge, identified areas of dispute or disagreement, and proposed experiments that need to be carried out to resolve such disputes so as to advance our understanding of this important research area. All the papers presented at the workshop are collected in this volume, together with summaries of the conclusions reached at the Round Table discussions. The workshop could not have taken place without financial support from NATO, and donations were also received from Associated Octel, Ltd., STC Ltd., and Epichem Ltd., for which the organisers are very grateful. The orga...

  4. Organometallic chemistry of bimetallic compounds. Progress report, January 1992--July 1995

    Energy Technology Data Exchange (ETDEWEB)

    Casey, C.P.

    1994-07-01

    Four main projects at the interface between organometallic chemistry and homogeneous catalysis were pursued. All were designed to give increased understanding of the mechanisms of organometallic reactions related to homogeneous and heterogeneous catalysis. In addition, a minor study involving {eta}{sup 5}-to {eta}{sup 1}-cyclopentadienyl ring slippage in catalysis was completed.

  5. Synthesis of heterometallic compounds with uncommon combinations of elements for oxide nanomaterials using organometallics.

    Science.gov (United States)

    John, Łukasz; Sobota, Piotr

    2014-02-18

    Oxide nanomaterials with interesting electronic and magnetic properties have applications including superconductors, magnetic core materials, high-frequency devices, and gas sensors. They can also serve as efficient oxide lattices for luminescent ions. Highly phase-pure BaHfO3 nanopowders are extremely desirable as matrices for luminescent doping, and barium hafnate is an attractive host lattice for new X-ray phosphors, which are much more effective than the phosphors currently used in radiology and computed tomography. This wide range of applications creates a strong impetus for novel and inexpensive methods for their synthesis. Classically, mixed-cation oxide ceramics are synthesized according to conventional solid-state reactions involving oxides, carbonates, or nitrates at relatively high temperatures (∼1500 °C). These procedures are inefficient and often lead to inhomogeneous by-products and poor control over the stoichiometry and phase purity. Among the new preparation techniques are those involving metal alkoxides and aryloxides with strictly defined metal stoichiometries at the molecular level. In this Account, we describe several structurally interesting heterometallic alkoxoorganometallic compounds prepared via reactions of organometallic compounds (MMe3 where M = Al, In, Ga) with group 2 alkoxides having additional protonated hydroxyl group(s) in the alcohol molecule present in the metal coordination sphere. Using lower temperatures than in the conventional solid-state thermal routes involving carbonate/oxide mixtures, we can easily transform these new complexes, with rarely found combinations of metallic precursors (Ba/In, Sr/Al, and Ba/Ga), into highly pure binary oxide materials that can be used, in a similar manner to perovskites and spinels, as host matrices for various lanthanide ions. Furthermore, our studies on titanium, zirconium, and hafnium metallocenes showed them to be attractive and cheap precursors for an extensive range of novel

  6. Strategy to tether organometallic ruthenium-arene anticancer compounds to recombinant human serum albumin.

    Science.gov (United States)

    Ang, Wee Han; Daldini, Elisa; Juillerat-Jeanneret, Lucienne; Dyson, Paul J

    2007-10-29

    In order to utilize macromolecules for drug targeting and delivery, a strategy to tether organometallic ruthenium-arene drugs to carrier protein molecules was developed. The approach involves the design of a drug fragment capable of conjugating to linker molecules on a modified carrier protein via hydrazone bond formation. The proof-of-concept using recombinant human serum albumin is described.

  7. Organometallic chemistry in non-classical environments.

    Science.gov (United States)

    Dyson, Paul J

    2011-01-01

    A summary of our on-going research on organometallic chemistry is provided with an emphasis on the function, reactivity and mechanisms of organometallic compounds in water, ionic liquids and in living systems. The role of organometallic compounds in both catalysis and medicinal chemistry are briefly described.

  8. Development of Ni-Based Catalysts Derived from Hydrotalcite-Like Compounds Precursors for Synthesis Gas Production via Methane or Ethanol Reforming

    Directory of Open Access Journals (Sweden)

    Ya-Li Du

    2017-02-01

    Full Text Available As a favorably clean fuel, syngas (synthesis gas production has been the focus of concern in past decades. Substantial literatures reported the syngas production by various catalytic reforming reactions particularly in methane or ethanol reforming. Among the developed catalysts in these reforming processes, Ni-based catalysts from hydrotalcite-like compounds (HTLcs precursors have drawn considerable attention for their preferable structural traits. This review covers the recent literature reporting syngas production with Ni-based catalysts from HTLc precursors via methane or ethanol reforming. The discussion was initiated with catalyst preparation (including conventional and novel means, followed by subsequent thermal treatment processes, then composition design and the addition of promoters in these catalysts. As Ni-based catalysts have thermodynamic potential to deactivate because of carbon deposition or metal sintering, measures for dealing with these problems were finally summarized. To obtain optimal catalytic performances and resultantly better syngas production, based on analyzing the achievements of the references, some perspectives were finally proposed.

  9. QSPR modeling for enthalpies of formation of organometallic compounds by means of SMILES-based optimal descriptors

    Science.gov (United States)

    Toropov, A. A.; Toropova, A. P.; Benfenati, E.

    2008-08-01

    A quantitative structure-property relationship (QSPR) model for a predicting gas-phase enthalpy of formation have been developed, using as chemical information descriptors based on the simplified molecular input line entry system (SMILES). The model is one-variable equation. The SMILES-based descriptors calculated with correlation weights of SMILES attributes which are obtained by the Monte Carlo method. The model addressed organometallic compounds. Statistical characteristics of the model are the following: n = 104, R2 = 0.9943, Q2 = 0.9940, s = 19.9 (kJ/mol), F = 17701 (training set); n = 28, R2 = 0.9908, Q2 = 0.9892, s = 29.4 (kJ/mol), F = 2788 (test set).

  10. Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds. Sublimation, Vaporization and Fusion Enthalpies From 1880 to 2015. Part 1. C1 - C10

    Science.gov (United States)

    Acree, William; Chickos, James S.

    2016-09-01

    A compendium of phase change enthalpies published in 2010 is updated to include the period 1880-2015. Phase change enthalpies including fusion, vaporization, and sublimation enthalpies are included for organic, organometallic, and a few inorganic compounds. Part 1 of this compendium includes organic compounds from C1 to C10. Part 2 of this compendium, to be published separately, will include organic and organometallic compounds from C11 to C192. Sufficient data are presently available to permit thermodynamic cycles to be constructed as an independent means of evaluating the reliability of the data. Temperature adjustments of phase change enthalpies from the temperature of measurement to the standard reference temperature, T = 298.15 K, and a protocol for doing so are briefly discussed.

  11. Functional Organometallics

    Institute of Scientific and Technical Information of China (English)

    K.H.DTZ

    2007-01-01

    1 Results The lecture will address aspects of functional organometallics related to the development of novel organometallic materials.In chromium complexes of fused arenes-regio-and diastereoselectively accessible by chromium-templated benzannulation of arylcarbenes by alkynes[1]-a haptotropic migration of the chromium fragment along the π-face of fused arenes is controlled by both thermodynamics and the substitution pattern of the arene and the metal coligand sphere,and can be applied towards an organo...

  12. Toward organometallic antischistosomal drug candidates.

    Science.gov (United States)

    Hess, Jeannine; Keiser, Jennifer; Gasser, Gilles

    2015-01-01

    In the recent years, there has been a growing interest in the use of novel approaches for the treatment of parasitic diseases such as schistosomiasis. Among the different approaches used, organometallic compounds were found to offer unique opportunities in the design of antiparasitic drug candidates. A ferrocenyl derivative, namely ferroquine, has even entered clinical trials as a novel antimalarial. In this short review, we report on the studies describing the use of organometallic compounds against schistosomiasis.

  13. First-principles study of the organometallic S =1/2 kagome compound Cu(1,3-bdc)

    Science.gov (United States)

    Liu, Zheng; Mei, Jia-Wei; Liu, Feng

    2015-10-01

    Cu(1,3-benzenedicarboxylate) [Cu(1,3-bdc)] contains structurally perfect kagome planes formed by Cu2 + ions without the presence of diamagnetic defects. This organometallic compound should serve as a precious platform to explore quantum frustrated magnetism, yet the experimental results so far are mysterious, leading to questions such as, "Is Cu(1,3-bdc) just a trivial weak ferromagnet?" Using the density functional theory, we have systematically studied the electronic and magnetic properties of Cu(1,3-bdc), putting forth a theoretical basis to clarify this novel material. We present numerical evidence of a dominating antiferromagnetic (AFM) exchange between nearest-neighbor (NN) Cu2 + as experimentally extracted from the high-temperature susceptibility data. We further show that beyond the NN AFM exchange, the additional interactions in Cu(1,3-bdc) have similar strength as those in the well-studied kagome antiferromagnet, herbertsmithite, by designing a comparative study. In the end, we discuss our understanding of the phase transition and FM signals observed under low temperature.

  14. Reactive organometallics from organotellurides: application in organic synthesis

    OpenAIRE

    PRINCIVAL, Jefferson L.; Santos,Alcindo A. Dos; Comasseto,João V

    2010-01-01

    In this paper the preparation of reactive organometallics starting from organotellurides is reviewed. The application of the reactive organometallics prepared in this way in the synthesis of bioactive compounds is commented.

  15. Synthesis and purification of some main group organometallic precursors for compound semiconductors

    Indian Academy of Sciences (India)

    Vimal K Jain

    2005-07-01

    Metal–organic vapour phase epitaxy/chemical vapour deposition (MOVPE/MOCVD) has emerged recently as the method of choice for large scale preparation of a variety of low dimension inorganic materials; particularly compound semiconductors, used in modern electronic and opto-electronic devices. The success of this process depends on the availability of suitable molecular precursors of desired purity. Group V hydrides (e.g. NH3, PH3, AsH3, SbH3) have been employed conventionally for deposition of III–V semiconductor materials. Inherent weakness of this hydride source, particularly heavier ones (for instance very low utilization (> 0.1%) of AsH3 in GaAs synthesis; ∼ 4 h half life of SbH3 at room temperature) has been a driving force to develop new molecular precursors with desirable properties. This talk will briefly review synthesis and purification of several precursors of groups III (Ga, In), IV, V (As, Sb) and VI (Se, Te).

  16. Organometallic Radiopharmaceuticals

    Science.gov (United States)

    Alberto, Roger

    Although molecular imaging agents have to be synthesized ultimately from aqueous solutions, organometallic complexes are becoming more and more important as flexible yet kinetically stable building blocks for radiopharmaceutical drug discovery. The diversity of ligands, targets, and targeting molecules related to these complexes is an essential base for finding novel, noninvasive imaging agents to diagnose and eventually treat widespread diseases such as cancer. This review article covers the most important findings toward these objectives accomplished during the past 3-4 years. The two major available organometallic building blocks will be discussed in the beginning together with constraints for market introduction as imposed by science and industry. Since targeting radiopharmaceuticals are a major focus of current research in molecular imaging, attempts toward so-called technetium essential radiopharmaceuticals will be briefly touched in the beginning followed by the main discussion about the labeling of targeting molecules such as folic acid, nucleosides, vitamins, carbohydrates, and fatty acids. At the end, some new strategies for drug discovery will be introduced together with results from organometallic chemistry in water. The majority of the new results have been achieved with the [99mTc(OH2)3(CO)3]+ complex which will, though not exclusively, be a focus of this review.

  17. Organometallic complexes: new tools for chemotherapy.

    Science.gov (United States)

    Chavain, N; Biot, C

    2010-01-01

    The importance of organometallics can be noticed by their presence in all life organisms. The most known natural organometallic molecule is vitamin B12, a porphyrin containing a cobalt atom, useful for several enzymatic transformations. Based on the remarkable properties of this class of compounds, a new area of medicinal research was developed. Gérard Jaouen was the first to introduce the term of "bioorganometallic chemistry" in 1985 although the first organometallic therapeutical was Salvarsan®, discovered by Paul Ehrlich (Nobel Prize in Medicine in 1908). Bioorganometallic chemistry consists of the synthesis and the study of organometallic complexes, complexes with at least one metal-carbon bond, in a biological and medicinal interest. This field of research was accentuated by the discovery of the ferrocene in 1951 by Pauson and Kealy, confirmed in 1952 by Wilkinson (Nobel Prize in 1973). Today, bioorganometallic chemistry includes 5 main domains: (1) organometallic therapeuticals, (2) toxicology and environment, (3) molecular recognition in aqueous phases, (4) enzymes, proteins and peptides, (5) bioanalysis and pharmaceutical sensors. In this review, we focused on organometallic therapeuticals. The exceptional properties of organometallics are first described and then, an overview on the main organometallic complexes used for drug design is presented. This review gives an idea how organometallics can be used for the rational design of new drugs.

  18. Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds and Ionic Liquids. Sublimation, Vaporization, and Fusion Enthalpies from 1880 to 2015. Part 2. C11-C192

    Science.gov (United States)

    Acree, William; Chickos, James S.

    2017-03-01

    The second part of this compendium concludes with a collection of phase change enthalpies of organic molecules inclusive of C11-C192 reported over the period 1880-2015. Also included are phase change enthalpies including fusion, vaporization, and sublimation enthalpies for organometallic, ionic liquids, and a few inorganic compounds. Paper I of this compendium, published separately, includes organic compounds from C1 to C10 and describes a group additivity method for evaluating solid, liquid, and gas phase heat capacities as well as temperature adjustments of phase changes. Paper II of this compendium also includes an updated version of a group additivity method for evaluating total phase change entropies which together with the fusion temperature can be useful in estimating total phase change enthalpies. Other uses include application in identifying potential substances that either form liquid or plastic crystals or exhibit additional phase changes such as undetected solid-solid transitions or behave anisotropically in the liquid state.

  19. Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds. Sublimation, Vaporization and Fusion Enthalpies From 1880 to 2015. Part 1. C{sub 1} − C{sub 10}

    Energy Technology Data Exchange (ETDEWEB)

    Acree, William [Department of Chemistry, University of North Texas, Denton, Texas 76203 (United States); Chickos, James S. [Department of Chemistry and Biochemistry, University of Missouri—St. Louis, One University Boulevard, St. Louis, Missouri 63121 (United States)

    2016-09-15

    A compendium of phase change enthalpies published in 2010 is updated to include the period 1880–2015. Phase change enthalpies including fusion, vaporization, and sublimation enthalpies are included for organic, organometallic, and a few inorganic compounds. Part 1 of this compendium includes organic compounds from C{sub 1} to C{sub 10}. Part 2 of this compendium, to be published separately, will include organic and organometallic compounds from C{sub 11} to C{sub 192}. Sufficient data are presently available to permit thermodynamic cycles to be constructed as an independent means of evaluating the reliability of the data. Temperature adjustments of phase change enthalpies from the temperature of measurement to the standard reference temperature, T = 298.15 K, and a protocol for doing so are briefly discussed.

  20. Structure of organometallic compounds obtained by plasma of titanium isopropoxide; Estructura de compuestos organometalicos obtenidos por plasma de isopropoxido de titanio

    Energy Technology Data Exchange (ETDEWEB)

    Arreola R, M. L.

    2012-07-01

    This work presents a study on the synthesis and characterization of organometallic compounds of titanium oxide obtained from glow discharges of titanium tetraisopropoxide (TTIP) and water on glass and polyethylene. The objective is the synthesis of titanium oxide particles which can be fixed on different supports for use in further studies of contaminants degradation in effluent streams. The synthesis was carried out by plasma in a glass tubular reactor of 750 cm{sup 3} and 15 cm length at 10{sup -1} mbar with power between 100 and 150 W during 2, 3 and 4 h. The precursors were TTIP and water vapor. TTIP is an organometallic compound composed of a central atom of Ti surrounded by 4 O atoms, which in turn are connected with chains of 3 C (propane s). The objective is the use of plasma collisions to separate the organic and inorganic phases of TTIP, so that both structure independently in a single material. The result was the formation of white titanium oxide powder composed with agglomerates of spherical particles with average diameter between 160 and 452 nm adhered to small films. The agglomerates have a tendency to change from film to particles with the energy applied to the synthesis. The study of the chemical structure showed a great presence of O{sub 2}-Ti-O{sub 2} (Ti surrounded by O) which can be found in most titanium oxides. Other chemical groups belonging to the organic phase were C=C=C, C=C=O and C{sub 2}-C-Ch appearing from the dehydrogenation of TTIP, which can be a possible precursor of this reactions kind. The structural superficial analyses showed that the atomic composition varies according to type of substrate used. The greatest content of Ti was obtained on glass substrates. However, the synthesis conditions had not evident effect in the participation of chemical states found in the inorganic phase. The crystalline studies indicated that the material is amorphous, although the de convoluted X-ray spectra showed that the synthesized titanium oxides

  1. Insights into the Binding Sites of Organometallic Ruthenium Anticancer Compounds on Peptides Using Ultra-High Resolution Mass Spectrometry

    Science.gov (United States)

    Wills, Rebecca H.; Habtemariam, Abraha; Lopez-Clavijo, Andrea F.; Barrow, Mark P.; Sadler, Peter J.; O'Connor, Peter B.

    2014-04-01

    The binding sites of two ruthenium(II) organometallic complexes of the form [(η6-arene)Ru( N, N)Cl]+, where arene/ N, N = biphenyl (bip)/bipyridine (bipy) for complex AH076, and biphenyl (bip)/ o-phenylenediamine ( o-pda) for complex AH078, on the peptides angiotensin and bombesin have been investigated using Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. Fragmentation was performed using collisionally activated dissociation (CAD), with, in some cases, additional data being provided by electron capture dissociation (ECD). The primary binding sites were identified as methionine and histidine, with further coordination to phenylalanine, potentially through a π-stacking interaction, which has been observed here for the first time. This initial peptide study was expanded to investigate protein binding through reaction with insulin, on which the binding sites proposed are histidine, glutamic acid, and tyrosine. Further reaction of the ruthenium complexes with the oxidized B chain of insulin, in which two cysteine residues are oxidized to cysteine sulfonic acid (Cys-SO3H), and glutathione, which had been oxidized with hydrogen peroxide to convert the cysteine to cysteine sulfonic acid, provided further support for histidine and glutamic acid binding, respectively.

  2. Multiple spin-state scenarios in organometallic reactivity

    NARCIS (Netherlands)

    Dzik, W.I.; Böhmer, W.; de Bruin, B.; Swart, M.; Costas, M.

    2016-01-01

    This chapter gives an overview of the different spin-state crossing scenarios affecting the reactivity of organometallic compounds. It focuses on the effects of crossing spin states in a number of elementary reactions typically observed for organometallic compounds, such as ligand exchange,

  3. Organometallic neptunium(III) complexes.

    Science.gov (United States)

    Dutkiewicz, Michał S; Farnaby, Joy H; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G; Love, Jason B; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L

    2016-08-01

    Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on U(III) and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to Np(IV). Here we report the synthesis of three new Np(III) organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that Np(III) complexes could act as single-molecule magnets, and that the lower oxidation state of Np(II) is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key Np(III) orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

  4. Organometallic neptunium(III) complexes

    Science.gov (United States)

    Dutkiewicz, Michał S.; Farnaby, Joy H.; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G.; Love, Jason B.; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L.

    2016-08-01

    Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

  5. Drug delivery by water-soluble organometallic cages.

    Science.gov (United States)

    Therrien, Bruno

    2012-01-01

    Until recently, organometallic derivatives were generally viewed as moisture- and air-sensitive compounds, and consequently very challenging to synthesise and very demanding in terms of laboratory requirements (Schlenk techniques, dried solvent, glove box). However, an increasing number of stable, water-soluble organometallic compounds are now available, and organometallic chemistry in aqueous phase is a flourishing area of research. As such, coordination-driven self-assemblies using organometallic building blocks are compatible with water, thus opening new perspectives in bio-organometallic chemistry.This chapter gives a short history of coordination-driven self-assembly, with a special attention to organometallic metalla-cycles, especially those composed of half-sandwich complexes. These metalla-assemblies have been used as sensors, as anticancer agents, as well as drug carriers.

  6. Optimization of the quantitative direct solid total-reflection X-ray fluorescence analysis of glass microspheres functionalized with Zr organometallic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez-Ruiz, Ramon, E-mail: ramon.fernandez@uam.e [Servicio Interdepartamental de Investigacion, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco, E-28049, Madrid (Spain); Andres, Roman; Jesus, Ernesto de [Departamento de Quimica Inorganica, Universidad de Alcala, Campus Universitario, 28871, Alcala de Henares, Madrid (Spain); Terreros, Pilar [Instituto de Catalisis y Petroleo-Quimica, CSIC, Cantoblanco, 28049, Madrid (Spain)

    2010-06-15

    Quantitative determination of Zr in the system constituted by quartz microspheres functionalized with two kinds of organometallic compounds has been studied due to the importance of the correct quantization of the Zr from a catalytic point of view. Two parallel approximations were done, i.e. acid leaching and direct solid quantization. To validate the acid leaching TXRF measures, ICP-MS analysis were carried out. The results obtained by means of the optimization of the quantitative direct solid procedure show that, with a previous particle size distribution modification, TXRF obtain the same analytical results as ICP-MS and TXRF by acid leaching way but without previous chemical acid manipulation. This fact implies an important improvement for the analysis time, reagents costs and analysis facility and it proves again the versatility of TXRF to solve analytical problems in an easy, quick and accurate way. Additionally and for the direct solid TXRF measurements, a deeper study was done to evaluate the intrinsic analytical parameters of the Zr TXRF analysis of this material. So, the influence of the particle size distributions (modified by means of a high power ultrasound probe) with respect to uncertainty and detection limits for Zr were developed. The main analytical conclusion was the strong correlation between the average particle sizes and the TXRF analytical parameters of Zr measurements, i.e. concentration, accuracy, uncertainty and detection limits.

  7. Estanilenos: organometálicos de estanho (II σ - ligados a grupos orgânicos Stannylenes: organometallic compounds of tin (II σ-bonded to organic groups

    Directory of Open Access Journals (Sweden)

    Geraldo M. de Lima

    2010-01-01

    Full Text Available This article provides a short review of the chemistry of stannylenes and their derivatives, including the preparation, spectroscopic properties, molecular structure and reactivity of the various species. The organometallic chemistry of Sn(II is far less explored than that of its much more common Sn(IV counterpart. Organometallics of main group metals have become increasingly important in recent years, which prompted us to present an overview of the situation regarding the case of Sn(II.

  8. Studies in group IV organometallic chemistry XXX. Synthesis of compounds containing tin---titanium and tin---zirconium bonds

    NARCIS (Netherlands)

    Creemers, H.M.J.C.; Verbeek, F.; Noltes, J.G.

    1968-01-01

    Starting from the tetrakis(diethylamino) derivatives of titanium and zirconium and pheyltin hydrides six intermetalic compounds contianing up to nine tin and titanium(or zirconium) atoms have been obtained by hydrostannolysis type reactions.

  9. Studies in group IV organometallic chemistry XXX. Synthesis of compounds containing tin---titanium and tin---zirconium bonds

    NARCIS (Netherlands)

    Creemers, H.M.J.C.; Verbeek, F.; Noltes, J.G.

    Starting from the tetrakis(diethylamino) derivatives of titanium and zirconium and pheyltin hydrides six intermetalic compounds contianing up to nine tin and titanium(or zirconium) atoms have been obtained by hydrostannolysis type reactions.

  10. Bis{2-[(dimethylamino)methyl]phenyl}silverlithium. A tetranuclear organometallic compound with bridging aryl groups between silver and lithium

    NARCIS (Netherlands)

    Koten, G. van; Leusink, A.J.; Marsman, J.W.; Noltes, J.G.

    1973-01-01

    Bis{2-[(dimethylamino)methyl]phenyl}silverlithium has been prepared and characterized. Molecular weight determinations, and }1{}3{C NMR and }1{H NMR spectra reveal that the compound exists (in benzene) as a tetranuclear mixed metal cluster containing aryl groups bridging the silver and lithium

  11. Separation of Metal Chelates and Organometallic Compounds by Supercritical Fluid Chromatography%超临界流体色谱在金属络合物和金属有机化合物中的分析应用

    Institute of Scientific and Technical Information of China (English)

    王少芬; 魏建谟

    2001-01-01

    超临界流体色谱(SFC)在色谱分离过程中能在较低的温度下分析对热不稳定的化合物,包括金属络合物和金属有机化合物。本文总结了近来文献报道的各种过渡金属、重金属、镧系和锕系以及铅、汞和锡的金属有机化合物的SFC分离,还讨论了SFC检测系统和金属有机化合物的溶解度的测定。%Supercritical fluid chromatography (SFC) combines the hig h diffusion coefficients of gas chromatography (GC) and the solubility propertie s of liquid chromatography (LC). SFC generally requires lower temperatures for chromatographic separations and thus is more suitable for analyzing thermally l abile compounds including a number of metal chelates and organometallic compound s. SFC also allows interfacing between supercritical fluid extraction (SFE) and chromatographic analysis of metal-containing compounds. A large number of metal chelates and organometallic compounds can be separated b y SFC. This article summarizes SFC separation of various chelates of transitio n metals, heavy metals, lanthanides and actinides as well as organometallic comp ounds of lead, mercury and tin reported in the recent literature. This articl e also discusses SFC detection systems and the determination of solubility of or ganometallic compounds by SFC.

  12. Anthracene-tethered ruthenium(II) arene complexes as tools to visualize the cellular localization of putative organometallic anticancer compounds.

    Science.gov (United States)

    Nazarov, Alexey A; Risse, Julie; Ang, Wee Han; Schmitt, Frederic; Zava, Olivier; Ruggi, Albert; Groessl, Michael; Scopelitti, Rosario; Juillerat-Jeanneret, Lucienne; Hartinger, Christian G; Dyson, Paul J

    2012-03-19

    Anthracene derivatives of ruthenium(II) arene compounds with 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane (pta) or a sugar phosphite ligand, viz., 3,5,6-bicyclophosphite-1,2-O-isopropylidene-α-d-glucofuranoside, were prepared in order to evaluate their anticancer properties compared to the parent compounds and to use them as models for intracellular visualization by fluorescence microscopy. Similar IC(50) values were obtained in cell proliferation assays, and similar levels of uptake and accumulation were also established. The X-ray structure of [{Ru(η(6)-C(6)H(5)CH(2)NHCO-anthracene)Cl(2)(pta)] is also reported.

  13. Iron(III-salophene: an organometallic compound with selective cytotoxic and anti-proliferative properties in platinum-resistant ovarian cancer cells.

    Directory of Open Access Journals (Sweden)

    Thilo S Lange

    Full Text Available BACKGROUND: In this pioneer study to the biological activity of organometallic compound Iron(III-salophene (Fe-SP the specific effects of Fe-SP on viability, morphology, proliferation, and cell-cycle progression on platinum-resistant ovarian cancer cell lines were investigated. METHODOLOGY/PRINCIPAL FINDINGS: Fe-SP displayed selective cytotoxicity against SKOV-3 and OVCAR-3 (ovarian epithelial adenocarcinoma cell lines at concentrations between 100 nM and 1 microM, while the viability of HeLa cells (epithelial cervix adenocarcinoma or primary lung or skin fibroblasts was not affected. SKOV-3 cells in contrast to fibroblasts after treatment with Fe-SP revealed apparent hallmarks of apoptosis including densely stained nuclear granular bodies within fragmented nuclei, highly condensed chromatin and chromatin fragmentation. Fe-SP treatment led to the activation of markers of the extrinsic (Caspase-8 and intrinsic (Caspase-9 pathway of apoptosis as well as of executioner Caspase-3 while PARP-1 was deactivated. Fe-SP exerted effects as an anti-proliferative agent with an IC(50 value of 300 nM and caused delayed progression of cells through S-phase phase of the cell cycle resulting in a complete S-phase arrest. When intra-peritoneally applied to rats Fe-SP did not show any systemic toxicity at concentrations that in preliminary trials were determined to be chemotherapeutic relevant doses in a rat ovarian cancer cell model. CONCLUSION/SIGNIFICANCE: The present report suggests that Fe-SP is a potent growth-suppressing agent in vitro for cell lines derived from ovarian cancer and a potential therapeutic drug to treat such tumors in vivo.

  14. s-Block organometallics: analysis of ion-association and noncovalent interactions on structure and function in benzyl-based compounds.

    Science.gov (United States)

    Torvisco, Ana; Ruhlandt-Senge, Karin

    2011-12-19

    The organometallic chemistry of alkali and alkaline-earth metals has been marred by synthetic setbacks because of their high reactivity. Advances in their synthesis and a better understanding of the stabilization effects of ligands and coligands have resulted in the revolution of s-block organometallics. Among those, benzyl-based derivatives have played a key role in developing this chemistry because factors such as the ligand size, charge delocalization, and introduction of electronic parameters along with metal effects can be analyzed. This article will focus on s-block benzylates and di- and triphenylmethanide derivatives with specific emphasis on the factors that stabilize the highly reactive metal species.

  15. Application of imaging spectroscopic reflectometry for characterization of gold reduction from organometallic compound by means of plasma jet technology

    Science.gov (United States)

    Vodák, Jiří; Nečas, David; Pavliňák, David; Macak, Jan M.; Řičica, Tomáš; Jambor, Roman; Ohlídal, Miloslav

    2017-02-01

    This work presents a new application of imaging spectroscopic reflectometry to determine a distribution of metallic gold in a layer of an organogold precursor which was treated by a plasma jet. Gold layers were prepared by spin coating from a solution of the precursor containing a small amount of polyvinylpyrrolidone on a microscopy glass, then they were vacuum dried. A difference between reflectivity of metallic gold and the precursor was utilized by imaging spectroscopic reflectometry to create a map of metallic gold distribution using a newly developed model of the studied sample. The basic principle of the imaging spectroscopic reflectometry is also shown together with the data acquisition principles. XPS measurements and microscopy observations were made to complete the imaging spectroscopic reflectometry results. It is proved that the imaging spectroscopic reflectometry represents a new method for quantitative evaluation of local reduction of metallic components from metaloorganic compounds.

  16. Application of a novel superposition technique to the structure of an organophosphorus insecticide and an organometallic compound

    Energy Technology Data Exchange (ETDEWEB)

    Beckman, D.E.

    1979-01-01

    The structures of 0-0-dimethyl-0-(3,5,6-trichloro-2-pyridyl) phosphorothioate (Dowco 214) and dicarbonylbis(eta-cyclopentadienyl)-..mu..-carbonyl-..mu..-thiocarbonyldiiron have been solved by single crystal x-ray diffraction and use of a modified Patterson superposition technique that uses two multiple vectors to define a structural parallelogram. This method results in a simpler and more accurate shift vector position determination and a general improvement in map clarity. Dowco 214 crystallizes in the space group P/sub 1//sup -/ with a = 11.598(2) A, b = 13.619(3) A, c = 8.281(1) A, ..cap alpha.. = 94.65(1)/sup 0/, ..beta.. = 94.87(2)/sup 0/, ..gamma.. = 79.97(2)/sup 0/ and four molecules per cell (two per asymmetric unit). A CNDO II calculation was performed and partial charge densities assigned. The molecule contains distances between positively charged centers that correspond well to the reported anionic-esteratic distance (a possible reaction variable) in AChE. Additional reaction variables are discussed. Cp/sub 2/Fe/sub 2/(CO)/sub 3/CS crystallizes in the space group P2/sub 1//c with a = 14.508(8) A, b = 13.618(5) A, c = 15.193(7) A, ..beta.. = 110.50(6)/sup 0/ and eight molecules per unit cell (two per asymmetric unit). The compound contains both a carbonyl and thiocarbonyl bridge and ..pi..-bonded cyclopentadienyl rings that are cis to one another. The iron--iron bond length is intermediate to that of its carbonyl and thiocarbonyl analogs.

  17. Organometallic Chemistry of Molybdenum.

    Science.gov (United States)

    Lucas, C. Robert; Walsh, Kelly A.

    1987-01-01

    Suggests ways to avoid some of the problems students have learning the principles of organometallic chemistry. Provides a description of an experiment used in a third-year college chemistry laboratory on molybdenum. (TW)

  18. Multifold and sequential cross-coupling reactions with indium organometallics.

    Science.gov (United States)

    Pena, Miguel A; Pérez, Ignacio; Pérez Sestelo, José; Sarandeses, Luis A

    2002-10-07

    Multifold and sequential palladium-catalyzed cross-coupling reactions can be performed between triorganoindium compounds and oligohaloarenes using only a small excess of the organometallic reagent, low catalyst charge loading and short reaction times.

  19. First-principles study of Ni-based metal compound%Ni基金属间化合物第一性原理研究

    Institute of Scientific and Technical Information of China (English)

    唐志强; 齐砚勇; 易勇; 丁志杰

    2012-01-01

    稀上(R)-过渡族(T)金属间化合物具有优异的物理和化学性质.本研究考虑电子自旋极化作用,基于第一性原理的全电子投影缀加平面波赝势法理论,采用局域自旋密度近似(LSDA),对Ni_(13)Nd_3B_2金属间化合物进行结构优化,计算体系晶格常数、电子结构和磁性能.结果表明,Ni_(13)Nd_3B_2为带隙很小的金属导体.LSDA近似下体系原子间存在复杂作用类型,Nd原子与近邻Ni,B原子以离子键作用为主,Ni原子与近邻Ni原子间表现共价作用情形.体系存在Nd-Ni铁磁耦合,总磁矩约8.4329μ_B,主要由Nd原子磁矩提供,自旋极化引起的体系Nd-4f,Ni-3p,Nd-5p电子自旋劈裂为体系表现磁性的根本原因.%The rare earth-transition(R-T) intermetallics has excellent physical and chemical properties.The electronic structure,the band structure and the magnetic properties of the compound Ni_(13)Nd_3B_2 are studied by using the first-principles plane wave pseudopotential method and the local spin-density approximation(LSDA).The calculation results indicate that this system is a metallic conductor with a very small band gap.The system has very complex bonding,where Nd atoms and the neighboring Ni and B atoms form ionic banding,whereas Ni atoms and the neighboring Ni atoms form covalent bonding.Under LSDA approximation,the system has Nd-Ni ferromagnetic coupling,and the total magnetic moment(≈8.4329μb) is provided by the local Nd magnetic moment.The Nd-4f, Ni-3p,Nd-5p electron spin splittings due to spin polarization result in the magnetic system.

  20. Coupling of a gas chromatograph to a simultaneous-detection inductively coupled plasma mass spectrograph for speciation of organohalide and organometallic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, James H.; Schilling, G; Sperline, Roger; Denton, M Bonner B.; Young, Erick T.; Barinaga, Charles J.; Koppenaal, David W.; Hieftje, Gary M.

    2004-06-01

    A gas chromatograph (GC) has been coupled to an inductively coupled plasma Mattauch-Herzog geometry mass spectrograph (ICP-MHMS) equipped with a novel detector array. In its current state of development the detector array, termed the focal plan camera (FPC), permits the simultaneous monitoring of up to 15 m/z values. A heated line was used to transfer the capillary-column effluent from the GC to the ICP torch, though due to instrument operating conditions, the transfer line was terminated 50 mm ahead of the ICP torch. Minimal tailing was observed, with the most severe effect seen for high-boiling analytes. With the coupling, absolute limits of detection are in the tens to hundreds of femtogram regime for organometallic species and in the single pictogram regime for halogenated hydrocarbons.

  1. The potential of organometallic complexes in medicinal chemistry.

    Science.gov (United States)

    Gasser, Gilles; Metzler-Nolte, Nils

    2012-04-01

    Organometallic complexes have unique physico-chemical properties, which have been widely used in homogenous catalysis, for example, for the synthesis of lead compounds and drug candidates. Over the past two decades, a few scientists from all over the world have extended the use of the specific characteristics of these compounds (e.g. structural diversity, possibility of ligand exchange, redox and catalytic properties) for medicinal purposes. The results are stunning. A few organometallic compounds have already entered clinical trials and it can be anticipated that several more will follow in coming years. In this short review, we present the specific advantages that organometallic metal complexes have over purely organic and also coordination compounds. Furthermore, using specific examples, we illustrate how these particular properties can be put to good use in medicinal chemistry. The examples we present have an emphasis on, but are not restricted to, anti-cancer activity.

  2. Sterically Hindered Square-Planar Nickel(II) Organometallic Complexes: Preparation, Characterization, and Substitution Behavior

    Science.gov (United States)

    Martinez, Manuel; Muller, Guillermo; Rocamora, Merce; Rodriguez, Carlos

    2007-01-01

    The series of experiments proposed for advanced undergraduate students deal with both standard organometallic preparative methods in dry anaerobic conditions and with a kinetic study of the mechanisms operating in the substitution of square-planar complexes. The preparation of organometallic compounds is carried out by transmetallation or…

  3. Precise Synthesis of Organometallic Dendrimers

    Institute of Scientific and Technical Information of China (English)

    K. Onitsuka; S. Takahashi

    2005-01-01

    @@ 1Introduction Dendrimers possessing a regularly branched architecture and large spherical dimensions have attracted significant attention because of their unique and tunable properties as well as their potential applications. The incorporation of organometallic species into dendritic molecules has been attracting much attention, because the addition of properties characteristic of organometallic complexes, such as magnetic, electronic, and photo-optical properties, as well as reactivity may lead to the realization of new functionalized dendrimers. Although there are many examples of organometallic dendrimers that contain metallic species at the core or at the periphery, dendrimers composed of organometallic complexes in each generation are still limited. We present here convergent and divergent approaches to novel organometallic dendrimers, of which the skeletons were built up with platinum-acetylide units.

  4. Organometallic frustrated Lewis pair chemistry.

    Science.gov (United States)

    Erker, Gerhard

    2011-08-07

    Frustrated Lewis pairs are playing an increasingly important role in organometallic chemistry. Examples are presented and discussed where organometallic systems themselves serve as the Lewis base or Lewis acid components in frustrated Lewis pair chemistry, mostly through their attached functional groups. Activation of dihydrogen takes place easily in many of these systems. This may lead to the generation of novel catalyst systems but also in many cases to the occurrence of specific reactions at the periphery of the organometallic frameworks. Increasingly, FLP reactions are used to carry out functional group conversions in organometallic systems under mild reaction conditions. The limits of typical FLP reactivity are explored with selected organometallic examples, a discussion that points toward new developments, such as the discovery of facile new 1,1-carboboration reactions. Learning more and more about the broad spectrum of frustrated Lewis pair chemistry helps us to find novel reactions and applications.

  5. Luminescent di- and polynuclear organometallic gold(I)-metal (Au2, {Au2Ag}n and {Au2Cu}n) compounds containing bidentate phosphanes as active antimicrobial agents.

    Science.gov (United States)

    Frik, Malgorzata; Jiménez, Josefina; Gracia, Ismael; Falvello, Larry R; Abi-Habib, Sarya; Suriel, Karina; Muth, Theodore R; Contel, María

    2012-03-19

    The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au(2)(mes)(2)(μ-LL)] (LL=dppe: 1,2-bis(diphenylphosphano)ethane 1a, and water-soluble dppy: 1,2-bis(di-3-pyridylphosphano)ethane 1b) with Ag(+) and Cu(+) lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au(2)M(μ-mes)(2) (μ-LL)][A] (M=Ag, A=ClO(4)(-), LL=dppe 2a, dppy 2b; M=Ag, A=SO(3)CF(3)(-), LL=dppe 3a, dppy 3b; M=Cu, A=PF(6)(-), LL=dppe 4a, dppy 4b). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au(2)(mes)(2)(μ-dppy)] (1b) and [Au(2)Ag(μ-mes)(2)(μ-dppe)][SO(3)CF(3)] (3a) were determined by a single-crystal X-ray diffraction study. 3a in solid state is not a cyclic trinuclear Au(2)Ag derivative but it gives an open polymeric structure instead, with the {Au(2)(μ-dppe)} fragments "linked" by {Ag(μ-mes)(2)} units. The very short distances of 2.7559(6) Å (Au-Ag) and 2.9229(8) Å (Au-Au) are indicative of gold-silver (metallophilic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77 K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self-aggregation of [Au(2)M(μ-mes)(2)(μ-LL)](+) units (M=Ag or Cu; LL=dppe or dppy) into an extended chain structure, through Au-Au and/or Au-M metallophilic interactions, as that observed for 3a. In solid state the heterometallic Au(2)M complexes with dppe (2a-4a) show a shift of emission maxima (from ca. 430 to the range of 520-540 nm) as compared to the parent dinuclear organometallic product 1a while the complexes with dppy (2b-4b) display a more moderate shift (505 for 1b to a max of 563 nm for 4b). More importantly, compound [Au(2)Ag(μ-mes)(2)(μ-dppy)]ClO(4) (2b) resulted

  6. Organometallics and renewables

    Energy Technology Data Exchange (ETDEWEB)

    Meier, Michael A.R. [Karlsruhe Institute of Technology (KIT), Karlsruhe (Germany). Inst. of Organic Chemistry; Weckhuysen, Bert M.; Bruijnincx, Pieter C.A. (eds.) [Utrecht Univ. (Netherlands). Debye Inst. of Nanomaterials Science

    2012-11-01

    USPs - BPF Each volume of Topics in Organometallic Chemistry provides the broad scientific readership with a comprehensive summary and critical overview of a specific topic in organometallic chemistry. Research in this rapidly developing transdisciplinary field is having profound influence on other areas of scientific investigation, ranging from catalytic organic synthesis to biology, medicine and material science. With contributions by international experts. Lucas Montero de Espinosa and Michael A. R. Meier: Olefin Metathesis of Renewable Platform Chemicals.- Pieter C. A. Bruijnincx, Robin Jastrzebski, Peter J. C. Hausoul, Robertus J. M. Klein Gebbink, and Bert M. Weckhuysen: Pd-Catalysed Telomerisation of 1,3-Dienes with Multifunctional Renewable Substrates - Versatile Routes for the Valorisation of Biomass-Derived Platform Molecules.- A Behr, A. J. Vorholt: Hydroformylation and related reactions of renewable resources.- Ties J. Korstanje, Robertus J.M. Klein Gebbink: Catalytic oxidation and deoxygenation of renewables with rhenium complexes.- Antoine Buchard, Clare M. Bakewell, Jonathan Weiner and Charlotte K. Williams: Recent Developments In Catalytic Activation Of Renewable Resources For Polymer Synthesis.

  7. Organometallics and related molecules for energy conversion

    CERN Document Server

    Wong, Wai-Yeung

    2015-01-01

    This book presents a critical perspective of the applications of organometallic compounds (including those with metal or metalloid elements) and other related metal complexes as versatile functional materials in the transformation of light into electricity (solar energy conversion) and electricity into light (light generation in light emitting diode), in the reduction of carbon dioxide to useful chemicals, as well as in the safe and efficient production and utilization of hydrogen, which serves as an energy storage medium (i.e. energy carrier). This book focuses on recent research developmen

  8. Organometallic-Peptide Bioconjugates: Synthetic Strategies and Medicinal Applications.

    Science.gov (United States)

    Albada, Bauke; Metzler-Nolte, Nils

    2016-10-12

    Peptides are important biological molecular entities in biomedical research. They can be prepared in a large variety of shapes, with a host of chemical functions, and tailored for specific applications. Organometallic medicinal chemistry is a relatively young field that explores biomedical and bioanalytical applications of organometallic complexes, that is, metal compounds with at least one direct, covalent metal-carbon bond. The conjugation of peptides to such medicinally active organometallic moieties started only about 20 years ago, and it has been very beneficial for the development of bioorganometallic chemistry in general. Similarly, the biomedical properties of peptides have been altered by their conjugation to organometallic (OM) moieties. In this review, synthetic methods by which OM moieties can be conjugated to peptides via a carbon-metal bond are described, and selected medicinal applications of such conjugates are discussed. Inorganic coordination complexes between metal ions and peptides are excluded from this review. Also, the labeling of peptides with radiometals and applications of radiolabeled peptides will not be treated herein. First, modifications of the peptide backbone (either N- or C-terminally, or both) with organometallic moieties will be described, including the insertion of OM moieties as part of the peptide backbone. Then side-chain modifications will be reported, among them the most recent strategies for chemoselective arene metalation on peptides. Finally, approaches by which multiple metalation can be achieved are explored. In each section, selected examples of biological applications are highlighted.

  9. Materials science of Mg-Ni-based new hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Orimo, S.; Fujii, H. [Hiroshima Univ. (Japan). Faculty of Integrated Arts and Sciences

    2001-02-01

    One of the advantageous functional properties of Mg alloys (or compounds) is to exhibit the reversible hydriding reaction. In this paper, we present our systematic studies regarding the relationship between nanometer- or atomistic-scale structures and the specific hydriding properties of the Mg-Ni binary system, such as(1) nanostructured (n)-Mg{sub 2}Ni, (2) a mixture of n-Mg{sub 2}Ni and amorphous (a)-MgNi,(3) pure a-MgNi, and(4) n-MgNi{sub 2}. Further studies on(5) an a-MgNi-based system for clarifying the effect of the short-range ordering on the structural and hydriding properties and(6) a MgNi{sub 2}-based system for synthesizing the new Laves phase structure are also presented. The materials science of Mg-Ni-based new hydrides will provide indispensable knowledge for practically developing the Mg alloys as hydrogen-storage materials. (orig.)

  10. Soluble molecular compounds with the Mg-O-Al structural motif: a model approach for the fixation of organometallics on a MgO surface.

    Science.gov (United States)

    Nembenna, Sharanappa; Roesky, Herbert W; Mandal, Swadhin K; Oswald, Rainer B; Pal, Aritra; Herbst-Irmer, Regine; Noltemeyer, Mathias; Schmidt, Hans-Georg

    2006-10-11

    We report a facile route to the molecular compounds with the Mg-O-Al structural motif. The reaction of Mg[N(SiMe3)2]2 (1) with a stoichiometric amount of LAlOH(Me) (2) [L = CH{(CMe)(2,6-iPr2C6H3N)}2] in THF/n-hexane at 0 degrees C results in the formation of the heterobimetallic compound (Me3Si)2NMg(THF)2-O-Al(Me)L (3) in high yield. The similar reaction of 1 equiv of Mg[N(SiMe3)2]2 and 2 equiv of LAlOH(Me) results in the formation of trimetallic compound L(Me)Al-O-Mg(THF)2-O-Al(Me)L (4). Structural analyses of 3 and 4 have been carried out, revealing the presence of the Mg-O-Al motif. A tentative assignment of the Mg-O-Al vibrations has been made and was supported by calculations.

  11. Organometallic Complexes of Graphene

    CERN Document Server

    Sarkar, Santanu; Bekyarova, Elena; Haddon, Robert C

    2013-01-01

    We demonstrate the organometallic hexahapto complexation of chromium with graphene, graphite and carbon nanotubes. All of these extended periodic pi-electron systems exhibit some degree of reactivity toward the reagents CrCO)6 and (eta6-benzene)Cr(CO)3, and we are able to demonstrate the formation of (eta6-rene)Cr(CO)3 or (eta6-arene)2Cr, where arene = single-walled carbon nanotubes (SWNT), exfoliated graphene (XG), epitaxial graphene (EG) and highly-oriented pyrolytic graphite (HOPG). We find that the SWNTs are the least reactive presumably as a result of the effect of curvature on the formation of the hexahapto bond; in the case of HOPG, (eta6-HOPG)Cr(CO)3 was isolated while the exfoliated graphene samples were found to give both (eta6-graphene)2Cr, and (eta6-graphene)Cr(CO)3 structures. We report simple and efficient routes for the mild decomplexation of the graphene-chromium complexes which appears to restore the original pristine graphene state. This study represents the first example of the use of graph...

  12. n-Doping of organic electronic materials using air-stable organometallics: a mechanistic study of reduction by dimeric sandwich compounds.

    Science.gov (United States)

    Guo, Song; Mohapatra, Swagat K; Romanov, Alexander; Timofeeva, Tatiana V; Hardcastle, Kenneth I; Yesudas, Kada; Risko, Chad; Brédas, Jean-Luc; Marder, Seth R; Barlow, Stephen

    2012-11-12

    Several 19-electron sandwich compounds are known to exist as "2×18-electron" dimers. Recently it has been shown that, despite their air stability in the solid state, some of these dimers act as powerful reductants when co-deposited from either the gas phase or from solution and that this behavior can be useful in n-doping materials for organic electronics, including compounds with moderate electron affinities, such as 6,13-bis[tri(isopropyl)silylethynyl]pentacene (3). This paper addresses the mechanisms by which the dimers of 1,2,3,4,5-pentamethylrhodocene (1 b(2)), (pentamethylcyclopentadienyl)(1,3,5-trialkylbenzene)ruthenium (alkyl=Me, 2 a(2); alkyl=Et, 2 b(2)), and (pentamethylcyclopentadienyl)(benzene)iron (2 c(2)) react with 3 in solution. Vis/NIR and NMR spectroscopy, and X-ray crystallography indicate that the products of these solution reactions are 3(·-) salts of the monomeric sandwich cations. Vis/NIR kinetic studies for the Group 8 dimers are consistent with a mechanism whereby an endergonic electron transfer from the dimer to 3 is followed by rapid cleavage of the dimer cation. NMR crossover experiments with partially deuterated derivatives suggest that the C-C bond in the 1 b(2) dimer is much more readily broken than that in 2 a(2); consistent with this observation, Vis/NIR kinetic measurements suggest that the solution reduction of 3 by 1 b(2) can occur by both the mechanism established for the Group 8 species and by a mechanism in which an endergonic dissociation of the dimer is followed by rapid electron transfer from monomeric 1 b to 3.

  13. Structure investigations of group 13 organometallic carboxylates.

    Science.gov (United States)

    Justyniak, Iwona; Prochowicz, Daniel; Tulewicz, Adam; Bury, Wojciech; Goś, Piotr; Lewiński, Janusz

    2017-01-17

    The octet-compliant group 13 organometallics with highly polarized bonds in the metal coordination sphere exhibit a significant tendency to maximize their coordination number through the formation of adducts with a wide range of neutral donor ligands or by self-association to give aggregates containing tetrahedral and higher coordinated aluminium centres, and even in some cases molecular complexes equilibrate with ionic species of different coordination numbers of the metal centre. This work provides a comprehensive overview of the structural chemistry landscape of the group 13 carboxylates. Aside from a more systematic approach to the general structural chemistry of the title compounds, the structure investigations of [R2M(μ-O2CPh)]2-type benzoate complexes (where M = B, Al and Ga) and their Lewis acid-base adducts [(R2M)(μ-O2CPh)(py-Me)] are reported. DFT calculations were also performed to obtain a more in-depth understanding of both the changes in the bonding of group 13 organometallic carboxylate adducts with a pyridine ligand.

  14. Organometallic B12-DNA conjugate

    DEFF Research Database (Denmark)

    Hunger, Miriam; Mutti, Elena; Rieder, Alexander

    2014-01-01

    Design, synthesis, and structural characterization of a B12-octadecanucleotide are presented herein, a new organometallic B12-DNA conjugate. In such covalent conjugates, the natural B12 moiety may be a versatile vector for controlled in vivo delivery of oligonucleotides to cellular targets in hum...

  15. Organometallic-inorganic hybrid electrodes for lithium-ion batteries

    Science.gov (United States)

    Huang, Qian; Lemmon, John P.; Choi, Daiwon; Cosimbescu, Lelia

    2016-09-13

    Disclosed are embodiments of active materials for organometallic and organometallic-inorganic hybrid electrodes and particularly active materials for organometallic and organometallic-inorganic hybrid cathodes for lithium-ion batteries. In certain embodiments the organometallic material comprises a ferrocene polymer.

  16. Mechanisms of inorganic and organometallic reactions

    CERN Document Server

    The purpose of this series is to provide a continuing critical review of the literature concerned with mechanistic aspects of inorganic and organo­ metallic reactions in solution, with coverage being complete in each volume. The papers discussed are selected on the basis of relevance to the elucidation of reaction mechanisms and many include results of a nonkinetic nature when useful mechanistic information can be deduced. The period of literature covered by this volume is July 1982 through December 1983, and in some instances papers not available for inclusion in the previous volume are also included. Numerical results are usually reported in the units used by the original authors, except where data from different papers are com­ pared and conversion to common units is necessary. As in previous volumes material included covers the major areas of redox processes, reactions of the nonmetallic elements, reaction of inert and labile metal complexes and the reactions of organometallic compounds. While m...

  17. NEW APPLICATIONS OF LC-MS AND LC-MS2 TOWARD UNDERSTANDING THE ENVIRONMENTAL FATE OF ORGANOMETALLICS

    Science.gov (United States)

    Over the last 40 years, many organometallic compounds have been synthesized and used in a variety of consumer, agricultural, and industrial products. Including wastewater effluents, leaching, and direct land and water applications, there are many pathways that can disperse organo...

  18. Stereochemistry of organometallic and inorganic compounds

    CERN Document Server

    2012-01-01

    The authors of this fourth volume in the series have reviewed the making and breaking of chemical bonds in a sophisticated manner. In particular, new pressures brought about by environmental concerns, larger demands for the medical and pharmaceutical sectors and economics of the market place are forcing us into demanding greater stereochemical control and better product yields for chemical reactions capable of producing useful products. The chapters are written by leading experts in this area and give excellent overviews of the strengths and weaknesses of the various methodologies.In C

  19. Nitriding behavior of Ni and Ni-based binary alloys

    Energy Technology Data Exchange (ETDEWEB)

    Fonovic, Matej

    2015-01-15

    Gaseous nitriding is a prominent thermochemical surface treatment process which can improve various properties of metallic materials such as mechanical, tribological and/or corrosion properties. This process is predominantly performed by applying NH{sub 3}+H{sub 2} containing gas atmospheres serving as the nitrogen donating medium at temperatures between 673 K and 873 K (400 C and 600 C). NH{sub 3} decomposes at the surface of the metallic specimen and nitrogen diffuses into the surface adjacent region of the specimen whereas hydrogen remains in the gas atmosphere. One of the most important parameters characterizing a gaseous nitriding process is the so-called nitriding potential (r{sub N}) which determines the chemical potential of nitrogen provided by the gas phase. The nitriding potential is defined as r{sub N} = p{sub NH{sub 3}}/p{sub H{sub 2}{sup 3/2}} where p{sub NH{sub 3}} and p{sub H{sub 2}} are the partial pressures of the NH{sub 3} and H{sub 2} in the nitriding atmosphere. In contrast with nitriding of α-Fe where the nitriding potential is usually in the range between 0.01 and 1 atm{sup -1/2}, nitriding of Ni and Ni-based alloys requires employing nitriding potentials higher than 100 atm{sup -1/2} and even up to ∞ (nitriding in pure NH{sub 3} atmosphere). This behavior is compatible with decreased thermodynamic stability of the 3d-metal nitrides with increasing atomic number. Depending on the nitriding conditions (temperature, nitriding potential and treatment time), different phases are formed at the surface of the Ni-based alloys. By applying very high nitriding potential, formation of hexagonal Ni{sub 3}N at the surface of the specimen (known as external nitriding) leads to the development of a compound layer, which may improve tribological properties. Underneath the Ni{sub 3}N compound layer, two possibilities exist: (i) alloying element precipitation within the nitrided zone (known as internal nitriding) and/or (ii) development of metastable and

  20. Organometallic Chemistry and Catalysis in Industry.

    Science.gov (United States)

    Parshall, George W.; Putscher, Richard E.

    1986-01-01

    Traces the growth in the industrial usage of organometallic chemistry from 1950 to 1977, pointing out that this growth involved the production of commodity chemicals. Indicates that one of the early successes of organometallic chemistry was the discovery of ethylene polymerization catalysts. (JN)

  1. Development of novel strategy for the synthesis of organometallic compounds usable as protein ligands: application to the human cyclophilin hCyp-18; Developpement de ligands de proteines par assemblage combinatoire autour d'un coeur de rhenium{sup V}: application a la cyclophiline hCyp-18

    Energy Technology Data Exchange (ETDEWEB)

    Clavaud, C

    2006-02-15

    This thesis describes a new strategy for the development of bioactive organometallic compounds, basing on the combinatorial assembly of sub-chemical libraries (A and B) independent but complementary and able to coordinate a metallic heart M to form A-M-B complex potential ligands of biomolecules. The coordination of metals, well adapted to the production of molecular variety is usually used in medicinal chemistry, in diagnostic and therapeutic nuclear medicine. Among the useful elements, the rhenium and the technetium are metals of choice for the development of the assembly strategy because of their chemical and radiochemical properties and of the structure analogy of their complexes. This strategy was validated in vitro. The protein chosen for this purpose was the cyclophilin hCyp-18. (N.C.)

  2. Atom-efficient metal-catalyzed cross-coupling reaction of indium organometallics with organic electrophiles.

    Science.gov (United States)

    Pérez, I; Sestelo, J P; Sarandeses, L A

    2001-05-09

    The novel metal-catalyzed cross-coupling reaction of indium organometallics with organic electrophiles is described. Triorganoindium compounds (R(3)In) containing alkyl, vinyl, aryl, and alkynyl groups are efficiently prepared from the corresponding lithium or magnesium organometallics by reaction with indium trichloride. The cross-coupling reaction of R(3)In with aryl halides and pseudohalides (iodide 2, bromide 5, and triflate 4), vinyl triflates, benzyl bromides, and acid chlorides proceeds under palladium catalysis in excellent yields and with high chemoselectivity. Indium organometallics also react with aryl chlorides as under nickel catalysis. In the cross-coupling reaction the triorganoindium compounds transfer, in a clear example of atom economy, all three of the organic groups attached to the metal, as shown by the necessity of using only 34 mol % of indium. The feasibility of using R(3)In in reactions with different electrophiles, along with the high yields and chemoselectivities obtained, reveals indium organometallics to be useful alternatives to other organometallics in cross-coupling reactions.

  3. Conjugated organometallic materials containing tungsten centers

    Science.gov (United States)

    Jones, Marya

    Our group is interested in the optical and electronic properties of organometallic analogues of conjugated organic compounds. Specifically, in this thesis we will discuss the properties of complexes in which W≡C moieties replace C≡C fragments within the framework of oligo(phenyleneethynylenes) and a C4-polyyne. A family of derivatives of the type Ph(C≡CC6H4 )m(L)4W≡C(C6H 4C≡C)nPh (m = 0, 1; n = 0, 1, 2) have been prepared and characterized by X-ray crystallography, electronic-absorption spectroscopy, and electrochemistry. This substitution has allowed us to directly compare the electronic and optical properties of these organometallic complexes with those of their organic analogues. We found that while these systems exhibit redox and spectroscopic properties similar to those of their organic counterparts they also exhibit new characteristics that are due to the incorporation of the metal center. The design of these compounds has also allowed us to address how the position of the metal within the backbone affects the electronic and optical properties of these compounds. We found that the position of the metal is important in controlling the electronic structure of the material, thus suggesting that the properties of these compounds can be further tuned by changing the position of the metal within the conjugated carbon chain. In addition, we have appended sulfur and isocyanide functionalities to oligo(phenyleneethynylene) analogues. A family of compounds of the type Cl(dppe) 2W(≡CC6H4-4-(C≡CC6H 4)m-4'-R) (m = l, 2; R = N≡C, SCH2CH 2Si(CH3)3) have been prepared and characterized by electronic-absorption spectroscopy and electrochemistry. Differences between the sulfur and isocyanide functionalities are examined, along with the effects of extending conjugation along the arylidyne chain. Evidence that the sulfur-containing arylidyne complexes form self-assembled monolayers on Au and Pt electrodes is presented. In addition, the electron-transfer rates for

  4. Organometallic and Bioorganometallic Chemistry - Ferrocene and Metal Carbonyls

    Directory of Open Access Journals (Sweden)

    Čakić Semenčić, M.

    2011-02-01

    Full Text Available Organometallic chemistry deals with compounds containing metal-carbon bonds. Basic organometallics derived from the s- and p-block metals (containing solely σ-bonds were understood earlier, while organometallic chemistry of the d- and f-block has developed much more recently. These compounds are characterized by three types of M-C bonds (σ, π and δand their structures are impossible to deduce by chemical means alone; fundamental advances had to await the development of X-ray diffraction, as well as IR- and NMR-spectroscopy. On the other hand, elucidation of the structure of e. g. vitamin B12 and ferrocene (discovered in 1951 contributed to progress in these instrumental analytical methods, influencing further phenomenal success of transition-metal organometallic chemistry in the second half of the twentieth century. The most thoroughly explored fields of application of organometallics were in the area of catalysis, asymmetric synthesis, olefin metathesis, as well as organic synthesis and access to new materials and polymers.The most usual ligands bound to d- and f-metals are carbon monoxide, phosphines, alkyls, carbenes and arenes, and in this review the bonding patterns in the metal carbonyls and ferrocene are elaborated. The common characteristics of these two classes are two-component bonds. The CO-M bonds include (i donation from ligand HOMO to vacant M d-orbitals (σ-bond, and (ii back-donation from the filled M d-orbitals in the ligand LUMO (π-bond. Similar (but much more complicated ferrocene contains delocalized bonds consisting of electron donation from Cp to Fe (σ-bonds- and π-bonding and δ-back-bonding from metal to Cp. In such a way ferrocene, i. e. (η5-Cp2Fe contains 18 bonding electrons giving to this compound "superaromatic" properties in the sense of stability and electrophilic substitution. In contrast to benzenoid aromatic compounds reactions in two Cp-rings can occur giving homo- and heteroannularly mono-, two-… per

  5. Sizable band gap in organometallic topological insulator

    Science.gov (United States)

    Derakhshan, V.; Ketabi, S. A.

    2017-01-01

    Based on first principle calculation when Ceperley-Alder and Perdew-Burke-Ernzerh type exchange-correlation energy functional were adopted to LSDA and GGA calculation, electronic properties of organometallic honeycomb lattice as a two-dimensional topological insulator was calculated. In the presence of spin-orbit interaction bulk band gap of organometallic lattice with heavy metals such as Au, Hg, Pt and Tl atoms were investigated. Our results show that the organometallic topological insulator which is made of Mercury atom shows the wide bulk band gap of about ∼120 meV. Moreover, by fitting the conduction and valence bands to the band-structure which are produced by Density Functional Theory, spin-orbit interaction parameters were extracted. Based on calculated parameters, gapless edge states within bulk insulating gap are indeed found for finite width strip of two-dimensional organometallic topological insulators.

  6. Low-valent organometallics--synthesis, reactivity, and potential applications.

    Science.gov (United States)

    Schulz, Stephan

    2010-06-11

    General concepts for the synthesis and stabilization of low-valent organometallic complexes of Groups 2, 12, 13, and 15 metals and common structural motifs are described. While kinetically stabilized complexes are in the focus for more than two decades, the principle of base-stabilization only recently allowed the synthesis of unforeseen compounds. As-prepared complexes not only show fascinating structural diversities, but exhibit also very interesting chemical properties. Low-valent complexes are of particular interest in the synthesis of novel molecular complexes, but may also find applications as tailor-made precursors for the synthesis of nanosized materials.

  7. Palladium-catalyzed cross-coupling reactions of allylic halides and acetates with indium organometallics.

    Science.gov (United States)

    Rodríguez, David; Pérez Sestelo, José; Sarandeses, Luis A

    2004-11-12

    The palladium(0)-catalyzed cross-coupling reaction of allylic halides and acetates with indium organometallics is reported. In this synthetic transformation, triorganoindium compounds and tetraorganoindates (aryl, alkenyl, and methyl) react with cinnamyl and geranyl halides and acetates to afford the S(N)2 product regioselectively and in good yield. The reaction proceeds with net inversion of the stereochemical configuration.

  8. Organometallic nucleoside analogues with ferrocenyl linker groups: synthesis and cancer cell line studies.

    Science.gov (United States)

    Nguyen, Huy V; Sallustrau, Antoine; Balzarini, Jan; Bedford, Matthew R; Eden, John C; Georgousi, Niki; Hodges, Nikolas J; Kedge, Jonathan; Mehellou, Youcef; Tselepis, Chris; Tucker, James H R

    2014-07-10

    Examples of organometallic compounds as nucleoside analogues are rare within the field of medicinal bioorganometallic chemistry. We report on the synthesis and properties of two chiral ferrocene derivatives containing a nucleobase and a hydroxyalkyl group. These so-called ferronucleosides show promising anticancer activity, with cytostatic studies on five different cancer cell lines indicating that both functional groups are required for optimal activity.

  9. One-pot synthesis of aryl sulfones from organometallic reagents and iodonium salts.

    Science.gov (United States)

    Margraf, Natalie; Manolikakes, Georg

    2015-03-06

    A transition-metal-free arylation of lithium, magnesium, and zinc sulfinates with diaryliodonium salts is described. The sulfinic acid salts were prepared from the reaction of the corresponding organometallic reagents and sulfur dioxide. Combination of the three single steps (preparation of the organometallic compound, sulfinate formation, and arylation) leads to a one-pot sequence for the synthesis of aryl sulfones from simple starting materials. The chemoselectivity of unsymmetrical diaryliodonium salts has been investigated. Potential and limitations of this method will be discussed.

  10. Uncatalyzed hydroamination of electrophilic organometallic alkynes: fundamental, theoretical, and applied aspects.

    Science.gov (United States)

    Wang, Yanlan; Latouche, Camille; Rapakousiou, Amalia; Lopez, Colin; Ledoux-Rak, Isabelle; Ruiz, Jaime; Saillard, Jean-Yves; Astruc, Didier

    2014-06-23

    Simple reactions of the most used functional groups allowing two molecular fragments to link under mild, sustainable conditions are among the crucial tools of molecular chemistry with multiple applications in materials science, nanomedicine, and organic synthesis as already exemplified by peptide synthesis and "click" chemistry. We are concerned with redox organometallic compounds that can potentially be used as biosensors and redox catalysts and report an uncatalyzed reaction between primary and secondary amines with organometallic electrophilic alkynes that is free of side products and fully "green". A strategy is first proposed to synthesize alkynyl organometallic precursors upon addition of electrophilic aromatic ligands of cationic complexes followed by endo hydride abstraction. Electrophilic alkynylated cyclopentadienyl or arene ligands of Fe, Ru, and Co complexes subsequently react with amines to yield trans-enamines that are conjugated with the organometallic group. The difference in reactivities of the various complexes is rationalized from the two-step reaction mechanism that was elucidated through DFT calculations. Applications are illustrated by the facile reaction of ethynylcobalticenium hexafluorophosphate with aminated silica nanoparticles. Spectroscopic, nonlinear-optical and electrochemical data, as well as DFT and TDDFT calculations, indicate a strong push-pull conjugation in these cobalticenium- and Fe- and Ru-arene-enamine complexes due to planarity or near-planarity between the organometallic and trans-enamine groups involving fulvalene iminium and cyclohexadienylidene iminium mesomeric forms.

  11. New Route to Synthesize Surface Organometallic Complexes (SOMC): An Approach by Alkylating Halogenated Surface Organometallic Fragments

    KAUST Repository

    Hamieh, Ali Imad

    2017-02-01

    The aim of this thesis is to explore new simpler and efficient routes for the preparation of surface organometallic complexes (SOMC) for the transformation of small organic molecules to valuable products. The key element in this new route relies on surface alkylation of various halogenated surface coordination complexes or organometallic fragments (SOMF).

  12. Organometallic chemistry meets crystal engineering to give responsive crystalline materials.

    Science.gov (United States)

    Bacchi, A; Pelagatti, P

    2016-01-25

    Dynamically porous crystalline materials have been obtained by engineering organometallic molecules. This feature article deals with organometallic wheel-and-axle compounds, molecules with two relatively bulky groups (wheels) connected by a linear spacer. The wheels are represented by half-sandwich Ru(ii) moieties, while the spacer can be covalent or supramolecular in character. Covalent spacers are obtained using divergent bidentate ligands connecting two [(arene)RuX2] groups. Supramolecular spacers are instead obtained by exploiting the dimerization of COOH or C(O)NH2 groups appended to N-based ligands. A careful choice of ligand functional groups and X ligands leads to the isolation of crystalline materials with remarkable host-guest properties, evidenced by the possibility of reversibly capturing/releasing volatile guests through heterogenous solid-gas reactions. Structural correlations between the crystalline arrangement of the apohost and the host-guest compounds allow us to envisage the structural path followed by the system during the exchange processes.

  13. Patterns in Organometallic Chemistry with Application in Organic Synthesis.

    Science.gov (United States)

    Schwartz, Jeffrey; Labinger, Jay A.

    1980-01-01

    Of interest in this discussion of organometallic complexes are stoichiometric or catalytic reagents for organic synthesis in the complex transformations observed during synthesis for transition metal organometallic complexes. Detailed are general reaction types from which the chemistry or many transition metal organometallic complexes can be…

  14. Organometallic chemistry of b(12) coenzymes.

    Science.gov (United States)

    Kräutler, Bernhard

    2009-01-01

    When coenzyme B(12) was identified as organometallic derivative of vitamin B(12), metal-carbon bonds were revealed to be relevant in life processes. Vitamin B(12), the "antipernicious anaemia factor" required for human health, was isolated earlier as a crystallizable cyano-Co(III)-complex. B(12) cofactors and other cobalt corrinoids play important roles not only in humans, but in the metabolism of archaea and other microorganisms, in particular. Indeed, the microorganisms are the only natural sources of the B(12) derivatives. For other B(12)-requiring organisms the corrinoids are thus "vitamins". However, vitamin B(12) also needs to be converted into organometallic B(12)-forms, which are the typical coenzymes in metabolically important enzymes. One of these, methionine synthase, catalyzes the transfer of a methyl group and its corrinoid cofactor is methylcobalamin. Another one, methylmalonyl-CoA mutase uses a reversible radical process, and coenzyme B(12) (adenosylcobalamin) as its cofactor, to transform methylmalonyl-CoA into succinyl-CoA. In such enzymes, the bound B(12) derivatives engage (or are formed) in exceptional organometallic enzymatic reactions, which depend upon the organometallic reactivity of the B(12) cofactors. Clearly, organometallic B(12) derivatives hold an important position in life and have thus attracted particular interest from the medical sciences, biology, and chemistry. This chapter outlines the unique structures of B(12) derivatives and recapitulates their redox properties and their organometallic chemistry, relevant in the context of the metabolic transformation of B(12) derivatives into the relevant coenzyme forms and for their use in B(12)-dependent enzymes.

  15. Microstructure of Ni-Based Self-Fluxing Alloy Sprayed Coating

    Institute of Scientific and Technical Information of China (English)

    WANG Jin-hua; Milan Friesel; Magnus Willander; Richard Warren

    2005-01-01

    The microstructure of Ni-based self-fluxing alloy thermal sprayed coating was investigated by microanal ysis methods.The sprayed coating was produced by the oxygen-acetylene gas flame spraying Ni-16.9Cr-3.5B4.5Si-4.6Fe-0.83C system alloy powder onto a common steel substrate.Different phases can be recognized from the morphology in the metallographic images and SEM images of compounds of high magnification.The TEM images of the (Cr,Fe,Ni) superlattice phase particles can be obtained in dark field,and the particle size is between 20 nm and 60 nm.The electron diffraction patterns of the superlattice phase and Ni-based solid solution phase can be found,as analyzed by the EDAX spectra chemical composition analysis method.

  16. Models of organometallic complexes for optoelectronic applications

    CERN Document Server

    Jacko, A C; Powell, B J

    2010-01-01

    Organometallic complexes have potential applications as the optically active components of organic light emitting diodes (OLEDs) and organic photovoltaics (OPV). Development of more effective complexes may be aided by understanding their excited state properties. Here we discuss two key theoretical approaches to investigate these complexes: first principles atomistic models and effective Hamiltonian models. We review applications of these methods, such as, determining the nature of the emitting state, predicting the fraction of injected charges that form triplet excitations, and explaining the sensitivity of device performance to small changes in the molecular structure of the organometallic complexes.

  17. Laser cladding of Ni-based alloy on stainless steel

    Institute of Scientific and Technical Information of China (English)

    XUE Chun-fang; TIAN Xin-li; TAN Yong-sheng; WU Zhi-yuan

    2004-01-01

    The coatings on a stainless steel substrate were conducted by laser cladding of Ni-based alloy, using a 5 kW continuous wave CO2 flow transverse laser. SEM, EDX and X-ray diffraction were used to analyze the microstructure and constituent phases of the obtained coatings by laser cladding with direct injection of the powder into the melt pool. Solidification planar, cellular and dendrite structures were observed in Ni-based alloy coating. There exists an optimum metallurgical bond between Ni-based laser cladding layer and the base material. The high hardness of the Ni-based alloy coating is attributed to the presence of M7C3-type carbides (essentially chromium-riched carbide) dispersed in the γ(Ni,Fe) phase matrix.

  18. Organometallic half-sandwich iridium anticancer complexes

    NARCIS (Netherlands)

    Liu, Z.; Habtemariam, A.; Pizarro, A.M.; Fletcher, S.A.; Kisova, A.; Vrana, O.; Salassa, L.; Bruijnincx, P.C.A.|info:eu-repo/dai/nl/33799529X; Clarkson, G.J.; Brabec, V.; Sadler, Peter J.

    2011-01-01

    The low-spin 5d6 IrIII organometallic half-sandwich complexes [(η5-Cpx)Ir(XY)Cl]0/+, Cpx = Cp*, tetramethyl(phenyl)cyclopentadienyl (Cpxph), or tetramethyl(biphenyl)cyclopentadienyl (Cpxbiph), XY = 1,10-phenanthroline (4−6), 2,2′-bipyridine (7−9), ethylenediamine (10 and 11), or picolinate (12−14),

  19. Organometallic and Bioorganometallic Chemistry – Ferrocene Amino Acids

    Directory of Open Access Journals (Sweden)

    Barišić, L.

    2012-01-01

    Full Text Available This article is the second part of a series dealing with organometallic and bioorganometallic chemistry. In the first part of this series a short review on the history and development of these disciplines was given, emphasizing the importance and scope of bioorganometallic chemistry as a new field dealing with conjugates of organometallics and biomolecules (DNA, PNA, amino acids, peptides.... From the variety of biorganometallics, syntheses and properties of simple conjugates of ferrocene with natural amino acids/peptides were elaborated inter alia. This material is the basis for the second part in which ferrocene amino acids are described. The introduction presents nonproteinogenic alicyclic and aromatic amino acids as the models for the title compounds. Naturally occurring amino acids labelled with ferrocene moiety mostly retain properties of the biomolecules included. Contrary to these ω-ferrocenylamino acids, one could imagine specific amino acids with inserted ferrocene core belonging to either homo- or heterodisubstituted type. The central part of this article is devoted to our investigations of the second type - H2N-(CH2m-Fn-(CH2n-COOH. The general rational procedure for synthesis of these compounds and of their N- and/or C-protected derivatives via the azide intermediates N3-CO-(CH2m- Fn-(CH2n-COOMe has been described. In the solid state derivatives of ferrocene amino acids contain intermolecular hydrogen bonds giving dimeric structures, three-dimensional networks or endless helical chains. The solutions of homologues Ac-NH-(CH2m-Fn-(CH2n-COOMe in nonpolar solvents are dominated by open form conformers. Compounds containing 2–3 ferrocene cores connected by amide, imide and oxalamide spacers were prepared by oligomerization of 1'-aminoferrocene-1-carboxylic acid (Fca or by its condensation with the appropriate reagents. Similar to natural amino acids, ferrocene amino acids are water-soluble substances with high melting points

  20. Cytotoxicity and preliminary mode of action studies of novel 2-aryl-4-thiopyrone-based organometallics.

    Science.gov (United States)

    Schmidlehner, Melanie; Flocke, Lea S; Roller, Alexander; Hejl, Michaela; Jakupec, Michael A; Kandioller, Wolfgang; Keppler, Bernhard K

    2016-01-14

    Organometallic complexes with thiopyrone-based ligands have shown promising cytotoxic activity in vitro. To investigate the impact of the ligand backbone modification of these biologically active compounds and enhance the solubility in aqueous solution, the (thio)pyrone scaffold was modified via Suzuki-Miyaura coupling reaction and converted into corresponding organometallic Ru(ii) and Rh(iii) complexes. Characterization of the synthesized compounds was carried out by means of 1D and 2D NMR, ESI MS, and also by X-ray diffraction analysis. The stability in aqueous solution was investigated via(1)H NMR spectroscopy. Due to the close structural resemblance to flavonoids, topoisomerase inhibition, the cytotoxicity in human cancer cell lines as well as ROS generation was investigated by means of the topoisomerase II drug screening assay, the MTT assay and DCFH-DA assay, respectively.

  1. On the π Coordination of Organometallic Fullerene Complexes

    Directory of Open Access Journals (Sweden)

    Bertha Molina

    2011-06-01

    Full Text Available Novel organometallic complexes of fullerene C80 and aryl ligands were simulated. The nature and characteristics of this family of complexes involving π coordination between the fullerene and a metal centre have been studied from a theoretical point of view. We are particularly interested in complexes where η6 coordination is present, this being the strangest manifestation of known coordinations, and thus we have studied several known and simulated compounds of this kind in order to understand the lack of examples. The presence of other η6 or η5 ligands on the opposite side seems to be an important element aiding the stabilization of these complexes, also inducing the conductive and semiconductive behaviour of the studied species.

  2. Cytotoxic properties of a new organometallic platinum(II) complex and its gold(I) heterobimetallic derivatives.

    Science.gov (United States)

    Serratrice, Maria; Maiore, Laura; Zucca, Antonio; Stoccoro, Sergio; Landini, Ida; Mini, Enrico; Massai, Lara; Ferraro, Giarita; Merlino, Antonello; Messori, Luigi; Cinellu, Maria Agostina

    2016-01-14

    A novel platinum(ii) organometallic complex, [Pt(pbi)(Me)(DMSO)], bearing the 2-(2'-pyridyl)-benzimidazole (pbiH) ligand, was synthesized and fully characterized. Interestingly, the reaction of this organometallic platinum(ii) complex with two distinct gold(i) phosphane compounds afforded the corresponding heterobimetallic derivatives with the pbi ligand bridging the two metal centers. The antiproliferative properties in vitro of [Pt(pbi)(Me)(DMSO)] and its gold(i) derivatives as well as those of the known coordination platinum(ii) and palladium(ii) complexes with the same ligand, of the general formula [MCl2(pbiH)], were comparatively evaluated against A2780 cancer cells, either sensitive or resistant to cisplatin. A superior biological activity of the organometallic compound clearly emerged compared to the corresponding platinum(ii) complex; the antiproliferative effects are further enhanced upon attaching the gold(i) triphenylphosphine moiety to the organometallic Pt compound. Remarkably, these novel metal species are able to overcome nearly complete resistance to cisplatin. Significant mechanistic insight into the study compounds was gained after investigating their reactions with a few representative biomolecules by electrospray mass spectrometry and X-ray crystallography. The obtained results are comprehensively discussed.

  3. Emprego de compostos organometálicos mononucleares de paládio(II na ativação de macrófagos peritoneais de camundongos Activation of mice peritoneal macrophages by palladium(II organometallic mononuclear compounds

    Directory of Open Access Journals (Sweden)

    Eduardo Tonon de Almeida

    2005-06-01

    Full Text Available The immune responses are mediated by a variety of cells that, when activated, produce a number of molecules. Macrophages are the first cells to take part in the immune response releasing many compounds in the extracellular environment such as H2O2. Taking into account this aspect we evaluated the activation of an immunological system, in vitro, by determining the H2O2 released in cultures of peritoneal macrophage cells from Swiss mice in the presence of organopalladated compounds of the type [Pd(dmba(X(dppp], dmba = N,N-dimethylbenzylamine, dppp = 1,3-bis(diphenylphosphinepropane, X = Cl, N3, NCO, NCS. An excellent activation of macrophages by the [Pd(dmba(X(dppp] compounds was observed and the influence of the X ligand on the immune response could be verified.

  4. A computational glance at organometallic cyclizations and coupling reactions

    OpenAIRE

    Fiser, Béla

    2016-01-01

    210 p. Organometallic chemistry is one of the main research topics in chemical science.Nowadays, organometallic reactions are the subject of intensive theoretical investigations.However, in many cases, only joint experimental and theoretical effortscould reveal the answers what we are looking for.The fruits of such experimental and theoretical co-operations will be presentedhere. In this work, we are going to deal with homogeneous organometallic catalysisusing computational chemical tools....

  5. Merging porphyrins with organometallics: synthesis and applications.

    Science.gov (United States)

    Suijkerbuijk, Bart M J M; Klein Gebbink, Robertus J M

    2008-01-01

    The coordination chemistry of porphyrins has traditionally involved the ability of the porphyrin's tetrapyrrolic core to accommodate metal ions of varying charges and sizes, and on the organometallic chemistry of the resulting metalloporphyrins. However, the organometallic chemistry of porphyrins is not necessarily restricted to the metal bound in the porphyrin core, but can also be extended to the porphyrin periphery, be it through direct metalation of the porphyrin macrocycle at the meso or beta position, or by attachment to or merger of the porphyrin skeleton with ligands, followed by metalation. This Review focuses on the synthetic strategies used for porphyrins with peripheral metal-carbon bonds. The exciting results that have been produced underscore the importance and future potential of this field.

  6. Group IB Organometallic Chemistry XXXIV: Thermal behavior and chemical reactivity of tetranuclear Me2N-substituted diarylpropenylcopper-copper anion (Vi2Cu4X2) and mixed diarylpropenyl/organocopper (Vi2Cu4R2) compounds

    NARCIS (Netherlands)

    Koten, G. van; Hoedt, R.W.M. ten; Noltes, J.G.

    1980-01-01

    Thermal decomposition of configurationally pure 1, 2-diarylpropenylcopper compounds Z-Vi{2}CU{4}Br{2} and Z-Vi{2}Cu{4}R{2} [Vi @? (2-Me{2}NC{6}H{4})C@?C(Me)-(C{6}H{4}Me-4), R @? 2-Me{2}NC{6}H{4} or 4-MeC{6}H{4}C@?C] predominantly results in the formation of ViH. In contrast, only dimers (ViVi) were

  7. An organometallic single-ion magnet.

    Science.gov (United States)

    Jiang, Shang-Da; Wang, Bing-Wu; Sun, Hao-Ling; Wang, Zhe-Ming; Gao, Song

    2011-04-06

    An organometallic single-ion magnet is synthesized with only 19 non-hydrogen atoms featuring an erbium ion sandwiched by two different aromatic ligands. This molecule displays a butterfly-shaped hysteresis loop at 1.8 K up to even 5 K. Alternating-current (ac) susceptibility measurement reveals the existence of two thermally activated magnetic relaxation processes with the energy barriers as high as 197 and 323 K, respectively.

  8. Group ib organometallic chemistry. XXXIV. Thermal behaviour and chemical reactivity of tetranuclear Me2N-substituted diarypropenylcopper-copper anion (Vi2Cu4X2) and mixed diarylpropenyl/organocopper (Vi2Cu4R2) compounds

    NARCIS (Netherlands)

    Hoedt, R.W.M. ten; Koten, G. van; Noltes, J.G.

    1980-01-01

    Thermal decomposition of configurationally pure 1,2-diarylpropenylcopper compounds Z-Vi2CU4Br2 and Z-Vi2Cu4R2 [Vi = (2-Me2NC6H4)C=C(Me)-(C6H4Me-4), R = 2-Me2NC6H4 or 4-MeC6H4CC] predominantly results in the formation of ViH. In contrast, only dimers (ViVi) were formed on thermolysis of (Z-ViCu2OTf)η

  9. Substituted tertiary phosphine Ru(II) organometallics: catalytic utility on the hydrolysis of etofibrate in pharmaceuticals.

    Science.gov (United States)

    Reddy, P Muralidhar; Shanker, Kanne; Rohini, Rondla; Sarangapani, M; Ravinder, Vadde

    2008-10-01

    Some new organometallics of ruthenium(II) of the type [RuCl2(COD)(CO)L] (1a-f) and [RuCl2(COD)L2] (2a-f) (where L is substituted tertiary phosphines), have been synthesized by using precursors [RuCl2(COD)(CO)(CH3CN)] (1) and [RuCl2(COD)(CH3CN)2] (2) with the substituted tertiary phosphine ligands in 1:1 and 1:2 molar ratio. The organometallics (2a-f) have been further reacted with carbonmonoxide to produce compounds of the type [RuCl2(CO)L2] (3a-f). These compounds were characterized by elemental analysis, IR, NMR (1H, 13C and 31P), mass and electronic spectral data. The catalytic activity of all these organometallics were studied and found that they are efficient catalysts for hydrolysis of etofibrate. The hydrolyzed product was separated by column chromatography and the percent yields are found in the range of 98.6-99.1%.

  10. Thiomaltol-Based Organometallic Complexes with 1-Methylimidazole as Leaving Group: Synthesis, Stability, and Biological Behavior.

    Science.gov (United States)

    Hackl, Carmen M; Legina, Maria S; Pichler, Verena; Schmidlehner, Melanie; Roller, Alexander; Dömötör, Orsolya; Enyedy, Eva A; Jakupec, Michael A; Kandioller, Wolfgang; Keppler, Bernhard K

    2016-11-21

    Thiomaltol, a potential S,O-coordinating molecule, has been utilized for the complexation of four different organometallic fragments, yielding the desired Ru(II) , Os(II) , Rh(III) , and Ir(III) complexes having a "piano-stool" configuration. In addition to the synthesis of these compounds with a chlorido leaving group, the analogous 1-methylimidazole derivatives have been prepared, giving rise to thiomaltol-based organometallics with enhanced stability under physiological conditions. The organometallic compounds have been characterized by NMR spectroscopy, elemental analysis, and X-ray diffraction analysis. Their behavior in aqueous solution and their interactions with certain amino acids have been studied by ESI mass spectrometry. Their pH-dependent stability has been investigated by (1) H NMR in aqueous solution, and their cytotoxicity against three different cancer cell lines has been investigated. Furthermore, their capacity as topoisomerase IIα inhibitors as well as their effect on the cell cycle distribution and reactive oxygen species (ROS) generation have been elucidated.

  11. Antileishmanial action of organometallic complexes of Pt(II and Rh(I

    Directory of Open Access Journals (Sweden)

    CM Mesa-Valle

    1996-10-01

    Full Text Available The three organometallic complexes [(Cis-PtII (DDH (2,5-Dihidroxibenzensulfonic2, RhI (CO2 Cl(2-Aminobenzothiazole and RhI (CO2 Cl(5-Cl-2-Methilbenzothiazole] used in this study had been previously found to have a high in vitro activity against promastigote and amastigote like forms of Leishmania donovani. Here, the cytotoxic effect of these new organometallic complexes on the J-774 macrophages were studied. Only the RhI(CO2 Cl (2-Aminobenzothiazole complex induced substantial toxicity in the cells. Also, we assayed the effect of this complex on the parasite's biosynthesis of macromolecules. The RhI(CO2Cl (5-Cl-2-Methylbenzothiazole complex inhibited DNA, RNA, and protein synthesis. On the other hand, the two other compounds tested did not inhibit the incorporation of radioactive precursors. Finally important ultrastructural alterations in the parasites treated with the two non-cytotoxic complexes were observed.

  12. Molecular alloys, linking organometallics with intermetallic Hume-Rothery phases: the highly coordinated transition metal compounds [M(ZnR)(n)] (n >or= 8) containing organo-zinc ligands.

    Science.gov (United States)

    Cadenbach, Thomas; Bollermann, Timo; Gemel, Christian; Tombul, Mustafa; Fernandez, Israel; von Hopffgarten, Moritz; Frenking, Gernot; Fischer, Roland A

    2009-11-11

    This paper presents the preparation, characterization and bonding analyses of the closed shell 18 electron compounds [M(ZnR)(n)] (M = Mo, Ru, Rh, Ni, Pd, Pt, n = 8-12), which feature covalent bonds between n one-electron organo-zinc ligands ZnR (R = Me, Et, eta(5)-C(5)(CH(3))(5) = Cp*) and the central metal M. The compounds were obtained in high isolated yields (>80%) by treatment of appropriate GaCp* containing transition metal precursors 13-18, namely [Mo(GaCp*)(6)], [Ru(2)(Ga)(GaCp*)(7)(H)(3)] or [Ru(GaCp*)(6)(Cl)(2)], [(Cp*Ga)(4)RhGa(eta(1)-Cp*)Me] and [M(GaCp*)(4)] (M = Ni, Pd, Pt) with ZnMe(2) or ZnEt(2) in toluene solution at elevated temperatures of 80-110 degrees C within a few hours of reaction time. Analytical characterization was done by elemental analyses (C, H, Zn, Ga), (1)H and (13)C NMR spectroscopy. The molecular structures were determined by single crystal X-ray diffraction. The coordination environment of the central metal M and the M-Zn and Zn-Zn distances mimic the situation in known solid state M/Zn Hume-Rothery phases. DFT calculations at the RI-BP86/def2-TZVPP and BP86/TZ2P+ levels of theory, AIM and EDA analyses were done with [M(ZnH)(n)] (M = Mo, Ru, Rh, Pd; n = 12, 10, 9, 8) as models of the homologous series. The results reveal that the molecules can be compared to 18 electron gold clusters of the type M@Au(n), that is, W@Au(12), but are neither genuine coordination compounds nor interstitial cage clusters. The molecules are held together by strong radial M-Zn bonds. The tangential Zn-Zn interactions are generally very weak and the (ZnH)(n) cages are not stable without the central metal M.

  13. 2012 Gordon Research Conference, Organometallic Chemistry, 8-13 2012

    Energy Technology Data Exchange (ETDEWEB)

    Hillhouse, Gregory [Univ. of Chicago, IL (United States)

    2012-07-13

    The 2012 Organometallic Chemistry Gordon Research Conference will highlight new basic science and fundamental applications of organometallic chemistry in industrial, academic, and national lab settings. Scientific themes of the conference will include chemical synthesis, reactivity, catalysis, polymer chemistry, bonding, and theory that involve transition-metal (and main-group) interactions with organic moieties.

  14. Synthesis of main-chain metal carbonyl organometallic macromolecules (MCMCOMs).

    Science.gov (United States)

    Cao, Kai; Murshid, Nimer; Wang, Xiaosong

    2015-04-01

    Synthesis of main-chain metal carbonyl organometallic macromolecules (MCMCOMs) is difficult, mainly due to the instability of metal carbonyl complexes. Despite its challenge a number of MCMCOMs has been prepared by strategically using organometallic, organic, and polymer synthetic chemistry. Main contributions to this research field were reported by the groups of Tyler, Pannell, and Wang and are briefly summarized in this article.

  15. Towards cancer cell-specific phototoxic organometallic rhenium(I) complexes

    OpenAIRE

    Leonidova, Anna; Pierroz, Vanessa; Rubbiani, Riccardo; Heier, Jakob; Ferrari, Stefano; Gasser, Gilles

    2014-01-01

    Over the recent years, several Re(i) organometallic compounds have been shown to be toxic to various cancer cell lines. However, these compounds lacked sufficient selectivity towards cancer tissues to be used as novel chemotherapeutic agents. In this study, we probe the potential of two known N,N-bis(quinolinoyl) Re(i) tricarbonyl complex derivatives, namely Re(i) tricarbonyl [N,N-bis(quinolin-2-ylmethyl)amino]-4-butane-1-amine () and Re(i) tricarbonyl [N,N-bis(quinolin-2-ylmethyl)amino]-5-va...

  16. Multifunctionality of organometallic quinonoid metal complexes: surface chemistry, coordination polymers, and catalysts.

    Science.gov (United States)

    Kim, Sang Bok; Pike, Robert D; Sweigart, Dwight A

    2013-11-19

    rhodium complex showed catalytic activity in Suzuki-Miyaura type reaction. As a result of the excellent stability of the homogeneous catalyst [(quinone)Rh(COD)](-) in water, we also successfully demonstrated catalyst recycling in 1,2- and 1,4-addition reactions. The compound [(quinone)Ir(COD)](-) showed significantly poorer catalytic activity in 1,4-addition reactions. Following upon the excellent coordination ability of the quinonoid rhodium complexes to metal centers, we synthesized organometallic coordination polymer nanocatalysts and silica gel-supported quinonoid rhodium catalysts, the latter using a surface sol-gel technique. The resulting heterogeneous catalysts showed activity in the stereospecific polymerization of phenylacetylene.

  17. Highly functionalized and potent antiviral cyclopentane derivatives formed by a tandem process consisting of organometallic, transition-metal-catalyzed, and radical reaction steps.

    Science.gov (United States)

    Jagtap, Pratap R; Ford, Leigh; Deister, Elmar; Pohl, Radek; Císařová, Ivana; Hodek, Jan; Weber, Jan; Mackman, Richard; Bahador, Gina; Jahn, Ullrich

    2014-08-11

    A simple modular tandem approach to multiply substituted cyclopentane derivatives is reported, which succeeds by joining organometallic addition, conjugate addition, radical cyclization, and oxygenation steps. The key steps enabling this tandem process are the thus far rarely used isomerization of allylic alkoxides to enolates and single-electron transfer to merge the organometallic step with the radical and oxygenation chemistry. This controlled lineup of multiple electronically contrasting reactive intermediates provides versatile access to highly functionalized cyclopentane derivatives from very simple and readily available commodity precursors. The antiviral activity of the synthesized compounds was screened and a number of compounds showed potent activity against hepatitis C and dengue viruses.

  18. The Application of Magnesium(I) Compounds to Energy Storage Materials - Phase 2

    Science.gov (United States)

    2013-06-24

    A. Stasch, A.F. Richards and C. Jones, Organometallics , 2011, 30, 5543-5550. 2. A Digermyne with a Ge-Ge Single Bond that Activates Dihydrogen...and Aminogermylene Complexes, J. Hicks, T.J. Hadlington, C. Schenk, J. Li and C. Jones, Organometallics , 2013, 32, 323-329. 8. Synthesis and...Inaccessible: Magnesium(I) Compounds as Specialist Reducing Agents for the Organometallic Chemist", Invited Keynote Lecture, ICOMC, Lisbon, Portugal, September

  19. Organometallic Derivatization of the Nematocidal Drug Monepantel Leads to Promising Antiparasitic Drug Candidates.

    Science.gov (United States)

    Hess, Jeannine; Patra, Malay; Rangasamy, Loganathan; Konatschnig, Sandro; Blacque, Olivier; Jabbar, Abdul; Mac, Patrick; Jorgensen, Erik M; Gasser, Robin B; Gasser, Gilles

    2016-11-07

    The discovery of novel drugs against animal parasites is in high demand due to drug-resistance problems encountered around the world. Herein, the synthesis and characterization of 27 organic and organometallic derivatives of the recently launched nematocidal drug monepantel (Zolvix(®) ) are described. The compounds were isolated as racemates and were characterized by (1) H, (13) C, and (19) F NMR spectroscopy, mass spectrometry, and IR spectroscopy, and their purity was verified by microanalysis. The molecular structures of nine compounds were confirmed by X-ray crystallography. The anthelmintic activity of the newly designed analogues was evaluated in vitro against the economically important parasites Haemonchus contortus and Trichostrongylus colubriformis. Moderate nematocidal activity was observed for nine of the 27 compounds. Three compounds were confirmed as potentiators of a known monepantel target, the ACR-23 ion channel. Production of reactive oxygen species may confer secondary activity to the organometallic analogues. Two compounds, namely, an organic precursor (3 a) and a cymantrene analogue (9 a), showed activities against microfilariae of Dirofilaria immitis in the low microgram per milliliter range.

  20. Zirconocene and Si-tethered diynes: a happy match directed toward organometallic chemistry and organic synthesis.

    Science.gov (United States)

    Zhang, Wen-Xiong; Zhang, Shaoguang; Xi, Zhenfeng

    2011-07-19

    Characterizing reactive organometallic intermediates is critical for understanding the mechanistic aspects of metal-mediated organic reactions. Moreover, the isolation of reactive organometallic intermediates can often result in the ability to design new synthetic methods. In this Account, we outline synthetic methods that we developed for a variety of diverse Zr/Si organo-bimetallic compounds and Si/N heteroatom-organic compounds through the detailed study of zirconacyclobutene-silacyclobutene fused compounds. Two basic components are involved in this chemistry. The first is the Si-tethered diyne, which owes its rich reactive palette to the combination of the Si-C bond and the C≡C triple bond. The second is the low-valent zirconocene species Cp(2)Zr(II), which has proven very useful in organic synthesis. The reaction of these two components affords the zirconacyclobutene-silacyclobutene fused compound, which is the key reactive Zr/Si organo-bimetallic intermediate discussed here. We discuss the three types of reactions that have been developed for the zirconacyclobutene-silacyclobutene fused intermediate. The reaction with nitriles (the C≡N triple bond) is introduced in the first section. In this one-pot reaction, up to four different components can be combined: the Si-tethered diyne can be reacted with three identical nitriles, with differing nitriles, or with a nitrile and other unsaturated organic substrates such as formamides, isocyanides, acid chlorides, aldehydes, carbodiimides, and azides. Several unexpected multiring, fused Zr/Si organo-bimetallic intermediates were isolated and characterized. A wide variety of N-heterocycles, such as 5-azaindole, pyrrole, and pyrroloazepine derivatives, were obtained. We then discuss the reaction with alkynes (the C≡C triple bond). A consecutive skeletal rearrangement, differing from that observed in the reactions with nitriles, takes place in this reaction. Finally, we discuss the reaction with the C═X substrates

  1. Organometallics and quaternary ammonium salts affect calcium ion desorption from lecithin liposome membranes

    Energy Technology Data Exchange (ETDEWEB)

    Kral, T.E.; Kuczera, J.; Przestalski, S. [Dept. of Physics and Biophysics, Agricultural Univ., Wroclaw (Poland)

    2001-06-01

    The objective of the present work was to compare the effects of groups of tin and lead organometallic compounds and their mixtures with amphiphilic quaternary ammonium salts (QAS) on the process of calcium ion desorption from lecithin liposome membranes, as dependent on the properties of the hydrophilic and hydrophobic parts of QAS. In the investigations the method of radioactive labels was applied. Synergism and antagonism in the action of both groups of compounds were found. The effectiveness of the cooperation depended more on chain length of QAS compounds than on the size and polarity of their hydrophobic parts. The most effective of all compounds studied was a the mixture of benzyldimethylammonium chloride in a mixture with tripropyltin. Since the rate of calcium desorption proved to be a good measure of efficacy of biologically active surfactants, it seems that the conclusions reached in this paper may be useful for choosing compounds which are able to decontaminate the environment polluted with heavy metals. (orig.)

  2. Organometallics and quaternary ammonium salts affect calcium ion desorption from lecithin liposome membranes.

    Science.gov (United States)

    Kral, T E; Kuczera, J; Przestalski, S

    2001-01-01

    The objective of the present work was to compare the effects of groups of tin and lead organometallic compounds and their mixtures with amphiphilic quaternary ammonium salts (QAS) on the process of calcium ion desorption from lecithin liposome membranes, as dependent on the properties of the hydrophilic and hydrophobic parts of QAS. In the investigations the method of radioactive labels was applied. Synergism and antagonism in the action of both groups of compounds were found. The effectiveness of the cooperation depended more on chain length of QAS compounds than on the size and polarity of their hydrophobic parts. The most effective of all compounds studied was a the mixture of benzyldimethylammonium chloride in a mixture with tripropyltin. Since the rate of calcium desorption proved to be a good measure of efficacy of biologically active surfactants, it seems that the conclusions reached in this paper may be useful for choosing compounds which are able to decontaminate the environment polluted with heavy metals.

  3. Organometallic Bonding in an Ullmann-Type On-Surface Chemical Reaction Studied by High-Resolution Atomic Force Microscopy.

    Science.gov (United States)

    Kawai, Shigeki; Sadeghi, Ali; Okamoto, Toshihiro; Mitsui, Chikahiko; Pawlak, Rémy; Meier, Tobias; Takeya, Jun; Goedecker, Stefan; Meyer, Ernst

    2016-10-01

    The on-surface Ullmann-type chemical reaction synthesizes polymers by linking carbons of adjacent molecules on solid surfaces. Although an organometallic compound is recently identified as the reaction intermediate, little is known about the detailed structure of the bonded organometallic species and its influence on the molecule and the reaction. Herein atomic force microscopy at low temperature is used to study the reaction with 3,9-diiododinaphtho[2,3-b:2',3'-d]thiophene (I-DNT-VW), which is polymerized on Ag(111) in vacuum. Thermally sublimated I-DNT-VW picks up a Ag surface atom, forming a CAg bond at one end after removing an iodine. The CAg bond is usually short-lived, and a CAgC organometallic bond immediately forms with an adjacent molecule. The existence of the bonded Ag atoms strongly affects the bending angle and adsorption height of the molecular unit. Density functional theory calculations reveal the bending mechanism, which reveals that charge from the terminus of the molecule is transferred via the Ag atom into the organometallic bond and strengths the local adsorption to the substrate. Such deformations vanish when the Ag atoms are removed by annealing and CC bonds are established.

  4. Nanostructure fabrication using electron beam irradiation of organometallic compounds

    CERN Document Server

    Bedson, T R

    2001-01-01

    Nanoelectronics- the quest to fabricate quantum devices- is the motivation for this thesis. The place of nanolithography is discussed amongst conventional microfabrication methods, together with the materials currently employed in lithography. The experimental methods, equipment and new resist materials (films of nanoparticles) are then explored in the work described. A summary of the results obtained by the research is presented, followed by the detailed results in the form of a series of published and submitted papers. A systematic study of the response of ferrocene adsorbed onto graphite at 160K to low energy electron beams, that results in varying behaviour depending on the energy of irradiation, is first described. Following are studies of the characteristics of passivated gold nanoclusters when used as a monolayer negative tone resist in direct electron beam writing. Fabrication of lines with widths as narrow as 26 nm has been achieved. Measurements of the linewidth as a function of electron dose allow ...

  5. Organometallic perovskites for optoelectronic applications (Conference Presentation)

    Science.gov (United States)

    Levchuk, Levgen; Hoegl, Florian; Brandl, Marco; Osvet, Andres; Hock, Rainer; Herre, Patrick; Wolfgang, Wolfgang; Schweizer, Peter; Spiecker, Erdmann; Batentschuk, Miroslaw; Brabec, Christoph

    2016-09-01

    Organometallic halide perovskites CH3NH3BX3 (B= Pb, Sn, Ge; X = I, Br, Cl) have become one of the most promising semiconductors for solar cell applications, reaching power conversion efficiencies beyond 20%. Improving our ability to harness the full potential of organometal halide perovskites requires the development of more reliable synthesis routines of well defined, reproducible and defect free reference systems allowing to study the fundamental photo-physical processes. In this study we present size and band gap engineering for organo-lead perovskites crystallites with various shapes and sizes ranging from the 5 nm regime all the way to 1 cm. Colloidal nano-crystals, micro-crystlline particles as well as single crystals are demonstrated with excellent purity and control in shape and size are demonstrated. The structural, optical and photo-physical properties of these reference materials are investigated and analyzed as function of their size and shape.

  6. Advanced polymer chemistry of organometallic anions

    Energy Technology Data Exchange (ETDEWEB)

    Chamberlin, R.M.; Abney, K.D. [Los Alamos National Lab., NM (United States); Balaich, G.J.; Fino, S.A. [Air Force Academy, CO (United States)

    1997-11-01

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The objective of the project was to prepare and characterize new polymers incorporating cobalt dicarbollide. Specific goals were to prepare polymerizable cobalt dicarbollide monomers using the nucleophilic substitution route discovered in laboratories and to establish the reaction conditions required to form polymers from these complexes. This one-year project resulted in two publications (in press), and provided the foundation for further investigations into polymer synthesis and characterization using cobalt dicarbollide and other metallocarboranes. Interest in synthesizing organometallic polymers containing the cobalt bis(dicarbollide) anion is motivated by their possible application as cation exchange materials for the remediation of cesium-137 and strontium-90 from nuclear wastes.

  7. Supported organometallic complexes: Surface chemistry, spectroscopy, and catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Marks, T.J.

    1990-02-01

    The goal of our program is to define those modes of interaction that take place between organometallic molecules and inorganic surfaces and, ultimately, to correlate various molecule-surface structures with catalytic properties.

  8. Some Tendencies in the Literature of Organometallic Chemistry

    Science.gov (United States)

    Haiduc, Ionel

    1972-01-01

    A survey of the number of references published annually for individual elements or groups of elements suggests that the organometallic chemistry literature is approaching a phase of slower increase. (Author/NH)

  9. Development of organometallic S6K1 inhibitors.

    Science.gov (United States)

    Qin, Jie; Rajaratnam, Rajathees; Feng, Li; Salami, Jemilat; Barber-Rotenberg, Julie S; Domsic, John; Reyes-Uribe, Patricia; Liu, Haiying; Dang, Weiwei; Berger, Shelley L; Villanueva, Jessie; Meggers, Eric; Marmorstein, Ronen

    2015-01-08

    Aberrant activation of S6 kinase 1 (S6K1) is found in many diseases, including diabetes, aging, and cancer. We developed ATP competitive organometallic kinase inhibitors, EM5 and FL772, which are inspired by the structure of the pan-kinase inhibitor staurosporine, to specifically inhibit S6K1 using a strategy previously used to target other kinases. Biochemical data demonstrate that EM5 and FL772 inhibit the kinase with IC50 value in the low nanomolar range at 100 μM ATP and that the more potent FL772 compound has a greater than 100-fold specificity over S6K2. The crystal structures of S6K1 bound to staurosporine, EM5, and FL772 reveal that the EM5 and FL772 inhibitors bind in the ATP binding pocket and make S6K1-specific contacts, resulting in changes to the p-loop, αC helix, and αD helix when compared to the staurosporine-bound structure. Cellular data reveal that FL772 is able to inhibit S6K phosphorylation in yeast cells. Together, these studies demonstrate that potent, selective, and cell permeable S6K1 inhibitors can be prepared and provide a scaffold for future development of S6K inhibitors with possible therapeutic applications.

  10. Alkynyl-ruthenium based azo-organometallics: Thermal evolution of thin films microstructure

    Science.gov (United States)

    Niziol, Jacek; Fillaut, Jean-Luc; Sniechowski, Maciek; Khammar, Farida; Sahraoui, Bouchta

    2012-08-01

    Alkynyl-ruthenium based azo-organometallics were studied in form of powders and thin layers obtained by conventional spin coating from solution. X-ray diffractometry revealed partly crystalline structure of powders while corresponding films were amorphous. Next, the films were subjected to a programmed heating and cooling. Meanwhile, their optical properties were monitored in situ using spectroscopic ellipsometry. It was found that upon thermic treatment films spontaneously adopted a crystalline structure, different from previously observed in the case of starting powders. This structure depended on chemical composition of a particular alkynyl-ruthenium compound.

  11. New preparation of benzylic aluminum and zinc organometallics by direct insertion of aluminum powder.

    Science.gov (United States)

    Blümke, Tobias D; Groll, Klaus; Karaghiosoff, Konstantin; Knochel, Paul

    2011-12-16

    The reaction of commercial Al-powder (3 equiv) and InCl(3) (1-5 mol %) with benzylic chlorides provides various functionalized benzylic aluminum sesquichlorides under mild conditions (THF, 20 °C, 3-24 h) without homocoupling (organometallics reacted smoothly with various electrophiles (Pd-catalyzed cross-couplings, or Cu-mediated acylations, allylations, or 1,4-addition reactions). Electron-poor benzylic chlorides or substrates prone to Wurtz coupling can be converted to benzylic zinc compounds by the reaction of Al-powder in the presence of ZnCl(2).

  12. Use of column V alkyls in organometallic vapor phase epitaxy (OMVPE)

    Science.gov (United States)

    Ludowise, M. J.; Cooper, C. B., III

    1982-01-01

    The use of the column V-trialkyls trimethylarsenic (TMAs) and trimethylantimony (TMSb) for the organometallic vapor phase epitaxy (OM-VPE) of III-V compound semiconductors is reviewed. A general discussion of the interaction chemistry of common Group III and Group V reactants is presented. The practical application of TMSb and TMAs for OM-VPE is demonstrated using the growth of GaSb, GaAs(1-y)Sb(y), Al(x)Ga(1-x)Sb, and Ga(1-x)In(x)As as examples.

  13. Determining the Quantum Efficiency for Activation of an Organometallic Photoinitiator for Cationic Polymerization: An Experiment for the Physical or Inorganic Chemistry Laboratory

    Science.gov (United States)

    Hayes, David M.; Mahar, Maura; Schnabel, R. Chris; Shah, Paras; Lees, Alistair J.; Jakubek, Vladimir

    2007-01-01

    We present a new laboratory experiment on the photochemistry of organometallic [eta][superscript 5],[eta][superscript 6]-mixed-sandwich compounds, which is suitable for both the physical chemistry and inorganic chemistry laboratory. Specifically, students use 1,10-phenanthroline to trap the intermediate formed when…

  14. Organometallic Ru(II) Photosensitizers Derived from π-Expansive Cyclometalating Ligands: Surprising Theranostic PDT Effects.

    Science.gov (United States)

    Sainuddin, Tariq; McCain, Julia; Pinto, Mitch; Yin, Huimin; Gibson, Jordan; Hetu, Marc; McFarland, Sherri A

    2016-01-04

    The purpose of the present study was to investigate the influence of π-expansive cyclometalating ligands on the photophysical and photobiological properties of organometallic Ru(II) compounds. Four compounds with increasing π conjugation on the cyclometalating ligand were prepared, and their structures were confirmed by HPLC, 1D and 2D (1)H NMR, and mass spectrometry. The properties of these compounds differed substantially from their Ru(II) polypyridyl counterparts. Namely, they were characterized by red-shifted absorption, very weak to no room temperature phosphorescence, extremely short phosphorescence state lifetimes ( 300 μM) but was phototoxic to cells in the nanomolar regime. Exceptionally large phototherapeutic margins, exceeding 3 orders of magnitude in some cases, were accompanied by bright ligand-centered intracellular fluorescence in cancer cells. Thus, Ru(II) organometallic systems derived from π-expansive cyclometalating ligands, such 4,9,16-triazadibenzo[a,c]napthacene (pbpn), represent the first class of potent light-responsive Ru(II) cyclometalating agents with theranostic potential.

  15. Half-metallicity in 2D organometallic honeycomb frameworks

    Science.gov (United States)

    Sun, Hao; Li, Bin; Zhao, Jin

    2016-10-01

    Half-metallic materials with a high Curie temperature (T C) have many potential applications in spintronics. Magnetic metal free two-dimensional (2D) half-metallic materials with a honeycomb structure contain graphene-like Dirac bands with π orbitals and show excellent aspects in transport properties. In this article, by investigating a series of 2D organometallic frameworks with a honeycomb structure using first principles calculations, we study the origin of forming half-metallicity in this kind of 2D organometallic framework. Our analysis shows that charge transfer and covalent bonding are two crucial factors in the formation of half-metallicity in organometallic frameworks. (i) Sufficient charge transfer from metal atoms to the molecules is essential to form the magnetic centers. (ii) These magnetic centers need to be connected through covalent bonding, which guarantee the strong ferromagnetic (FM) coupling. As examples, the organometallic frameworks composed by (1,3,5)-benzenetricarbonitrile (TCB) molecules with noble metals (Au, Ag, Cu) show half-metallic properties with T C as high as 325 K. In these organometallic frameworks, the strong electronegative cyano-groups (CN groups) drive the charge transfer from metal atoms to the TCB molecules, forming the local magnetic centers. These magnetic centers experience strong FM coupling through the d-p covalent bonding. We propose that most of the 2D organometallic frameworks composed by molecule—CN—noble metal honeycomb structures contain similar half metallicity. This is verified by replacing TCB molecules with other organic molecules. Although the TCB-noble metal organometallic framework has not yet been synthesized, we believe the development of synthesizing techniques and facility will enable the realization of them. Our study provides new insight into the 2D half-metallic material design for the potential applications in nanotechnology.

  16. Hydrotelluration of alkynes: a unique route to Z-vinyl organometallics

    Directory of Open Access Journals (Sweden)

    Vieira Maurício L.

    2001-01-01

    Full Text Available The hydrotelluration reaction of alkynes is reviewed. The transformation of vinylic tellurides into reactive vinyl organometallics and the coupling reactions of vinylic tellurides with alkynes and organometallics are presented.

  17. A robust microfluidic device for the synthesis and crystal growth of organometallic polymers with highly organized structures.

    Science.gov (United States)

    Liu, Xiao; Yi, Qiaolian; Han, Yongzhen; Liang, Zhenning; Shen, Chaohua; Zhou, Zhengyang; Sun, Jun-Liang; Li, Yizhi; Du, Wenbin; Cao, Rui

    2015-02-02

    A simple and robust microfluidic device was developed to synthesize organometallic polymers with highly organized structures. The device is compatible with organic solvents. Reactants are loaded into pairs of reservoirs connected by a 15 cm long microchannel prefilled with solvents, thus allowing long-term counter diffusion for self-assembly of organometallic polymers. The process can be monitored, and the resulting crystalline polymers are harvested without damage. The device was used to synthesize three insoluble silver acetylides as single crystals of X-ray diffraction quality. Importantly, for the first time, the single-crystal structure of silver phenylacetylide was determined. The reported approach may have wide applications, such as crystallization of membrane proteins, synthesis and crystal growth of organic, inorganic, and polymeric coordination compounds, whose single crystals cannot be obtained using traditional methods.

  18. Applications of and alternatives to pi-electron-deficient azine organometallics in metal catalyzed cross-coupling reactions.

    Science.gov (United States)

    Campeau, Louis-Charles; Fagnou, Keith

    2007-07-01

    While the use of pi-deficient azine halides in palladium catalyzed cross-coupling reactions is common, the use of pi-electron deficient azine organometallics has been less intensively examined. In recent years, important advances have been made that are beginning to address this deficiency and need. The purpose of this tutorial review is to highlight and discuss the innovations that facilitate the synthesis of azine-containing biaryls with a focus on the pyridine structural motif. Given the number of important compounds which exhibit azine-heterobiaryls and the wide use of cross-coupling methods in their synthesis, this review should be of interest among synthetic organic chemists and organometallic chemists alike.

  19. Isothermal Oxidation Comparison of Three Ni-Based Superalloys

    Science.gov (United States)

    Mallikarjuna, H. T.; Richards, N. L.; Caley, W. F.

    2017-05-01

    Ni-based superalloys are used for high-temperature components of gas turbines in both industrial and aerospace applications due to their ability to maintain dimensional stability under conditions of high stress and strain. The oxidation resistance of these alloys often dictates their service lifetime. This study focuses on the isothermal oxidation behavior of three Ni-based superalloys, namely, polycrystalline cast IN738LC, single-crystal N5, and a ternary Ni-Fe-Cr (TAS) powder metallurgy alloy. The isothermal oxidation tests were conducted at 900 °C in the static air up to 1000 h, and the specific aspects studied were the oxidation behavior of these chromia-forming and alumina-forming alloys that are used extensively in industry. In particular, the behavior of oxide scale growth and subsurface changes were analyzed in detail using various techniques such as SEM, EDS, and AFM. From the isothermal oxidation kinetics, the oxidation rate constant, k p, was calculated for each alloy and found to be; k p = 2.79 × 10-6 mg2 cm-4 s-1 for IN738LC, k p = 1.42 × 10-7 mg2 cm-4 s-1 for N5 and k p = 1.62 × 10-7 mg2 cm-4 s-1 for TAS. Based on a microstructural analysis, IN738LC exhibited a continuous dense outer scale of Cr2O3 and discontinuous inner scale of Al2O3, whereas N5 and TAS showed a dense outer scale of Al2O3 alone. The results suggested that the N5 and PM-TAS alloys are more oxidation resistant than the IN738LC under these conditions.

  20. Tuning exchange interactions in organometallic semiconductors

    Science.gov (United States)

    Rawat, Naveen; Manning, Lane W.; Hua, Kim-Ngan; Headrick, Randall L.; Cherian, Judy G.; Bishop, Michael M.; McGill, Stephen A.; Furis, Madalina I.

    2015-09-01

    Organic semiconductors are emerging as a leading area of research as they are expected to overcome limitations of inorganic semiconductor devices for certain applications where low cost manufacturing, device transparency in the visible range or mechanical flexibility are more important than fast switching times. Solution processing methods produce thin films with millimeter sized crystalline grains at very low cost manufacturing prices, ideally suited for optical spectroscopy investigations of long range many-body effects in organic systems. To this end, we synthesized an entire family of organosoluble 3-d transition metal Pc's and successfully employed a novel solution-based pen-writing deposition technique to fabricate long range ordered thin films of mixtures of metal-free (H2Pc) molecule and organometallic phthalocyanines (MPc's). Our previous studies on the parent MPc crystalline thin films identified different electronic states mediating exchange interactions in these materials. This understanding of spin-dependent exchange interaction between delocalized π-electrons with unpaired d spins enabled the further tuning of these interactions by mixing CoPc and H2Pc in different ratios ranging from 1:1 to 1000:1 H2Pc:MPc. The magnitude of the exchange is also tunable as a function of the average distance between unpaired spins in these materials. Furthermore, high magnetic field (B materials.

  1. Organometallic chemistry using partially fluorinated benzenes.

    Science.gov (United States)

    Pike, Sebastian D; Crimmin, Mark R; Chaplin, Adrian B

    2017-03-28

    Fluorobenzenes, in particular fluorobenzene (FB) and 1,2-difluorobenzene (1,2-DiFB), are increasingly becoming recognised as versatile solvents for conducting organometallic chemistry and transition-metal-based catalysis. The presence of fluorine substituents reduces the ability to donate π-electron density from the arene and consequently fluorobenzenes generally bind weakly to metal centres, allowing them to be used as essentially non-coordinating solvents or as readily displaced ligands. In this context, examples of well-defined complexes of fluorobenzenes are discussed, including trends in binding strength with increasing fluorination and different substitution patterns. Compared to more highly fluorinated benzenes, FB and 1,2-DiFB typically demonstrate greater chemical inertness, however, C-H and C-F bond activation reactions can be induced using appropriately reactive transition metal complexes. Such reactions are surveyed, including catalytic examples, not only to provide perspective for the use of FB and 1,2-DiFB as innocent solvent media, but also to highlight opportunities for their exploitation in contemporary organic synthesis.

  2. Ultrafast studies of organometallic photochemistry: The mechanism of carbon-hydrogen bond activation in solution

    Energy Technology Data Exchange (ETDEWEB)

    Bromberg, S.E.

    1998-05-01

    When certain organometallic compounds are photoexcited in room temperature alkane solution, they are able to break or activate the C-H bonds of the solvent. Understanding this potentially practical reaction requires a detailed knowledge of the entire reaction mechanism. Because of the dynamic nature of chemical reactions, time-resolved spectroscopy is commonly employed to follow the important events that take place as reactants are converted to products. For the organometallic reactions examined here, the electronic/structural characteristics of the chemical systems along with the time scales for the key steps in the reaction make ultrafast UV/Vis and IR spectroscopy along with nanosecond Step-Scan FTIR spectroscopy the ideal techniques to use for this study. An initial study of the photophysics of (non-activating) model metal carbonyls centering on the photodissociation of M(CO){sub 6} (M = Cr, W, Mo) was carried out in alkane solutions using ultrafast IR spectroscopy. Next, picosecond UV/vis studies of the C-H bond activation reaction of Cp{sup *}M(CO){sub 2} (M = Rh, Ir), conducted in room temperature alkane solution, are described in an effort to investigate the origin of the low quantum yield for bond cleavage ({approximately}1%). To monitor the chemistry that takes place in the reaction after CO is lost, a system with higher quantum yield is required. The reaction of Tp{sup *}Rh(CO){sub 2} (Tp{sup *} = HB-Pz{sub 3}{sup *}, Pz{sup *} = 3,5-dimethylpyrazolyl) in alkanes has a quantum yield of {approximately}30%, making time resolved spectroscopic measurements possible. From ultrafast IR experiments, two subsequently formed intermediates were observed. The nature of these intermediates are discussed and the first comprehensive reaction mechanism for a photochemical C-H activating organometallic complex is presented.

  3. Modules for Introducing Organometallic Reactions: A Bridge between Organic and Inorganic Chemistry

    Science.gov (United States)

    Schaller, Chris P.; Graham, Kate J.; Johnson, Brian J.

    2015-01-01

    Transition metal organometallic reactions have become increasingly important in the synthesis of organic molecules. A new approach has been developed to introduce organometallic chemistry, along with organic and inorganic chemistry, at the foundational level. This change highlights applications of organometallic chemistry that have dramatically…

  4. Solar cells, structures including organometallic halide perovskite monocrystalline films, and methods of preparation thereof

    KAUST Repository

    Bakr, Osman M.

    2017-03-02

    Embodiments of the present disclosure provide for solar cells including an organometallic halide perovskite monocrystalline film (see fig. 1.1B), other devices including the organometallic halide perovskite monocrystalline film, methods of making organometallic halide perovskite monocrystalline film, and the like.

  5. Modules for Introducing Organometallic Reactions: A Bridge between Organic and Inorganic Chemistry

    Science.gov (United States)

    Schaller, Chris P.; Graham, Kate J.; Johnson, Brian J.

    2015-01-01

    Transition metal organometallic reactions have become increasingly important in the synthesis of organic molecules. A new approach has been developed to introduce organometallic chemistry, along with organic and inorganic chemistry, at the foundational level. This change highlights applications of organometallic chemistry that have dramatically…

  6. Studies on MgNi-Based Metal Hydride Electrode with Aqueous Electrolytes Composed of Various Hydroxides

    Directory of Open Access Journals (Sweden)

    Jean Nei

    2016-08-01

    Full Text Available Compositions of MgNi-based amorphous-monocrystalline thin films produced by radio frequency (RF sputtering with a varying composition target have been optimized. The composition Mg52Ni39Co3Mn6 is identified to possess the highest initial discharge capacity of 640 mAh·g−1 with a 50 mA·g−1 discharge current density. Reproduction in bulk form of Mg52Ni39Co3Mn6 alloy composition was prepared through a combination of melt spinning (MS and mechanical alloying (MA, shows a sponge-like microstructure with >95% amorphous content, and is chosen as the metal hydride (MH alloy for a sequence of electrolyte experiments with various hydroxides including LiOH, NaOH, KOH, RbOH, CsOH, and (C2H54N(OH. The electrolyte conductivity is found to be closely related to cation size in the hydroxide compound used as 1 M additive to the 4 M KOH aqueous solution. The degradation performance of Mg52Ni39Co3Mn6 alloy through cycling demonstrates a strong correlation with the redox potential of the cation in the alkali hydroxide compound used as 1 M additive to the 5 M KOH aqueous solution. NaOH, CsOH, and (C2H54N(OH additions are found to achieve a good balance between corrosion and conductivity performances.

  7. Organometallic iron complexes as potential cancer therapeutics.

    Science.gov (United States)

    Mojžišová, Gabriela; Mojžiš, Ján; Vašková, Janka

    2014-01-01

    Metal-containing drugs have long been used for medicinal purposes in more or less empirical way. The potential of these anticancer agents has only been fully realised and explored since the discovery of the biological activity of cisplatin. Cisplatin and carboplatin have been two of the most successful anti-cancer agents ever developed, and are currently used to treat ovarian, lung and testicular cancers. They share certain side effects, so their clinical use is severely limited by dose-limiting toxicity. Inherent or acquired resistance is a second problem often associated with platinum-based drugs, with further limits of their clinical use. These problems have prompted chemists to employ different strategies in development of the new metal-based anticancer agents with different mechanisms of action. There are various metal complexes still under development and investigation for the future cancer treatment use. In the search for novel bio-organometallic molecules, iron containing anti-tumoral agents are enjoying an increasing interest and appear very promising as the potential drug candidates. Iron, as an essential cofactor in a number of enzymes and physiological processes, may be less toxic than non essential metals, such as platinum. Up to now, some of iron complexes have been tested as cytotoxic agents and found to be endowed with an antitumor activity in several in vitro tests (on cultured cancer cell lines) and few in vivo experiments (e. g. on Ehrlich's ascites carcinoma). Although the precise molecular mechanism is yet to be defined, a number of observations suggest that the reactive oxygen species can play important role in iron-induced cytotoxicty. This review covers some relevant examples of research on the novel iron complexes.

  8. Organometallic vapor-phase epitaxy theory and practice

    CERN Document Server

    Stringfellow, Gerald B

    1989-01-01

    Here is one of the first single-author treatments of organometallic vapor-phase epitaxy (OMVPE)--a leading technique for the fabrication of semiconductor materials and devices. Also included are metal-organic molecular-beam epitaxy (MOMBE) and chemical-beam epitaxy (CBE) ultra-high-vacuum deposition techniques using organometallic source molecules. Of interest to researchers, students, and people in the semiconductor industry, this book provides a basic foundation for understanding the technique and the application of OMVPE for the growth of both III-V and II-VI semiconductor materials and the

  9. Medicinal organometallic chemistry: designing metal arene complexes as anticancer agents.

    Science.gov (United States)

    Peacock, Anna F A; Sadler, Peter J

    2008-11-13

    The field of medicinal inorganic chemistry is rapidly advancing. In particular organometallic complexes have much potential as therapeutic and diagnostic agents. The carbon-bound and other ligands allow the thermodynamic and kinetic reactivity of the metal ion to be controlled and also provide a scaffold for functionalization. The establishment of structure-activity relationships and elucidation of the speciation of complexes under conditions relevant to drug testing and formulation are crucial for the further development of promising medicinal applications of organometallic complexes. Specific examples involving the design of ruthenium and osmium arene complexes as anticancer agents are discussed.

  10. Group IB Organometallic Chemistry XXXI. Synthesis and characterization of tetranuclear Me2N- and Me2NCH2-substituted diarylpropenylcopper-copper anion compounds (Vi2Cu4X2) containing bridging propenyl ligands. Isolation of a thermally stable mixed diarylpropenyl/arylcopper compound (Vi2Cu4Ar2)

    NARCIS (Netherlands)

    Koten, G. van; Hoedt, R.W.M. ten; Noltes, J.G.

    1979-01-01

    Thermally stable 1, 2-diarylpropenylcopper compounds (ViCu{2}X){n} (Vi = (2-Me{2}NC{6}H{4})C@?C(Me)(C{6}H{4}Me-4), X = Br (n = 2) or OTf2OTf = trifluoromethanesulphonate = triflate. and Vi = (2-Me{2}NCH{2}C{6}H{4})C@?C(Me)(C{6}H{4}Me-4), X = Br (n = 2)) have been prepared by reaction of configuratio

  11. Direct borohydride fuel cell using Ni-based composite anodes

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Jia; Sahai, Yogeshwar; Buchheit, Rudolph G. [Department of Materials Science and Engineering, The Ohio State University, 2041 College Rd., Columbus, OH 43210 (United States)

    2010-08-01

    In this study, nickel-based composite anode catalysts consisting of Ni with either Pd on carbon or Pt on carbon (the ratio of Ni:Pd or Ni:Pt being 25:1) were prepared for use in direct borohydride fuel cells (DBFCs). Cathode catalysts used were 1 mg cm{sup -2} Pt/C or Pd electrodeposited on activated carbon cloth. The oxidants were oxygen, oxygen in air, or acidified hydrogen peroxide. Alkaline solution of sodium borohydride was used as fuel in the cell. High power performance has been achieved by DBFC using non-precious metal, Ni-based composite anodes with relatively low anodic loading (e.g., 270 mW cm{sup -2} for NaBH{sub 4}/O{sub 2} fuel cell at 60 C, 665 mW cm{sup -2} for NaBH{sub 4}/H{sub 2}O{sub 2} fuel cell at 60 C). Effects of temperature, oxidant, and anode catalyst loading on the DBFC performance were investigated. The cell was operated for about 100 h and its performance stability was recorded. (author)

  12. Microstructure stability: Optimisation of 263 Ni-based superalloy

    Directory of Open Access Journals (Sweden)

    Crozet Coraline

    2014-01-01

    Full Text Available To reduce CO2 emissions on coal-fired power plant, A-ultra supercritical (A-USC power plant whose steam conditions exceed 700 °C are being developed. At these elevated temperatures, the use of Ni-base superalloys becomes necessary. In this context and within the European project NextGenPower, focus is made on commercial Nimonic C-263 as a candidate material for turbine rotors. Nimonic C-263 is known to have low sensitivity to segregation, high workability and high weldability which are major properties for the manufacture of large shafts. Long-term creep strength is also required for this application and unfortunately Nimonic C-263 shows η-phase precipitation after long-time exposure between 700 °C–900 °C which is detrimental for long-term creep properties. The composition of Nimonic C-263 was thus optimised to overcome the formation of η-phase. Trial tests were made in order to study the effect of hardening contribution elements on microstructural and mechanical properties. Then, a 500 mm diameter forged rotor was made from optimised 263 alloy and shows promising properties.

  13. Kinetics of Grain Growth in 718 Ni-Base Superalloy

    Directory of Open Access Journals (Sweden)

    Huda Z.

    2014-10-01

    Full Text Available The Haynes® 718 Ni-base superalloy has been investigated by use of modern material characterization, metallographic and heat treatment equipment. Grain growth annealing experiments at temperatures in the range of 1050 – 1200 oC (1323–1473K for time durations in the range of 20 min-22h have been conducted. The kinetic equations and an Arrhenius-type equation have been applied to compute the grain-growth exponent n and the activation energy for grain growth, Qg, for the investigated alloy. The grain growth exponent, n, was computed to be in the range of 0.066-0.206; and the n values have been critically discussed in relation to the literature. The activation energy for grain growth, Qg, for the investigated alloy has been computed to be around 440 kJ/mol; and the Qg data for the investigated alloy has been compared with other metals and alloys and ceramics; and critically analyzed in relation to our results.

  14. FATIGUE CRACK PROPAGATION OF Ni-BASE SUPERALLOYS

    Institute of Scientific and Technical Information of China (English)

    X.B.Liu; L.Z.Ma; K.M.Chang; E.Barbero

    2005-01-01

    Time-dependent Fatigue Crack Propagation (FCP) behaviors of five Ni-base superalloys were investigated at various temperatures under fatigue with various holding times and sustained loading conditions.The new concept of damage zone is defined and employed to evaluate the alloys' resistance to hold-time FCP.A special testing procedure is designed to get the maximum damage zone of the alloys.Udimet 720 and Waspaloy show shorter damage zones than alloys 706 and 718.The fractographical analyses show that the fracture surfaces of the specimens under hold-time fatigue conditions are mixtures with intergranular and transgranular modes.As the extension of holding time per cycle, the portion of intergranular fracture increases.The effects of loading stress intensity, temperature, holding time, alloy chemistry, and alloy microstructure on damage zone and the crack growth behaviors are studied.Hold-time usually increases the alloy's FCP rate, but there are few exemptions.For instance, the steady state hold-time FCP rate of Waspaloy at 760℃ is lower than that without hold-time.The beneficial effect of hold-time was attributed to the creep caused stress relaxation during the hold-time.

  15. Microstructural and Chemical Rejuvenation of a Ni-Based Superalloy

    Science.gov (United States)

    Yao, Zhiqi; Degnan, Craig C.; Jepson, Mark A. E.; Thomson, Rachel C.

    2016-10-01

    The microstructural evolution of the Ni-based superalloy CMSX-4 including the change in gamma prime morphology, size, and distribution after high-temperature degradation and subsequent rejuvenation heat treatments has been examined using field emission gun scanning electron microscopy and transmission electron microscopy. In this paper, it is shown that there are significant differences in the size of the `channels' between gamma prime particles, the degree of rafting, and the size of tertiary gamma prime particles in each of the different microstructural conditions studied. Chemical analysis has been carried out to compare rejuvenated and pre-service samples after the same subsequent degradation procedure. The results indicate that although the microstructures of pre-service and rejuvenated samples are similar, chemical differences are more pronounced in the rejuvenated samples, suggesting that chemical segregation from partitioning of the elements was not completely eliminated through the applied rejuvenation heat treatment. A number of modified rejuvenation heat treatment trials were carried out to reduce the chemical segregation prior to creep testing. The creep test results suggest that chemical segregation has an immeasurable influence on the short-term mechanical properties under the test conditions used here, indicating that further work is required to fully understand the suitability of specific rejuvenation heat treatments and their role in the extension of component life in power plant applications.

  16. Microstructural and Chemical Rejuvenation of a Ni-Based Superalloy

    Science.gov (United States)

    Yao, Zhiqi; Degnan, Craig C.; Jepson, Mark A. E.; Thomson, Rachel C.

    2016-12-01

    The microstructural evolution of the Ni-based superalloy CMSX-4 including the change in gamma prime morphology, size, and distribution after high-temperature degradation and subsequent rejuvenation heat treatments has been examined using field emission gun scanning electron microscopy and transmission electron microscopy. In this paper, it is shown that there are significant differences in the size of the `channels' between gamma prime particles, the degree of rafting, and the size of tertiary gamma prime particles in each of the different microstructural conditions studied. Chemical analysis has been carried out to compare rejuvenated and pre-service samples after the same subsequent degradation procedure. The results indicate that although the microstructures of pre-service and rejuvenated samples are similar, chemical differences are more pronounced in the rejuvenated samples, suggesting that chemical segregation from partitioning of the elements was not completely eliminated through the applied rejuvenation heat treatment. A number of modified rejuvenation heat treatment trials were carried out to reduce the chemical segregation prior to creep testing. The creep test results suggest that chemical segregation has an immeasurable influence on the short-term mechanical properties under the test conditions used here, indicating that further work is required to fully understand the suitability of specific rejuvenation heat treatments and their role in the extension of component life in power plant applications.

  17. ROMP Synthesis of Iron-Containing Organometallic Polymers.

    Science.gov (United States)

    Dragutan, Ileana; Dragutan, Valerian; Filip, Petru; Simionescu, Bogdan C; Demonceau, Albert

    2016-02-06

    The paper overviews iron-containing polymers prepared by controlled "living" ring-opening metathesis polymerization (ROMP). Developments in the design and synthesis of this class of organometallic polymers are highlighted, pinpointing methodologies and newest trends in advanced applications of hybrid materials based on polymers functionalized with iron motifs.

  18. Rational design of an organometallic glutathione transferase inhibitor

    Energy Technology Data Exchange (ETDEWEB)

    Ang, W.H.; Parker, L.J.; De Luca, A.; Juillerat-Jeanneret, L.; Morton, C.J.; LoBello, M.; Parker, M.W.; Dyson, P.J.; (ISIC)

    2010-08-17

    A hybrid organic-inorganic (organometallic) inhibitor was designed to target glutathione transferases. The metal center is used to direct protein binding, while the organic moiety acts as the active-site inhibitor. The mechanism of inhibition was studied using a range of biophysical and biochemical methods.

  19. Open-shell organometallics: reactivity at the ligand

    NARCIS (Netherlands)

    W.I. Dzik; B. de Bruin

    2011-01-01

    The purpose of this review is to show that (cooperative) ligand radical reactivity can be effectively employed in synthetic organometallic chemistry and catalysis to achieve selectivity in radical-type transformations. The ‘redox non-innocence’ of ligands, and the controlled reactivity of ‘ligand ra

  20. A "Classic Papers" Approach to Teaching Undergraduate Organometallic Chemistry

    Science.gov (United States)

    Duncan, Andrew P.; Johnson, Adam R.

    2007-01-01

    We have structured an upper-level undergraduate course in organometallic chemistry on a selection of "classic" publications in the field. This approach offers students a richly contextual introduction to many of the fundamental tenets of the discipline. After a brief introduction to the field led by the faculty, the students themselves are…

  1. Recent applications of polymer supported organometallic catalysts in organic synthesis.

    Science.gov (United States)

    Kann, Nina

    2010-09-07

    Recent developments concerning the application of polymer supported organometallic reagents in solid phase synthesis are reviewed, with a special focus on methodology for carbon-carbon formation. Examples of reactions that are covered include the classical Suzuki, Sonogashira and Heck coupings, but also aryl amination, epoxide opening, rearrangements, metathesis and cyclopropanation. Applications in the field of asymmetric synthesis are also discussed.

  2. Recent Applications of Polymer Supported Organometallic Catalysts in Organic Synthesis

    Directory of Open Access Journals (Sweden)

    Nina Kann

    2010-09-01

    Full Text Available Recent developments concerning the application of polymer supported organometallic reagents in solid phase synthesis are reviewed, with a special focus on methodology for carbon-carbon formation. Examples of reactions that are covered include the classical Suzuki, Sonogashira and Heck coupings, but also aryl amination, epoxide opening, rearrangements, metathesis and cyclopropanation. Applications in the field of asymmetric synthesis are also discussed.

  3. Ligand Rearrangements of Organometallic Complexes inSolution

    Energy Technology Data Exchange (ETDEWEB)

    Shanoski, Jennifer E. [Univ. of California, Berkeley, CA (United States)

    2006-01-01

    Many chemical reactions utilize organometallic complexes as catalysts. These complexes find use in reactions as varied as bond activation, polymerization, and isomerization. This thesis outlines the construction of a new ultrafast laser system with an emphasis on the generation of tunable mid-infrared pulses, data collection, and data analysis.

  4. Precipitation hardening in Fe--Ni base austenitic alloys

    Energy Technology Data Exchange (ETDEWEB)

    Chang, K.M.

    1979-05-01

    The precipitation of metastable Ni/sub 3/X phases in the austenitic Fe--Ni-base alloys has been investigated by using various combinations of hardening elements, including Ti, Ta, Al, and Nb. The theoretical background on the formation of transition precipitates has been summarized based on: atomic size, compressibility, and electron/atom ratio. A model is proposed from an analysis of static concentration waves ordering the fcc lattice. Ordered structure of metastable precipitates will change from the triangularly ordered ..gamma..', to the rectangularly ordered ..gamma..'', as the atomic ratio (Ti + Al)/(Ta + Nb) decreases. The concurrent precipitation of ..gamma..' and ..gamma..'' occurs at 750/sup 0/C when the ratio is between 1.5 and 1.9. Aging behavior was studied over the temperature range of 500/sup 0/C to 900/sup 0/C. Typical hardness curves show a substantial hardening effect due to precipitation. A combination of strength and fracture toughness can be developed by employing double aging techniques. The growth of these coherent intermediate precipitates follows the power law with the aging time t : t/sup 1/3/ for the spherical ..gamma..' particles; and t/sup 1/2/ for the disc-shaped ..gamma..''. The equilibrium ..beta.. phase is observed to be able to nucleate on the surface of imbedded carbides. The addition of 5 wt % Cr to the age-hardened alloys provides a non-magnetic austenite which is stable against the formation of mechanically induced martensite.Cr addition retards aging kinetics of the precipitation reactions, and suppresses intergranular embrittlement caused by the high temperature solution anneal. The aging kinetics are also found to be influenced by solution annealing treatments.

  5. Strategies to prepare and use functionalized organometallic reagents.

    Science.gov (United States)

    Klatt, Thomas; Markiewicz, John T; Sämann, Christoph; Knochel, Paul

    2014-05-16

    Polyfunctional zinc and magnesium organometallic reagents occupy a central position in organic synthesis. Most organic functional groups are tolerated by zinc organometallic reagents, and Csp(2)-centered magnesium organometallic reagents are compatible with important functional groups, such as the ester, aryl ketone, nitro, cyano, and amide functions. This excellent chemoselectivity gives zinc- and magnesium-organometallic reagents a central position in modern organic synthesis. Efficient and general preparations of these organometallic reagents, as well as their most practical and useful reactions, are presented in this Perspective. As starting materials, a broad range of organic halides (iodides, bromides, and also to some extent chlorides) can be used for the direct insertion of magnesium or zinc powder; the presence of LiCl very efficiently promotes such insertions. Alternatively, aromatic or heterocyclic bromides also undergo a smooth bromine-magnesium exchange when treated with i-PrMgCl·LiCl. Alternative precursors of zinc and magnesium reagents are polyfunctionalized aryl and heteroaryl molecules, which undergo directed metalations with sterically hindered TMP bases (TMP = 2,2,6,6-tetramethylpiperide) of magnesium and zinc. This powerful C-H functionalization method gives access to polyfunctional heterocyclic zinc and magnesium reagents, which undergo efficient reactions with numerous electrophiles. The compatibility of the strong TMP-bases with BF3·OEt2 (formation of frustrated Lewis pairs) dramatically increases the scope of these metalations, giving for example, a practical access to magnesiated pyridines and pyrazines, which can be used as convenient building blocks for the preparation of biologically active molecules.

  6. Influence of Al on the microstructure and carburization performance of a Ni-based alloy coating

    Energy Technology Data Exchange (ETDEWEB)

    Cangue, Feliciano Jose Ricardo, E-mail: fcangue@yahoo.com [Federal University of Parana, Centro Politecnico, s/n - Bairro Jardim das Americas, Curitiba, Parana, Cx P. 19011, CEP: 81531-990 (Brazil); D' Oliveira, Ana Sofia Climaco Monteiro, E-mail: sofmat@ufpr.br [Mechanical Engineering Department, Federal University of Parana, Centro Politecnico, s/n - Bairro Jardim das Americas, Curitiba, Parana, Cx P. 19011, CEP: 81531-990 (Brazil)

    2010-04-15

    Carburization is a degradation mechanism involving the diffusion of carbon into a metal alloy and its accumulation on the surface. Coke forms on the internal walls of crude oil refining equipment and adversely affects its efficiency and service life. In an attempt to enhance the service life of materials exposed to these aggressive environments, this work investigated the development of a protective coating to reduce the diffusion of carbon into the surfaces of components. Coatings were tailored by mixing the atomized Ni alloy (Hastealloy C) with 5 wt% and 15 wt% Al powders and deposited by Plasma Transferred Arc hardfacing. Pack carburizing was carried out at 650 deg. C and 850 deg. C for 6 h, and temperature stability was tested in an air furnace to evaluate the performance of the coatings. Characterization included measurement of Vickers microhardness profiles and microstructure analysis by optical and scanning electron microscopy and X-ray diffraction. The good weldability of the original Ni-based alloy was not altered by the presence of Al. Richer Al coatings developed ordered aluminide compounds in a Ni matrix and exhibited increased hardness and dilution. Exposure to temperatures of 650 deg. C and 850 deg. C in an air furnace and to a carburizing environment neither compromised coating hardness nor produced a carburizing layer, although carbides were identified at the top surface. Our results will be of benefit in the development of an alternative solution for the protection of components operating in carburizing environments.

  7. Reaction mechanisms in the organometallic vapor phase epitaxial growth of GaAs

    Science.gov (United States)

    Larsen, C. A.; Buchan, N. I.; Stringfellow, G. B.

    1988-01-01

    The decomposition mechanisms of AsH3, trimethylgallium (TMGa), and mixtures of the two have been studied in an atmospheric-pressure flow system with the use of D2 to label the reaction products which are analyzed in a time-of-flight mass spectrometer. AsH3 decomposes entirely heterogeneously to give H2. TMGa decomposes by a series of gas-phase steps, involving methyl radicals and D atoms to produce CH3D, CH4, C2H6, and HD. TMGa decomposition is accelerated by the presence of AsH3. When the two are mixed, as in the organometallic vapor phase epitaxial growth of GaAs, both compounds decompose in concert to produce only CH4. A likely model is that of a Lewis acid-base adduct that forms and subsequently eliminates CH4.

  8. Iron-Catalyzed C-C Cross-Couplings Using Organometallics.

    Science.gov (United States)

    Guérinot, Amandine; Cossy, Janine

    2016-08-01

    Over the last decades, iron-catalyzed cross-couplings have emerged as an important tool for the formation of C-C bonds. A wide variety of alkenyl, aryl, and alkyl (pseudo)halides have been coupled to organometallic reagents, the most currently used being Grignard reagents. Particular attention has been devoted to the development of iron catalysts for the functionalization of alkyl halides that are generally challenging substrates in classical cross-couplings. The high functional group tolerance of iron-catalyzed cross-couplings has encouraged organic chemists to use them in the synthesis of bioactive compounds. Even if some points remain obscure, numerous studies have been carried out to investigate the mechanism of iron-catalyzed cross-coupling and several hypotheses have been proposed.

  9. Synthesis and structure-activity relationship study of organometallic bioconjugates of the cyclic octapeptide octreotate.

    Science.gov (United States)

    Gross, Annika; Habig, Daniel; Metzler-Nolte, Nils

    2013-12-16

    The chemically stabilized somatostatin-derived cyclic octapeptide octreotate has a number of interesting applications in medicinal chemistry. Here, a number of different organometallic derivatives of octreotate were prepared, and their properties were investigated. Specifically, we report the synthesis and characterization of ruthenocene, ferrocene, and cobaltocenium octreotate derivatives and their fluorophore-labeled conjugates as well as a dicobalt hexacarbonyl alkyne functionalized octreotate. To provide further insights into their characteristics, the log P values and electrochemical properties of the novel metal conjugates were compared. For biological activity, we determined their toxicity in three different cell lines. Cellular uptake and colocalization of selected compounds were studied by fluorescence microscopy with particular focus on efficiency and specificity of their uptake through the somatostatin receptor SSTR to elucidate the value of the metallocene head group for its potential use as a nontoxic and universal peptide label.

  10. MALDI-TOFMS analysis of coordination and organometallic complexes: a nic(h)e area to work in.

    Science.gov (United States)

    Wyatt, Mark F

    2011-07-01

    A mini-review of the characterisation of metal-containing compounds by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) is presented. Organometallic and coordination compounds have many varied applications, most notably in industrial catalytic processes and also in the electronics and healthcare sectors. In general, the compounds discussed, be they small or large molecules, have a high percentage metal content, rather than simply containing 'a metal atom'. A brief history of the field is given, but the main scope over the last 5 years is covered in some detail. How MALDI-TOFMS compliments electrospray for metal-containing compounds is highlighted. Perspectives on recent advances, such as solvent-free and air/moisture-sensitive sample preparation, and potential future challenges and developments, such as nanomaterials and metallodrug/metallometabolite imaging, are given.

  11. Aromaticity of group 14 organometallics: experimental aspects.

    Science.gov (United States)

    Lee, Vladimir Ya; Sekiguchi, Akira

    2007-01-01

    The long story of aromatic compounds has extended over almost two centuries, since the discovery by Faraday of "bicarburet of hydrogen", or C(6)H(6), now called benzene. Since then, the chemistry of aromatic compounds has been developed extensively; this is reflected in the synthesis of novel classes of aromatic derivatives including charged species, nonclassical (Möbius, three-dimensional, homo-, metalla-) aromatics, and fullerenes. The theory of aromaticity has also undergone a spectacular evolution since the first definition of aromaticity by Hückel; the classification of aromaticity now requires the consideration of versatile criteria: energetic, structural, magnetic, among others. In this Review, we discuss the current state of affairs in the chemistry of aromatic compounds of the heavier Group 14 elements, the latest experimental achievements, as well as future prospects in the field.

  12. Effectiveness of various organometallics as antiwear additives in mineral oil

    Science.gov (United States)

    Buckley, D. H.

    1977-01-01

    Sliding friction experiments were conducted with 1045 steel contacting 302 stainless steel and lubricated with various organometallics in mineral oil. Auger emission spectroscopy was used to determine the element present in the wear contact zone. The results indicate that there are organometallics which are as effective an antiwear additives as the commonly used zinc dialkyl dithiophosphate. These include dimethyl cadmium, triphenyl lead thiomethoxide, and triphenyl tin chloride. The additives were examined in concentrations to 1 weight percent. With dimethyl cadmium at concentrations of 0.5 weight percent and above, cadmium was detected in the contact zone. Coincident with the detection of cadmium, a marked decrease in the friction coefficient was observed. All additives examined reduced friction, but only the aforementioned reduced wear to a level comparable to that observed with zinc dialkyl dithiophosphate.

  13. An Organometallic Future in Green and Energy Chemistry?

    Energy Technology Data Exchange (ETDEWEB)

    Crabtree, Robert H

    2011-01-10

    The title topic is reviewed with selected examples taken from recent work, such as: the 'hydrogen borrowing' amine alkylation by alcohols; the dehydrogenative coupling of amine and alcohol to give amide; Ru complexes as solar cell photosensitizers; Ir organometallics as water oxidation catalyst precursors and as OLED emitters; as well as recent hydrogen storage strategies involving catalytic dehydrogenation of ammonia-borane and of organic heterocycles.

  14. Organic/Organometallic Hybrids as Broadband Nonlinear Transmission Materials

    Science.gov (United States)

    2010-06-01

    property correlation in organometallic complexes in order to develop broadband nonlinear transmission materials . To realize this goal, we have...platinum complexes and 10 zinc phthalocyanine derivatives provided by collaborators in China. From these studies, we have discovered that in order to...in the near-IR region still limited their application as broadband nonlinear absorbing materials . To solve this problem, two approaches were

  15. Porous protein crystals as catalytic vessels for organometallic complexes.

    Science.gov (United States)

    Tabe, Hiroyasu; Abe, Satoshi; Hikage, Tatsuo; Kitagawa, Susumu; Ueno, Takafumi

    2014-05-01

    Porous protein crystals, which are protein assemblies in the solid state, have been engineered to form catalytic vessels by the incorporation of organometallic complexes. Ruthenium complexes in cross-linked porous hen egg white lysozyme (HEWL) crystals catalyzed the enantioselective hydrogen-transfer reduction of acetophenone derivatives. The crystals accelerated the catalytic reaction and gave different enantiomers based on the crystal form (tetragonal or orthorhombic). This method represents a new approach for the construction of bioinorganic catalysts from protein crystals.

  16. Pyrazine-based organometallic complex: synthesis, characterization, and supramolecular chemistry.

    Science.gov (United States)

    Bhowmick, Sourav; Chakraborty, Sourav; Das, Atanu; Rajamohanan, P R; Das, Neeladri

    2015-03-16

    The design, synthesis, and characterization of a new pyrazine-based ditopic platinum(II) organometallic complex are reported. The molecular structure of the organoplatinum pyrazine dipod was determined by single-crystal X-ray crystallography. The potential utility of this organometallic ditopic acceptor as a building block in the construction of neutral metallasupramolecular macrocycles containing the pyrazine motif was explored. Pyrazine motifs containing supramolecules were characterized by multinuclear NMR (including (1)H DOSY), mass spectrometry, and elemental analysis. The geometry of each supramolecular framework was optimized by employing the PM6 semiempirical molecular orbital method to predict its shape and size. The ability of the pyrazine-based organoplatinum complex to act as a host for nitroaromatic guest (2,4-dinitrotoluene and PA) molecules was explored by isothermal titration calorimetry (ITC). The binding stoichiometry and thermodynamic parameters of these host-guest complexation reactions were evaluated using ITC. Theoretical calculations were performed to obtain insight into the binding pattern between the organometallic host and nitroaromatic guests. The preferable binding propensity of the binding sites of complex 1 for both nitroaromatics (PA and 2,4-dinitrotoluene) determined by molecular simulation studies corroborates well with the experimental results as obtained by ITC experiments.

  17. Structure and bonding in some organotitanium and related compounds

    NARCIS (Netherlands)

    Zeinstra, Jabik Dominicus

    1981-01-01

    In this thesis investigations on the structure and chemical bonding in some organometallic compounds of transition metals with few d electrons are described. Structural studies involve the X-ray diffraction analyses of two titanium compounds. Theoretical studies deal with the electronic structure of

  18. Chemistry Related to Semiconductor Growth Involving Organometallics

    Science.gov (United States)

    1990-05-11

    NDR ) was also observed in a 50-period GaInAs (150A)/InP (80,k) superlattice. These NDRs may be interpreted as being caused by the resonant tunneling...impurity level of the Group V sources. Commercial arsine contains various concentrations of a germanium speciW which provides germanium donors to the... silicon compound. Most of the TEG/TBA and TEG/arsine growth investigations were carried out at 76 Torr. Atmospheric pressure growth showed that under these

  19. Computational Raman spectroscopy of organometallic reaction products in lithium and sodium-based battery systems.

    Science.gov (United States)

    Sánchez-Carrera, Roel S; Kozinsky, Boris

    2014-11-28

    A common approach to understanding surface reaction mechanisms in rechargeable lithium-based battery systems involves spectroscopic characterization of the product mixtures and matching of spectroscopic features to spectra of pure candidate reference compounds. This strategy, however, requires separate chemical synthesis and accurate characterization of potential reference compounds. It also assumes that atomic structures are the same in the actual product mixture as in the reference samples. We propose an alternative approach that uses first-principles computations of spectra of the possible reaction products and by-products present in advanced battery systems. We construct a library of computed Raman spectra for possible products, achieving excellent agreement with reference experimental data, targeting solid-electrolyte interphase in Li-ion cells and discharge products of Li-air cells. However, the solid-state crystalline structure of Li(Na) metal-organic compounds is often not known, making the spectra computations difficult. We develop and apply a novel technique of simplifying spectra calculations by using dimer-like representations of the solid state structures. On the basis of a systematic investigation, we demonstrate that molecular dimers of Li(Na)-based organometallic material provide relevant information about the vibrational properties of many possible solid reaction products. Such an approach should serve as a basis to extend existing spectral libraries of molecular structures relevant for understanding the link between atomic structures and measured spectroscopic data of materials in novel battery systems.

  20. An electrochemical investigation of mechanical alloying of MgNi-based hydrogen storage alloys

    Science.gov (United States)

    Jiang, Jian-Jun; Gasik, Michael

    The electrochemical properties of amorphous MgNi-based hydrogen storage alloys synthesized by mechanical alloying (MA) were evaluated. The results show that these amorphous Mg 50Ni 50 alloys exhibit a higher discharge capacity and relatively good rate capacity at a suitable grinding time while their cycle life is very poor. In order to improve the cycle life, the surface of the amorphous Mg 50Ni 50 alloy was coated with Ti, Al and Zr in Spex 8000 mill/mixer and the coating effects were further investigated. Based on experimental results, two kinds of MgNi-based amorphous alloys are designed by substituting part of Mg in MgNi-based alloys by suitable elements. These alloys are then composed of four components. Thus, the cycle life of electrodes consisting of these quaternary amorphous alloys is greatly improved.

  1. Electrochemical properties of Ni-based inert phases incorporated Si/graphite composite anode

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hansu; Im, Dongmin; Doo, Seok Gwang [Energy and Materials Research Lab., Samsung Advanced Institute of Technology, Giheung-Gu, Yong-In City (Korea)

    2007-12-06

    Ni-based inert phases incorporated Si/graphite composite, prepared by thermal decomposition of a mixture of nickel stearate and Si/graphite composite, was investigated as an anode material for lithium-ion batteries. The first discharge and charge capacities of this material were 940 and 640 mAh g{sup -1}, respectively, with 72% of the first cycle coulombic efficiency. Back scattered electron image of the cross section of this material revealed that Ni-based inert phases, i.e., Ni and Ni{sub 2}Si were finely dispersed in the Si/graphite matrix. Ex situ X-ray diffraction results indicated that those Ni-based inert phases were inactive against lithium, and they are believed to improve the electrical conduction network inside the active material and to alleviate to some extent the mechanical stresses associated with volume changes during cycling. (author)

  2. ROLE OF GRAIN BOUNDARY CARBIDES IN CRACKING BEHAVIOR OF Ni BASE ALLOYS

    Directory of Open Access Journals (Sweden)

    SEONG SIK HWANG

    2013-02-01

    Full Text Available The primary water stress corrosion cracking (PWSCC of Alloy 600 in a PWR has been reported in the control rod drive mechanism (CRDM, pressurizer instrumentation, and the pressurizer heater sleeves. Recently, two cases of boric acid precipitation that indicated leaking of the primary cooling water were reported on the bottom head surface of steam generators (SG in Korea. The PWSCC resistance of Ni base alloys which have intergranular carbides is higher than those which have intragranular carbides. Conversely, in oxidized acidic solutions like sodium sulfate or sodium tetrathionate solutions, the Ni base alloys with a lot of carbides at the grain boundaries and shows less stress corrosion cracking (SCC resistance. The role of grain boundary carbides in SCC behavior of Ni base alloys was evaluated and effect of intergranular carbides on the SCC susceptibility were reviewed from the literature.

  3. Alloying effects of refractory elements in the dislocation of Ni-based single crystal superalloys

    Directory of Open Access Journals (Sweden)

    Shiyu Ma

    2016-12-01

    Full Text Available The alloying effects of W, Cr and Re in the [100] (010 edge dislocation cores (EDC of Ni-based single crystal superalloys are investigated using first-principles based on the density functional theory (DFT. The binding energy, Mulliken orbital population, density of states, charge density and radial distribution functions are discussed, respectively. It is clearly demonstrated that the addition of refractory elements improves the stability of the EDC systems. In addition, they can form tougher bonds with their nearest neighbour (NN Ni atoms, which enhance the mechanical properties of the Ni-based single crystal superalloys. Through comparative analysis, Cr-doped system has lower binding energy, and Cr atom has evident effect to improve the systemic stability. However, Re atom has the stronger alloying effect in Ni-based single crystal superalloys, much more effectively hindering dislocation motion than W and Cr atoms.

  4. Sequential insertion of three different organometallics into a versatile building block containing a PNA backbone.

    Science.gov (United States)

    Patra, Malay; Gasser, Gilles; Bobukhov, Dmytro; Merz, Klaus; Shtemenko, Alexander V; Metzler-Nolte, Nils

    2010-06-28

    In the view of developing a synthetic route for the controlled insertion of distinct organometallic moieties into peptide nucleic acid (PNA) oligomers, a proof-of-principle study of the chemoselective insertion of three different organometallics into a building block containing both a PNA backbone and an alkyne side-chain is presented in this study.

  5. New Twists and Turns for Actinide Chemistry: Organometallic Infinite Coordination Polymers of Thorium Diazide.

    Science.gov (United States)

    Monreal, Marisa J; Seaman, Lani A; Goff, George S; Michalczyk, Ryszard; Morris, David E; Scott, Brian L; Kiplinger, Jaqueline L

    2016-03-07

    Two organometallic 1D infinite coordination polymers and two organometallic monometallic complexes of thorium diazide have been synthesized and characterized. Steric control of these self-assembled arrays, which are dense in thorium and nitrogen, has also been demonstrated: infinite chains can be circumvented by using steric bulk either at the metallocene or with a donor ligand in the wedge.

  6. A Review on Inertia and Linear Friction Welding of Ni-Based Superalloys

    Science.gov (United States)

    Chamanfar, Ahmad; Jahazi, Mohammad; Cormier, Jonathan

    2015-04-01

    Inertia and linear friction welding are being increasingly used for near-net-shape manufacturing of high-value materials in aerospace and power generation gas turbines because of providing a better quality joint and offering many advantages over conventional fusion welding and mechanical joining techniques. In this paper, the published works up-to-date on inertia and linear friction welding of Ni-based superalloys are reviewed with the objective to make clarifications on discrepancies and uncertainties reported in literature regarding issues related to these two friction welding processes as well as microstructure, texture, and mechanical properties of the Ni-based superalloy weldments. Initially, the chemical composition and microstructure of Ni-based superalloys that contribute to the quality of the joint are reviewed briefly. Then, problems related to fusion welding of these alloys are addressed with due consideration of inertia and linear friction welding as alternative techniques. The fundamentals of inertia and linear friction welding processes are analyzed next with emphasis on the bonding mechanisms and evolution of temperature and strain rate across the weld interface. Microstructural features, texture development, residual stresses, and mechanical properties of similar and dissimilar polycrystalline and single crystal Ni-based superalloy weldments are discussed next. Then, application of inertia and linear friction welding for joining Ni-based superalloys and related advantages over fusion welding, mechanical joining, and machining are explained briefly. Finally, present scientific and technological challenges facing inertia and linear friction welding of Ni-based superalloys including those related to modeling of these processes are addressed.

  7. Irradiation effects in oxide dispersion strengthened (ODS) Ni-base alloys for Gen. IV nuclear reactors

    Science.gov (United States)

    Oono, Naoko; Ukai, Shigeharu; Kondo, Sosuke; Hashitomi, Okinobu; Kimura, Akihiko

    2015-10-01

    Oxide particle dispersion strengthened (ODS) Ni-base alloys are irradiated by using simulation technique (Fe/He dual-ion irradiation) to investigate the reliability to Gen. IV high-temperature reactors. The fine oxide particles with less than 10 nm in average size and approximately 8.0 × 1022 m-3 in number density remained after 101 dpa irradiation. The tiny helium bubbles were inside grains, not at grain-boundaries; it is advantageous effect of oxide particles which trap the helium atoms at the particle-matrix interface. Ni-base ODS alloys demonstrated their great ability to overcome He embrittlement.

  8. A new definition of coordination number and its use in lanthanide and actinide coordination and organometallic chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Marcalo, J.; Pires de Matos, A. (ICEN, LNETI, Sacavem (Portugal). Dept. de Quimica)

    1989-01-01

    A steric coordination number of a ligand is defined, based on the solid angle comprising the van der Waals' spheres of the atoms of that ligand, as an alternative to the formal coordination number in discussing structural aspects of lanthanide and actinide coordination and organometallic compounds. The study of the bond lengths in 274 structurally characterized compounds of the lanthanides (including scandium and Yttrium), in oxidation states II and III, and the actinides (thorium and uranium), in oxidation states III and IV, was the basis to derive ligand effective radii which are discussed in relation to bonding, coordination geometries, metal ionic radii and oxidation states. Potential uses of the new definition of coordination number and of the ligand effective radii obtained in molecular structure comparison and bond length prediction are also discussed. (author).

  9. Fundamental organometallic reactions: Applications on the CYBER 205

    Science.gov (United States)

    Rappe, A. K.

    1984-01-01

    Two of the most challenging problems of Organometallic chemistry (loosely defined) are pollution control with the large space velocities needed and nitrogen fixation, a process so capably done by nature and so relatively poorly done by man (industry). For a computational chemist these problems are on the fringe of what is possible with conventional computers (large models needed and accurate energetics required). A summary of the algorithmic modification needed to address these problems on a vector processor such as the CYBER 205 and a sketch of findings to date on deNOx catalysis and nitrogen fixation are presented.

  10. Supported organometallic complexes: Surface chemistry, spectroscopy, and catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Marks, T.J.

    1992-02-01

    The long-range goal of this project is to elucidate and understand the surface chemistry and catalytic properties of well-defined, highly-reactive organometallic molecules (principally based upon abundant actinide, lanthanide, and early transition elements) adsorbed on metal oxides and halides. The nature of the adsorbed species is probed by a battery of chemical and physicochemical techniques, to understand the nature of the molecular-surface coordination chemistry and how this can give rise to extremely high catalytic activity. A complementary objective is to delineate the scope and mechanisms of the heterogeneous catalytic reactions, as well as to relate them both conceptually and functionally to model systems generated in solution.

  11. Antitumor and biological investigation of doubly cyclometalated ruthenium(II) organometallics derived from benzimidazolyl derivatives.

    Science.gov (United States)

    Elumalai, Palani; Jeong, Yong Joon; Park, Dae Won; Kim, Dong Hwan; Kim, Hyunuk; Kang, Se Chan; Chi, Ki-Whan

    2016-04-21

    In this study, we report the synthesis, anticancer and biological properties of three doubly cyclometalated phenylbenzimidazole derived ruthenium(ii) organometallics () and their corresponding three organic ligands. The structures of were fully characterized by various analytical techniques, and the meso stereoisomer of the doubly cyclometalated ruthenacycle was unambiguously confirmed by single crystal X-ray diffraction. The anticancer effects of the newly synthesized compounds were tested against selected human cancer cell lines AGS (gastric carcinoma), SK-hep-1 (hepatocellular carcinoma), and HCT-15 (colorectal carcinoma). The growth inhibitory effects of ruthenacycles on cancer cells were found to be considerably more effective against the abovementioned cancer cells than the reference drug oxaliplatin. Compound exhibited a more specific effect on the AGS cells. Gene-fishing and ELISA array were performed to analyze the target genes and cytokine secretion by . As a result, a significant reduction was observed in RPS21 by . Moreover, increased the secretion of cytokines such as IFNγ in macrophages and reduced the release of cytokines such as rantes and IGF-1. These results show that could be a very good anticancer drug through the regulation of the RPS21 gene and cytokines.

  12. Time-incremental creep–fatigue damage rule for single crystal Ni-base superalloys

    NARCIS (Netherlands)

    Tinga, T.; Brekelmans, W.A.M.; Geers, M.G.D.

    2009-01-01

    In the present paper a damage model for single crystal Ni-base superalloys is proposed that integrates time-dependent and cyclic damage into a generally applicable time-incremental damage rule. A criterion based on the Orowan stress is introduced to detect slip reversal on the microscopic level and

  13. EXPERIMENTAL STUDY ON ENHANCED HEAT TRANSFER WITH NI-BASED IMPLANTED SPIRAL FINNED TUBES

    Institute of Scientific and Technical Information of China (English)

    Sun Feng-zhong; Huang Xin-yuan; Wang Nai-hua; Shi Yue-tao; Ping Ya-ming

    2003-01-01

    The new type of heat exchanger elements-Ni-based Implanted Spiral Finned Turbes (NISFT) was studied and tested, which can contribute to increase the efficiency and reliability. The relation of Nu, Eu and Re with different fin pitch, fin height, transverse pitch and longitudinal pitch were gained, which constituted the basic foundation for the engineering application of NISFT.

  14. Combustion Synthesis of NiAl and In-situ Joining to Ni-based Superalloy

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Combustion synthesis is used as a joining technology to join Ni-based superalloys with in-situ synthesized NiAl filler. The synthesis mechanism is discussed. The microstructure of the joints is investigated and the joint strength is also evaluated by tensile testing.

  15. Cube slip and non-Schmid effects in single crystal Ni-base superalloys

    NARCIS (Netherlands)

    Tinga, T.; Brekelmans, W.A.M.; Geers, M.G.D.

    2010-01-01

    An advanced constitutive model incorporating two specific aspects of Ni-base superalloy deformation behaviour is proposed. Several deformation mechanisms are active in these two-phase materials. In the matrix phase, cube slip plays an important role in the orientation dependence of the material. Mor

  16. Development of Ni-based multilayers for future focusing soft gamma ray telescopes

    DEFF Research Database (Denmark)

    Girou, David A.; Massahi, Sonny; Sleire, Erlend K.

    2015-01-01

    Ni-based multilayers are a possible solution to extend the upper energy range of hard X-ray focusing telescopes currently limited at ≈79:4 keV by the Pt-K absorption edge. In this study 10 bilayers multilayers with a constant bilayer thickness were coated with the DC magnetron sputtering facility...

  17. Design and characterization of novel precipitation hardenable high Cr Ni-based superalloys

    DEFF Research Database (Denmark)

    Bihlet, Uffe; Dahl, Kristian Vinter; Somers, Marcel A. J.

    2012-01-01

    Among the Ni-based superalloys, Alloy 718 stands apart with the ability to be precipitation hardened after welding, by the slow formation of nano-scale γ’’ (Ni3Nb) particles. This slow formation gives it a very low crack susceptibility, which has made it widely applied since its introduction...

  18. Two-Photon Absorption in Organometallic Bromide Perovskites

    KAUST Repository

    Walters, Grant

    2015-07-21

    Organometallic trihalide perovskites are solution processed semiconductors that have made great strides in third generation thin film light harvesting and light emitting optoelectronic devices. Recently it has been demonstrated that large, high purity single crystals of these perovskites can be synthesized from the solution phase. These crystals’ large dimensions, clean bandgap, and solid-state order, have provided us with a suitable medium to observe and quantify two-photon absorption in perovskites. When CH3NH3PbBr3 single crystals are pumped with intense 800 nm light, we observe band-to-band photoluminescence at 572 nm, indicative of two-photon absorption. We report the nonlinear absorption coefficient of CH3NH3PbBr3 perovskites to be 8.6 cm GW-1 at 800 nm, comparable to epitaxial single crystal semiconductors of similar bandgap. We have leveraged this nonlinear process to electrically autocorrelate a 100 fs pulsed laser using a two-photon perovskite photodetector. This work demonstrates the viability of organometallic trihalide perovskites as a convenient and low-cost nonlinear absorber for applications in ultrafast photonics.

  19. Two-Photon Absorption in Organometallic Bromide Perovskites.

    Science.gov (United States)

    Walters, Grant; Sutherland, Brandon R; Hoogland, Sjoerd; Shi, Dong; Comin, Riccardo; Sellan, Daniel P; Bakr, Osman M; Sargent, Edward H

    2015-09-22

    Organometallic trihalide perovskites are solution-processed semiconductors that have made great strides in third-generation thin film light-harvesting and light-emitting optoelectronic devices. Recently, it has been demonstrated that large, high-purity single crystals of these perovskites can be synthesized from the solution phase. These crystals' large dimensions, clean bandgap, and solid-state order have provided us with a suitable medium to observe and quantify two-photon absorption in perovskites. When CH3NH3PbBr3 single crystals are pumped with intense 800 nm light, we observe band-to-band photoluminescence at 572 nm, indicative of two-photon absorption. We report the nonlinear absorption coefficient of CH3NH3PbBr3 perovskites to be 8.6 cm GW(-1) at 800 nm, comparable to epitaxial single-crystal semiconductors of similar bandgap. We have leveraged this nonlinear process to electrically autocorrelate a 100 fs pulsed laser using a two-photon perovskite photodetector. This work demonstrates the viability of organometallic trihalide perovskites as a convenient and low-cost nonlinear absorber for applications in ultrafast photonics.

  20. Use of Manganese(II)-Schiff Base Complexes for Carrying Polar Organometallics and Inorganic Ion Pairs.

    Science.gov (United States)

    Gallo, Emma; Solari, Euro; Floriani, Carlo; Chiesi-Villa, Angiola; Rizzoli, Corrado

    1997-05-07

    This report concerns the carrier properties of [Mn(acacen)]-derived compounds toward polar organometallics, inorganic ion pairs, and salts. Such properties are the consequence of Mn(II) behaving as a Lewis acid and the O&arcraise;O bite of the bidentate Schiff base ligand toward alkali cations. The starting compounds, which occur in a dimeric form, [Mn(acac-L-en)](2) [L' = CH(2)CH(2) (1); L" = C(6)H(10) (2); L"' = R,R-C(6)H(10) (3)] have been synthesized either via a metathesis reaction from MnCl(2) or using [Mn(3)Mes(6)]. The reaction of 1-3 with lithium organometallics allowed the isolation of [Mn(acac-L-en)(R)Li(DME)] [R = Me, L = L' (4); R = Ph, L = L' (5); R = Mes, L = L' (6); R = Me, L = L" (7); R = Me, L = L"' (8)] as metalated forms, where the alkyl or aryl group is sigma-bonded to Mn(II), while the lithium cation is anchored to the Schiff base ligand. The metalated forms 4-8 react with PhCHO to give the corresponding lithium alkoxide, which remains bound in its ion-pair form to the [Mn(acacen)] skeleton in [Mn(2)(acac-L'-en)(2)Li(2)(OCH(Ph)Me)(2)](n)() (9). The use of 8, which has a chiral bridge across two nitrogen atoms, did not lead to a significant asymmetric induction in the reaction with PhCHO, because of the long separation between the lithium cation and the stereogenic center. The metalated form 4 was able to transfer the methyl group to the nitrile function to give the corresponding lithium-imide which then remains bonded to [Mn(acacen)] as the ion pair in a dimeric structure, as revealed for [Mn(2)(acac-L'-en)(2)Li(2)(DME){N=C(Ph)Me}(2)](n)() (10). Their reaction with 1 appears to depend on the steric bulkiness of the alkyl group in NaOR, resulting in either monomeric adducts, i.e. in [Mn(acac-L'-en)(2,6-Bu(t)(2)C(6)H(3)O)Na(DME)(2)] (11.2DME), or polymeric structures, like in [Mn(acac-L'-en)Na(DME)(&mgr;-OEt)](n)() (13). All the dimeric units reported in this paper show a slight antiferromagnetic coupling between the two Mn(II) assisted by

  1. Towards cancer cell-specific phototoxic organometallic rhenium(I) complexes.

    Science.gov (United States)

    Leonidova, Anna; Pierroz, Vanessa; Rubbiani, Riccardo; Heier, Jakob; Ferrari, Stefano; Gasser, Gilles

    2014-03-21

    Over the recent years, several Re(I) organometallic compounds have been shown to be toxic to various cancer cell lines. However, these compounds lacked sufficient selectivity towards cancer tissues to be used as novel chemotherapeutic agents. In this study, we probe the potential of two known N,N-bis(quinolinoyl) Re(I) tricarbonyl complex derivatives, namely Re(I) tricarbonyl [N,N-bis(quinolin-2-ylmethyl)amino]-4-butane-1-amine (Re-NH₂) and Re(I) tricarbonyl [N,N-bis(quinolin-2-ylmethyl)amino]-5-valeric acid (Re-COOH), as photodynamic therapy (PDT) photosensitizers. Re-NH₂ and Re-COOH proved to be excellent singlet oxygen generators in a lipophilic environment with quantum yields of about 75%. Furthermore, we envisaged to improve the selectivity of Re-COOH via conjugation to two types of peptides, namely a nuclear localization signal (NLS) and a derivative of the neuropeptide bombesin, to form Re-NLS and Re-Bombesin, respectively. Fluorescent microscopy on cervical cancer cells (HeLa) showed that the conjugation of Re-COOH to NLS significantly enhanced the compound's accumulation into the cell nucleus and more specifically into its nucleoli. Importantly, in view of PDT applications, the cytotoxicity of the Re complexes and their bioconjugates increased significantly upon light irradiation. In particular, Re-Bombesin was found to be at least 20-fold more toxic after light irradiation. DNA photo-cleavage studies demonstrated that all compounds damaged DNA via singlet oxygen and, to a minor extent, superoxide production.

  2. Development of ultrafast photochromic organometallics and photoinduced linkage isomerization of arene chromium carbonyl derivatives.

    Science.gov (United States)

    To, Tung T; Heilweil, Edwin J; Duke, Charles B; Ruddick, Kristie R; Webster, Charles Edwin; Burkey, Theodore J

    2009-03-26

    We review recent studies of processes relevant to photoinduced linkage isomerization of organometallic systems with the goal of preparing organometallics with an efficient and ultrafast photochromic response. The organometallic system thus corresponds to two linkage isomers with different electronic environments that are responsible for different optical properties. Much of this work has focused on examining processes following irradiation of cyclopentadienyl manganese tricarbonyl derivatives (compounds 3-21) including solvent coordination, thermal relaxation, solvent displacement by tethered functional groups (chelation), dissociation of tethered functional groups, and linkage isomerization. A new platform is investigated for obtaining a photochromic response in new experiments with arene chromium dicarbonyl complexes. A photochromic response is observed for arene chromium dicarbonyl complexes with tethered pyridine and olefin functional groups based on light-driven linkage isomerization on the nanosecond time scale. Irradiation at 532 nm of 23 ([Cr{eta(6)-C(6)H(5)CH(2-Py-kappaN)CH(2)CH=CH(2)}(CO)(2)]) (Py = pyridine) results in the isomerization to 22 ([Cr{eta(6)-C(6)H(5)CH(2-Py)CH(2)-eta(2)-CH=CH(2)}(CO)(2)]), and 355 nm irradiation isomerizes 22 to 23. The ultrafast linkage isomerization has been investigated at room temperature in n-heptane solution on the picosecond to microsecond time scale with UV- or visible-pump and IR-probe transient absorption spectroscopy by comparing the dynamics with model compounds containing only a tethered pyridine. Irradiation of 24 ([Cr{eta(6)-C(6)H(5)(CH(2))(3)(2-Py)}(CO)(3)]) and 25 ([Cr{eta(6)-C(6)H(5)(CH(2))(2)(2-Py)}(CO)(3)]) at 289 nm induces CO loss to immediately yield a Cr-heptane solvent coordinated intermediate of the unsaturated Cr fragment, which then converts to the kappaN(1)-pyridine chelate within 200 and 100 ns, respectively. Irradiation of 26 ([Cr{eta(6)-C(6)H(5)CH(2)(2-Py)}(CO)(3)]) also induces CO loss to

  3. The organometallic fluorine chemistry of palladium and rhodium: studies toward aromatic fluorination.

    Science.gov (United States)

    Grushin, Vladimir V

    2010-01-19

    Although springing from two established fields, organometallic chemistry and fluorine chemistry, organometallic fluorine chemistry is still in its early stages. However, developments in this area are expected to provide new tools for the synthesis of selectively fluorinated organic compounds that have been in high demand. Selectively fluorinated organic molecules currently account for up to 40% of all agrochemicals and 20% of all pharmaceuticals on the market. Our research efforts have been focused on the development of new organometallic and catalytic methods for the selective introduction of fluorine and the CF(3) group into the aromatic ring. Monofluorinated and trifluoromethylated aromatic compounds are still made by the old technologies that employ stoichiometric quantities of hazardous and costly materials. In this Account, we describe our studies toward the development of safe, catalytic alternatives to these methods. We have synthesized, characterized, and studied the reactivity of the first aryl palladium(II) fluoride complexes. We have demonstrated for the first time that a Pd-F bond can be formed in a soluble and isolable molecular complex: this bond is more stable than previously thought. Toward the goal of fluoroarene formation via Ar-F reductive elimination, we have studied a number of sigma-aryl Pd(II) fluorides stabilized by various P, N, and S ligands. It has been established that numerous conventional tertiary phosphine ligands, most popular in Pd catalysis, are unlikely to be useful for the desired C-F bond formation at the metal center because of the competing, kinetically preferred P-F bond-forming reaction. A metallophosphorane mechanism has been demonstrated for the P-F bond-forming processes at Rh(I) and Pd(II), which rules out the possibility of controlling these reactions by varying the amount of phosphine in the system, a most common and often highly efficient technique in homogeneous catalysis. The novel F/Ph rearrangement of the fluoro

  4. New Organometallic Polymeric Materials: The Search for X(2) NLO organometallic Polymers.

    Science.gov (United States)

    1994-05-28

    copolymer 6. Cyclic voltametry of complex 7 shows two reversible oxidation events, one at +0.11 V (two-electron event) and another at +0.71 V (one...award). A special thanks to Prof. Vernon Parker for helpful discussions and Dr. Kishan Handoo for obtaining the cyclic voltammetry data for compounds 6

  5. Development of Non-Noble Metal Ni-Based Catalysts for Dehydrogenation of Methylcyclohexane

    KAUST Repository

    Al-ShaikhAli, Anaam H.

    2016-11-30

    Liquid organic chemical hydride is a promising candidate for hydrogen storage and transport. Methylcyclohexane (MCH) to toluene (TOL) cycle has been considered as one of the feasible hydrogen carrier systems, but selective dehydrogenation of MCH to TOL has only been achieved using the noble Pt-based catalysts. The aim of this study is to develop non-noble, cost-effective metal catalysts that can show excellent catalytic performance, mainly maintaining high TOL selectivity achievable by Pt based catalysts. Mono-metallic Ni based catalyst is a well-known dehydrogenation catalyst, but the major drawback with Ni is its hydrogenolysis activity to cleave C-C bonds, which leads to inferior selectivity towards dehydrogenation of MCH to TOL. This study elucidate addition of the second metal to Ni based catalyst to improve the TOL selectivity. Herein, ubiquitous bi-metallic nanoparticles catalysts were investigated including (Ni–M, M: Ag, Zn, Sn or In) based catalysts. Among the catalysts investigated, the high TOL selectivity (> 99%) at low conversions was achieved effectively using the supported NiZn catalyst under flow of excess H2. In this work, a combined study of experimental and computational approaches was conducted to determine the main role of Zn over Ni based catalyst in promoting the TOL selectivity. A kinetic study using mono- and bimetallic Ni based catalysts was conducted to elucidate reaction mechanism and site requirement for MCH dehydrogenation reaction. The impact of different reaction conditions (feed compositions, temperature, space velocity and stability) and catalyst properties were evaluated. This study elucidates a distinctive mechanism of MCH dehydrogenation to TOL reaction over the Ni-based catalysts. Distinctive from Pt catalyst, a nearly positive half order with respect to H2 pressure was obtained for mono- and bi-metallic Ni based catalysts. This kinetic data was consistent with rate determining step as (somewhat paradoxically) hydrogenation

  6. Organometallic complexes with terminal imidazolato ligands and their use as metalloligands.

    Science.gov (United States)

    Gómez, Eva; Huertos, Miguel A; Pérez, Julio; Riera, Lucía; Menéndez-Velázquez, Amador

    2010-10-18

    Compounds [Re(bipy)(CO)(3)(HIm)]OTf (1) and [Mo(η(3)-C(3)H(4)-R-2)(CO)(2)(HIm)(phen)]BAr'(4) [R = Me (2a), H (2b); Ar' = 3,5-bis(trifluoromethyl)phenyl; HIm = 1H-imidazole] were prepared from 1H-imidazole and either [Re(OTf)(bipy)(CO)(3)] or [MoCl(η(3)-C(3)H(4)-R-2)(CO)(2)(phen)]. Compounds 1, 2a, and 2b were deprotonated to afford the terminal κ-N-imidazolate complexes [Re(bipy)(CO)(3)(Im)] (3) and [Mo(η(3)-C(3)H(4)-R-2)(CO)(2)(Im)(phen)] [R = Me (4a), H (4b)], which were fully characterized, including an X-ray structural determination of 3. The topological analysis of the electron density (obtained from the X-ray diffraction study) and its Laplacian were used to characterize the differences in the electron density at the five-membered ring ligand between the imidazole and imidazolate complexes 1 and 3. The reaction of complexes 3, 4a, and 4b with the appropriate organometallic complexes afforded the bimetallic imidazolate-bridged compounds [{Re(bipy)(CO)(3)}(2)(μ-Im)]OTf (5), [{Mo(η(3)-C(4)H(7))(CO)(2)(phen)}(2)(μ-Im)]OTf (6), and [{Mo(η(3)-C(3)H(5))(CO)(2)(phen)}(μ-Im){Re(phen)(CO)(3)}]OTf (7). The reaction of [Mo(η(3)-C(4)H(7))(CO)(2)(Im)(phen)] (4a) with SnClPh(3) led to the formation of the trinuclear complex [{Mo(η(3)-C(4)H(7))(CO)(2)(phen)(μ-Im)}(2){SnPh(3)}]BAr'(4) (8).

  7. Flat Chern band in a two-dimensional organometallic framework.

    Science.gov (United States)

    Liu, Zheng; Wang, Zheng-Fei; Mei, Jia-Wei; Wu, Yong-Shi; Liu, Feng

    2013-03-01

    By combining exotic band dispersion with nontrivial band topology, an interesting type of band structure, namely, the flat Chern band, has recently been proposed to spawn high-temperature fractional quantum Hall states. Despite the proposal of several theoretical lattice models, however, it remains doubtful whether such a "romance of flatland" could exist in a real material. Here, we present a first-principles design of a two-dimensional indium-phenylene organometallic framework that realizes a nearly flat Chern band right around the Fermi level by combining lattice geometry, spin-orbit coupling, and ferromagnetism. An effective four-band model is constructed to reproduce the first-principles results. Our design, in addition, provides a general strategy to synthesize topologically nontrivial materials by virtue of organic chemistry and nanotechnology.

  8. PREPARATION OF TANTALUM CARBIDE FROM AN ORGANOMETALLIC PRECURSOR

    Directory of Open Access Journals (Sweden)

    C. P. SOUZA

    1999-03-01

    Full Text Available In this work we have synthesized an organometallic oxalic precursor from tantalum oxide. This oxide was solubilized by heating with potassium hydrogen sulfate. In order to precipitate Ta2O5.nH2O, the fused mass obtained was dissolved in a sulfuric acid solution and neutralized with ammonia. The hydrated tantalum oxide precipitated was dissolved in an equimolar solution of oxalic acid/ammonium oxalate. The synthesis and the characterization of the tantalum oxalic precursor are described. Pyrolysis of the complex in a mixture of hydrogen and methane at atmospheric pressure was studied. The gas-solid reaction made it possible to obtain tantalum carbide, TaC, in the powder form at 1000oC. The natural sintering of TaC powder in an inert atmosphere at 1400°C during 10 hours, under inert atmosphere made it possible to densify the carbide to 96% of the theoretical value.

  9. Preparation of tantalum carbide from an organometallic precursor

    Energy Technology Data Exchange (ETDEWEB)

    Souza, C.P. [Rio Grande do Norte Univ., Natal, RN (Brazil). Programa de Pos-graduacao em Geoquimica. Lab. de Termodinamica e Reatores]. E-mail: carlson at ufrnet.ufrn.br; Favotto, C.; Satre, P.; L' Honore, A.; Roubin, M. [Universite du Toulon et de Var B.P. (France). Equipe der Materiaux a Finalite Specifique. Lab. de Physicochimie du Materiaux et du Milieu Marin]. E-mail: roubin at univ-tln.fr

    1999-03-01

    In this work we have synthesized an organometallic oxalic precursor from tantalum oxide. This oxide was solubilized by heating with potassium hydrogen sulfate. In order to precipitate Ta{sub 2} O{sub 5} nH{sub 2}O, the fused mass obtained was dissolved in a sulfuric acid solution and neutralized with ammonia. The hydrated tantalum oxide precipitated was dissolved in an equimolar solution of oxalic acid/ammonium oxalate. The synthesis and the characterization of the tantalum oxalic precursor are described. Pyrolysis of the complex in a mixture of hydrogen and methane at atmospheric pressure was studied. The gas-solid reaction made it possible to obtain tantalum carbide, Ta C, in the powder form at 1000 deg C. The natural sintering of Ta C powder in an inert atmosphere at 1400 deg C during 10 hours, under inert atmosphere made it possible to density the carbide to 96% of the theoretical value. (author)

  10. Supported organometallic complexes: Surface chemistry, spectroscopy, and catalysis. Progress report, March 15, 1988--July 14, 1989

    Energy Technology Data Exchange (ETDEWEB)

    Marks, T.J.

    1990-02-01

    The goal of our program is to define those modes of interaction that take place between organometallic molecules and inorganic surfaces and, ultimately, to correlate various molecule-surface structures with catalytic properties.

  11. Effect of organometallic fuel additives on nanoparticle emissions from a gasoline passenger car.

    Science.gov (United States)

    Gidney, Jeremy T; Twigg, Martyn V; Kittelson, David B

    2010-04-01

    Particle size measurements were performed on the exhaust of a car operating on a chassis dynamometer fueled with standard gasoline and gasoline containing low levels of Pb, Fe, and Mn organometallic additives. When additives were present there was a distinct nucleation mode consisting primarily of sub-10 nm nanoparticles. At equal molar dosing Mn and Fe gave similar nanoparticle concentrations at the tailpipe, whereas Pb gave a considerably lower concentration. A catalytic stripper was used to remove the organic component of these particles and revealed that they were mainly solid and, because of their association with inorganic additives, presumably inorganic. Solid nucleation mode nanoparticles of similar size and concentration to those observed here from a gasoline engine with Mn and Fe additives have also been observed from modern heavy-duty diesel engines without aftertreatment at idle, but these solid particles are a small fraction of the primarily volatile nucleation mode particles emitted. The solid nucleation mode particles emitted by the diesel engines are likely derived from metal compounds in the lubrication oil, although carbonaceous particles cannot be ruled out. Significantly, most of these solid nanoparticles emitted by both engine types fall below the 23 nm cutoff of the PMP number regulation.

  12. Selective Organic and Organometallic Reactions in Water-Soluble Host-Guest Supramolecular Systems

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael D.; Raymond, Kenneth N.; Bergman, Robert G.

    2008-02-16

    Inspired by the efficiency and selectivity of enzymes, synthetic chemists have designed and prepared a wide range of host molecules that can bind smaller molecules with their cavities; this area has become known as 'supramolecular' or 'host-guest' chemistry. Pioneered by Lehn, Cram, Pedersen, and Breslow, and followed up by a large number of more recent investigators, it has been found that the chemical environment in each assembly - defined by the size, shape, charge, and functional group availability - greatly influences the guest-binding characteristics of these compounds. In contrast to the large number of binding studies that have been carried out in this area, the exploration of chemistry - especially catalytic chemistry - that can take place inside supramolecular host cavities is still in its infancy. For example, until the work described here was carried out, very few examples of organometallic reactivity inside supramolecular hosts were known, especially in water solution. For that reason, our group and the group directed by Kenneth Raymond decided to take advantage of our complementary expertise and attempt to carry out metal-mediated C-H bond activation reactions in water-soluble supramolecular systems. This article begins by providing background from the Raymond group in supramolecular coordination chemistry and the Bergman group in C-H bond activation. It goes on to report the results of our combined efforts in supramolecular C-H activation reactions, followed by extensions of this work into a wider range of intracavity transformations.

  13. Synthesis and characterization of organometallic macrocyclic rhodium (Ⅲ) complex with pyrazine ligands

    Institute of Scientific and Technical Information of China (English)

    WANG Jianqiang; ZHANG Zheng; WENG Linhong; JIN Guoxin

    2004-01-01

    The reaction of half-sandwich complex (Cptt Rh)2Cl2(μ-Cl)2 (1) (Cptt = η5-tBu2C5H3) with 1 equiv. Of AgSO3CF3 in CH2Cl2 affords tri-μ-chloro dirhodium (2) cation compound, with 2 equiv. Of AgSO3CF3 providing di-μ-chloro complex 3. The reaction of 3 with pyrazine gives a novel tetra-nuclear 14-member organometallic macrocyclic complex 4. FT-IR, 1H-NMR, and EA were used to characterize these complexes. The structures of complexes 2 and 4 are confirmed by X-ray analysis. In complex 2, the two Cptt ring and tri-chloro atoms faces are approximately parallel to each other. In complex 4, the complex cation has a rectangular cavity with the dimension of 0.3748 nm×0.7027 nm, and the two-pyrazine rings are parallel to each other with a distance of 0.3510 nm.

  14. Hydrothermal gasification of glucose using Raney nickel and homogeneous organometallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Azadi, P. [Department of Chemical Engineering and Applied Chemistry, University of Toronto, M5S 3E5, Toronto, Ontario (Canada); Khodadadi, A.A.; Mortazavi, Y. [Catalysis and Reaction Engineering Research Laboratory, School of Chemical Engineering, University of Tehran, Tehran (Iran); Farnood, R. [Department of Chemical Engineering and Applied Chemistry, University of Toronto, M5S 3E5, Toronto, Ontario (Canada); Catalysis and Reaction Engineering Research Laboratory, School of Chemical Engineering, University of Tehran, Tehran (Iran)

    2009-01-15

    Catalytic gasification of biomass to fuel gaseous in sub and super critical water is a promising method for production of sustainable energy. In this paper, a microreactor has been utilized to study the hydrothermal gasification of glucose in the presence of transition metal chelates consisting of nickel(II) acetylacetonate (Ni(acac){sub 2}), cobalt(II) acetylacetonate (Co(acac){sub 2}), iron(III) acetylacetonate (Fe(acac){sub 3}) and Raney-nickel particles. The reaction temperature and pressure were 310-350 C and 100-210 bar, respectively. Effects of addition of catalysts, reaction temperature, reaction time, glucose concentration and liquid water volume fraction on the amount of the generated gas as well as its composition were investigated. Results indicated that the presence of the organometallic compounds can slightly facilitate the rate of decomposition of glucose. This enhancement in reaction rate was more pronounced at higher concentrations of the feed ({proportional_to} 0.65 M) compared with lower concentrations ({proportional_to} 0.06 M). In contrast to these homogeneous catalysts, Raney-nickel catalyst improved the gas yield by a factor of 3 to 5. It has been observed that the amount of the produced gas almost doubles when the batch time increased from 3 to 30 min, while no significant change was observed from 30 to 60 min. Finally, remarks on optimization of the amount of added water into the reaction vessel are provided. (author)

  15. In situ derivatization of metals and organometallics using borate reagents in gas chromatographic speciation studies.

    Science.gov (United States)

    Zachariadis, George A

    2013-06-28

    Development of sensitive and selective analytical methods is required for trace metal and metalloids speciation analysis, including their alkyl-, phenyl- or other organometallic species. Gas chromatography is one of the most suitable techniques for effective separation of the above compounds however it requires that the analytes are volatile or semi-volatile. Today very popular derivatization methods make use of borate reagents for in situ derivatization of elements like Hg, Pb, Sn, Se, As, etc. Tetrahydroborates are suitable for hydride generation and alkylborates for alkylation of the inorganic ions of the above elements, as well as of several partially alkylated ones. This almost immediate reaction can be done in aqueous solutions and produces fully alkylated products of higher volatility suitable for separation by gas chromatography and measured by various detectors. The number of papers published in this field is constantly high, including many applications to various types of matrices, like biological, environmental, industrial, food, polymers, etc. For this reason, many articles of the last two decades are reviewed in this paper and emphasis is given to the use of borate reagents and the relative microreactions for selected elements.

  16. Phosphane-Based Cyclodextrins as Mass Transfer Agents and Ligands for Aqueous Organometallic Catalysis

    Directory of Open Access Journals (Sweden)

    Eric Monflier

    2012-11-01

    Full Text Available The replacement of hazardous solvents and the utilization of catalytic processes are two key points of the green chemistry movement, so aqueous organometallic catalytic processes are of great interest in this context. Nevertheless, these processes require not only the use of water-soluble ligands such as phosphanes to solubilise the transition metals in water, but also the use of mass transfer agents to increase the solubility of organic substrates in water. In this context, phosphanes based on a cyclodextrin skeleton are an interesting alternative since these compounds can simultaneously act as mass transfer agents and as coordinating species towards transition metals. For twenty years, various cyclodextrin-functionalized phosphanes have been described in the literature. Nevertheless, while their coordinating properties towards transition metals and their catalytic properties were fully detailed, their mass transfer agent properties were much less discussed. As these mass transfer agent properties are directly linked to the availability of the cyclodextrin cavity, the aim of this review is to demonstrate that the nature of the reaction solvent and the nature of the linker between cyclodextrin and phosphorous moieties can deeply influence the recognition properties. In addition, the impact on the catalytic activity will be also discussed.

  17. Organometallics meet colloid chemistry: a case study in three phases based on molecular carbonyl precursors containing zinc and manganese.

    Science.gov (United States)

    Orlov, A; Roy, A; Lehmann, M; Driess, M; Polarz, S

    2007-01-17

    Two organometallic compounds containing zinc and manganese in different ratios are used as single-source precursors for the preparation of various new, bimetallic oxide materials with nanoscaled dimensions. It is shown that the materials synthesis can be performed in the solid-state, the liquid-phase, and even in the gas-phase. The molecular composition of the precursors determines the composition of the resulting materials. In addition, two novel methods for the preparation of highly crystalline metal oxide colloids are presented: The coupling between a gas-phase process and a colloidal approach, and the application of ozone as an oxidant for the transformation of metal carbonyls into oxides in the liquid phase.

  18. Novel Two- and Three-Dimensional Organometallic-Organic Hybrid Materials Based on Polyphosphorus Complexes.

    Science.gov (United States)

    Attenberger, Bianca; Peresypkina, Eugenia V; Scheer, Manfred

    2015-07-20

    The reaction of the silver salt Ag[Al{OC(CF3)3}4] (1) with the P2 ligand complex [Cp2Mo2(CO)4(η(2)-P2)] (2) and the organic ditopic linker trans-1,2-di(pyridine-4-yl)ethene (dpe) results in the formation of four novel organometallic-organic hybrid compounds. Depending on the reaction conditions, the two-dimensional networks [{Cp2Mo2(CO)4(μ4,η(1:1:2:2)-P2)}(μ,η(1:1)-C12H10N2)Ag]n[Al{OC(CF3)3}4]n·0.075nCH2Cl2·1.425nC6H6 (3) and [{Cp2Mo2(CO)4(μ3,η(2:2:2)-P2)}2(μ,η(1:1)-C12H10N2)3Ag2]n[Al{OC(CF3)3}4]2n·2nC7H8 (4) are accessible. The latter shows a two-dimensional (2D) → 2D interpenetration structure. Furthermore, the formation of a unique three-dimensional polymer [{Cp2Mo2(CO)4(μ4,η(1:1:2:2)-P2)}(μ,η(1:1)-C12H10N2)Ag]n[Al{OC(CF3)3}4]n·0.3nCH2Cl2 (5b) together with another 2D polymer [{Cp2Mo2(CO)4(μ4,η(1:1:2:2)-P2)}(μ,η(1:1)-C12H10N2)3Ag2]n[Al{OC(CF3)3}4]2n·0.75CH2Cl2·0.5C7H8 (5a) was observed. In three of these polymers, unprecedented organometallic nodes were realized including one, two, or even four silver cations. All products were characterized by X-ray structural analysis and classified by the structural characteristics in three different network topologies.

  19. Organometallic catalysts for primary phosphoric acid fuel cells

    Science.gov (United States)

    Walsh, Fraser

    1987-01-01

    A continuing effort by the U.S. Department of Energy to improve the competitiveness of the phosphoric acid fuel cell by improving cell performance and/or reducing cell cost is discussed. Cathode improvement, both in performance and cost, available through the use of a class of organometallic cathode catalysts, the tetraazaannulenes (TAAs), was investigated. A new mixed catalyst was identified which provides improved cathode performance without the need for the use of a noble metal. This mixed catalyst was tested under load for 1000 hr. in full cell at 160 to 200 C in phosphoric acid H3PO4, and was shown to provide stable performance. The mixed catalyst contains an organometallic to catalyze electroreduction of oxygen to hydrogen peroxide and a metal to catalyze further electroreduction of the hydrogen peroxide to water. Cathodes containing an exemplar mixed catalyst (e.g., Co bisphenyl TAA/Mn) operate at approximately 650 mV vs DHE in 160 C, 85% H3PO4 with oxygen as reactant. In developing this mixed catalyst, a broad spectrum of TAAs were prepared, tested in half-cell and in a rotating ring-disk electrode system. TAAs found to facilitate the production of hydrogen peroxide in electroreduction were shown to be preferred TAAs for use in the mixed catalyst. Manganese (Mn) was identified as a preferred metal because it is capable of catalyzing hydrogen peroxide electroreduction, is lower in cost and is of less strategic importance than platinum, the cathode catalyst normally used in the fuel cell.

  20. Oxidation Resistance: One Barrier to Moving Beyond Ni-Base Superalloys

    Energy Technology Data Exchange (ETDEWEB)

    Pint, Bruce A [ORNL; Distefano, James R [ORNL; Wright, Ian G [ORNL

    2006-01-01

    The implementation of new high-temperature materials is often hampered by their lack of oxidation or environmental resistance. This failing is one of the strongest barriers to moving beyond Ni-base superalloys for many commercial applications. In practice, usable high-temperature alloys have at least reasonable oxidation resistance, but the current generation of single-crystal Ni-base superalloys has sufficient oxidation resistance that optimized versions can be used without a metallic bond coating and only an oxygen-transparent ceramic coating for thermal protection. The material development process often centers around mechanical properties, while oxidation resistance, along with other realities, is given minor attention. For many applications, the assumption that an oxidation-resistant coating can be used to protect a substrate is seriously flawed, as coatings often do not provide sufficient reliability for critical components. Examples of oxidation problems are given for currently used materials and materials classes with critical oxidation resistance problems.

  1. Microstructural Evolution During Friction Stir Welding of Mild Steel and Ni-Based Alloy 625

    Science.gov (United States)

    Fernandez, Johnnatan Rodriguez; Ramirez, Antonio J.

    2017-03-01

    Microstructure evolution during friction stir welding (FSW) of mild steel and Ni-based alloy 625 was studied. Regarding the Ni-based alloy, the welding process led to grain refinement caused by discontinuous and continuous dynamic recrystallization, where bulging of the pre-existing grains and subgrain rotation were the primary mechanisms of recrystallization. In the steel, discontinuous dynamic recrystallization was identified as the recovery process experienced by the austenite. Simple shear textures were observed in the regions affected by the deformation of both materials. Although the allotropic transformation obscured the deformation history, the thermo-mechanically affected zone was identified in the steel by simple shear texture components. A new methodology for the study of texture evolution based on rotations of the slip systems using pole figures is presented as an approximation to describe the texture evolution in FSW.

  2. Microstructural Evolution During Friction Stir Welding of Mild Steel and Ni-Based Alloy 625

    Science.gov (United States)

    Fernandez, Johnnatan Rodriguez; Ramirez, Antonio J.

    2017-01-01

    Microstructure evolution during friction stir welding (FSW) of mild steel and Ni-based alloy 625 was studied. Regarding the Ni-based alloy, the welding process led to grain refinement caused by discontinuous and continuous dynamic recrystallization, where bulging of the pre-existing grains and subgrain rotation were the primary mechanisms of recrystallization. In the steel, discontinuous dynamic recrystallization was identified as the recovery process experienced by the austenite. Simple shear textures were observed in the regions affected by the deformation of both materials. Although the allotropic transformation obscured the deformation history, the thermo-mechanically affected zone was identified in the steel by simple shear texture components. A new methodology for the study of texture evolution based on rotations of the slip systems using pole figures is presented as an approximation to describe the texture evolution in FSW.

  3. Aqueous phase reforming of glycerol over Ni-based catalysts for hydrogen production.

    Science.gov (United States)

    Cho, Su Hyun; Moon, Dong Ju

    2011-08-01

    Aqueous phase reforming of glycerol over Ni-based catalysts for hydrogen production was carried out at 225 degrees C, 23 bar and LHSV = 4 h(-1). The Ni-based catalyst was prepared by an incipient wetness impregnation method. The catalysts before and after the reaction were characterized by N2 physisorption, CO chemisorption, XRD, TPR, SEM and TEM techniques. It was found that Ni(20 wt%)-Co(3 wt%)/gamma-Al2O3 catalyst showed higher glycerol conversion and hydrogen selectivity than Ni(20 wt%)/gamma-Al2O3 catalyst. There are no major changes in Ni particles after the reaction over Ni-Co/gamma-Al2O3 catalyst. The results suggest that the Ni-Co/gamma-Al2O3 catalyst can be applied to the hydrogen production system using APR of glycerol.

  4. Study on residual stresses of Ni-based WC coating by laser remelting based on XRD

    Science.gov (United States)

    Chen, Zhigang; Kong, Dejun; Wang, Ling; Zhu, Xiaoron; Zhao, Xiaobing

    2007-12-01

    The morphologies of Ni-based WC coating by flame spraying and laser cladding respectively were observed with scanning electric microscope (SEM), respectively, and residual stresses were measured with XRD (X-ray diffraction). At the same time, the spectra of WC coating were analyzed by XRD, and the forming mechanisms of residual stress were analyzed. Experimental results are shown that residual stresses of Ni-based WC coating by flame spraying are all tensile while those by laser cladding are compressive, chemical-physical reaction of the coating is the cause to result in material volume change, which makes residual stress into compressive from tensile; when residual stress is changed into compressive from tensile, micro-cracks on the coating surface greatly decrease, which is illustrated that the effect of residual stress on micro-crack is obvious; XRD spectra peak of WC coating is only contained Ni and W, and has no impurity and other reaction productions.

  5. Desulphurization during VIM Refining Ni-base Superalloy using CaO Crucible

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The variation of S content during VIM refining Ni-base superalloy using CaO crucible was stud[ed. It was foundthat the desulphurization process could not be carried out by only using CaO crucible. The role of Al additionto desulphurization was also studied. Combining with the results of XRD and composition analysis of the CaOcrucible, the mechanism of desulphurization was proposed. Thermodynamical calculation about the reaction betweenthe interface of CaO crucible and liquid metal has been discussed. This work indicated that under proper refiningtechnology the S content in the liquid Ni-base alloy could be reduced from 3×10-5 to 2×10-6~4×10-6.

  6. Facile synthesis of Mo–Ni particles and their effect on the electrochemical kinetic properties of La–Mg–Ni-based alloy electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yuan; Tao, Yang; Ke, Dandan; Yang, Shuqin [College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004 (China); Han, Shumin, E-mail: hanshm@ysu.edu.cn [College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004 (China); State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China)

    2014-12-05

    Highlights: • We synthesized nano-Mo–Ni particles by a facile method. • The particles improve charge transfer rate at surface of metal hydride electrode. • HRD of electrodes with Mo–Ni particles increases remarkably. - Abstract: A simple method was developed to synthesize Mo–Ni compounds using a chemical reduction method. The compound was then added to La–Mg–Ni-based alloy electrodes in order to improve the electrochemical kinetics of the electrodes. Scanning electron microscopy and transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy showed that the as-synthesized compound consisted of nanoparticles with a chemical composition of MoNi{sub 2.5}. X-ray diffraction analysis revealed that the compound mainly consisted of a MoNi{sub 3} and a Ni phase. The Mo–Ni particles were added to the La–Mg–Ni-based alloy electrode material and uniformly distributed on the alloy surface. An improvement in initial discharge capacity and high rate dischargeability (HRD) could be observed, as well as an enhancement of cycle stability. At 1500 mA/g the HRD increased by 10.2%, and the initial discharge capacity increased from 286 mA h/g to 307 mA h/g. After adding the particles to the alloy, the Mo–Ni particles showed a high electro-catalytic activity due to a charge transfer reaction on the alloy surface, thereby decreasing the charge transfer resistance and increasing the exchange current density. Consequently, the kinetics of the electrode reaction was significantly improved due to an enhancement of the electro-catalytic activity.

  7. Scalable Synthesis of Piperazines Enabled by Visible-Light Irradiation and Aluminum Organometallics.

    Science.gov (United States)

    Suárez-Pantiga, Samuel; Colas, Kilian; Johansson, Magnus J; Mendoza, Abraham

    2015-11-16

    The development of more active C-H oxidation catalysts has inspired a rapid, scalable, and stereoselective assembly of multifunctional piperazines through a [3+3] coupling of azomethine ylides. A combination of visible-light irradiation and aluminum organometallics is essential to promote this transformation, which introduces visible-light photochemistry of main-group organometallics and sets the basis for new and promising catalysts.

  8. Cyclic deformation, fatigue and fatigue crack propagation in Ni-base alloys

    Science.gov (United States)

    Antolovich, Stephen D.; Lerch, Brad

    1989-01-01

    Ni-base superalloys' cumulative glide behavior, damage accumulation, low-cycle fatigue, and crack propagation characteristics are directly dependent on deformation behavior which is in turn a strong function of microstructural characteristics. Microstructural instabilities and environmental interactions become additional factors at elevated temperatures. An account is presently given of microstructural, chemical, and processing techniques that may be used to obtain the properties that appear most critical or desirable in specific applications.

  9. NI Based System for Seu Testing of Memory Chips for Avionics

    Directory of Open Access Journals (Sweden)

    Boruzdina Anna

    2016-01-01

    Full Text Available This paper presents the results of implementation of National Instrument based system for Single Event Upset testing of memory chips into neutron generator experimental facility, which used for SEU tests for avionics purposes. Basic SEU testing algorithm with error correction and constant errors detection is presented. The issues of radiation shielding of NI based system are discussed and solved. The examples of experimental results show the applicability of the presented system for SEU memory testing under neutrons influence.

  10. Fracture assessment for a dissimilar metal weld of low alloy steel and Ni-base alloy

    Energy Technology Data Exchange (ETDEWEB)

    Ogawa, Takuya, E-mail: takuya4.ogawa@toshiba.co.jp [Toshiba Corporation Power Systems Company, Power and Industrial Systems Research and Development Center, 8, Shinsugita-cho, Isogo-ku, Yokohama 235-8523 (Japan); Itatani, Masao; Saito, Toshiyuki; Hayashi, Takahiro; Narazaki, Chihiro; Tsuchihashi, Kentaro [Toshiba Corporation Power Systems Company, Power and Industrial Systems Research and Development Center, 8, Shinsugita-cho, Isogo-ku, Yokohama 235-8523 (Japan)

    2012-02-15

    Recently, instances of SCC in Ni-base alloy weld metal of light water reactor components have been reported. Despite the possibility of propagation of SCC crack to the fusion line between low alloy steel (LAS) of pressure vessel and Ni-base alloy of internal structure, a fracture assessment method of dissimilar metal welded joint has not been established. The objective of this study is to investigate a fracture mode of dissimilar metal weld of LAS and Ni-base alloy for development of a fracture assessment method for dissimilar metal weld. Fracture tests were conducted using two types of dissimilar metal weld test plates with semi-elliptical surface crack. In one of the test plates, the fusion line lies around the surface points of the surface crack and the crack tips at the surface points have intruded into LAS. Material ahead of the crack tip at the deepest point is Ni-base alloy. In the other, the fusion line lies around the deepest point of the surface crack and the crack tip at the deepest point has intruded into LAS. Material ahead of the crack tip at the deepest point is LAS. The results of fracture tests using the former type of test plate reveal that the collapse load considering the proportion of ligament area of each material gives a good estimation for fracture load. That is, fracture assessment based on plastic collapse mode is applicable to the former type of test plate. It is also understood that a fracture assessment method based on the elastic-plastic fracture mode is suitable for the latter type of test plate.

  11. Microstructure of Ni-Based Self-Fluxing Alloy Coating (PartⅠ)

    Institute of Scientific and Technical Information of China (English)

    WANG Jin-hua; Milan Friesel; Magnus Willander; Richard Warren

    2005-01-01

    The microstructure of a Ni-based self-fluxing alloy coating produced by an oxygen-acetylene flame spraying Ni-16.5Cr-3.3B-4.7Si-4. 4Fe-0. 8C system alloy powder onto a common steel substrate was investigated by microanalysis methods. The phases in the coating were observed by SEM and determined by XEDS X-Ray energy spectrum and X-Ray diffraction patterns. Meanwhile, some molecular formulas were calculated.

  12. Effects of Rare Earths on Properties of Ti-Zr-Cu-Ni Base Brazing Filler Alloys

    Institute of Scientific and Technical Information of China (English)

    Ma Tianjun; Kang Hui; Wu Yongqin; Qu Ping

    2004-01-01

    The effects of the addition of rare earths on the properties of Ti-Zr-Cu-Ni base brazing filler alloys and the mechanical microstructure and properties were studied for the brazed-joints in the vacuum brazing of TC4 by comparing synthetical properties of two kinds of filler metals.The results indicate that the filler metals added with rare earths have lower melting point, better wettability and higher mechanical properties in the brazing joints.

  13. Microstructural Stability and Hot Deformation of γ- γ'- δ Ni-Base Superalloys

    Science.gov (United States)

    Detrois, Martin; Helmink, Randolph C.; Tin, Sammy

    2014-11-01

    Nickel-base superalloys exhibit excellent high-temperature mechanical and physical properties and remain the first choice for structural components in advanced gas turbine engines for the aerospace propulsion and power generation applications. In response to the increasing demand for more efficient solutions and tighter requirements linked to gas turbine technologies, the properties of nickel-base superalloys can be improved by modification of their thermo-mechanical and/or compositional attributes. Recent investigations have revealed the potential use of ternary eutectic γ- γ'- δ Ni-base superalloys in advanced gas turbines due to high temperature mechanical properties that are comparable to state-of-the-art polycrystalline Ni-base superalloys. With properties largely dependent on microstructural strengthening mechanisms, both the composition and thermo-mechanical processing parameters of this novel class of alloys need to be optimized concurrently. The hot deformation characteristics of four γ- γ'- δ Ni-base superalloys with varying levels of Nb were evaluated at temperatures and strain rates between 1353 K and 1433 K (1080 °C and 1160 °C) and 0.01 to 0.001/s, respectively. Evidence of dislocation-based plasticity was observed following deformation at low temperatures and high strain rates, while high temperatures and low strain rates promoted superplasticity in these alloys. The extent of the microstructural changes and the magnitude of the cavitation damage which occurred during deformation was found to vary as a function of the alloy composition.

  14. Microstructures and Wear Performance of PTAW Deposited Ni-Based Coatings with Spherical Tungsten Carbide

    Directory of Open Access Journals (Sweden)

    Dewei Deng

    2015-10-01

    Full Text Available The Ni-based coatings with different content of spherical tungsten carbide were deposited by plasma transfer arc welding (PTAW method on 304 austenitic stainless steel sheets in this study. The microstructure and wear property of spherical tungsten carbide particle reinforced composite coatings were investigated by means of optical microscope, scanning electron microscope (SEM, X-ray diffraction (XRD, electron probe microanalysis (EPMA and sliding wear test. It is shown that the fraction of spherical tungsten carbides has an important influence on microstructure of Ni-based overlay. The Ni40 overlay consists of γ-Ni dendrites with interdendritic Ni-based eutectics, borides and carbides improving the wear resistance. In the case of composite coatings with different content of tungsten carbide, many new phases are observed, such as Ni2W4C and NiW. In addition, there are a large number of irregular structures in composite coatings, such as acicular structure and irregular stripe organization. The results of sliding wear test indicate that the mass loss of coatings is influenced by the content of tungsten carbide. The mass loss decreases with the increase of tungsten carbide fraction. At high load, the abrasive resistance of composite coating with 60 wt. % tungsten carbide is improved about 50-fold compared to that of Ni40 overlay.

  15. Effect of RE-Doped and RE Quantity of Ni-Based Catalysts on CH4/CO2 Reforming Reaction

    Institute of Scientific and Technical Information of China (English)

    Yang Yifeng; Li Xiancai; Dai Chao; Wang Chunfeng; Chen Juanrong

    2004-01-01

    RE-doped Ni-based catalysts were prepared by sol-gel method.These catalysts were applied to the reaction of CO2 reforming CH4 to syngas.The studies reveal that RE-doped ( RE = La, Ce, Sm, Yb) Ni-based catalysts show higher catalytic activity than undoped Ni-based catalyst, and with the increasing of RE-doped quantity, the catalytic activity of catalysts exhibits regular changes.When RE-doped quantity is 0.2% ( molar ratio), the catalysts show the best catalytic activity.

  16. EFFECT OF La2O3 ADDITION ON MICROSTRUCTURE AND WEAR BEHAVIOR OF ELECTROSPARK DEPOSITED Ni-BASED COATINGS

    OpenAIRE

    GAO YUXIN; YI JIAN

    2013-01-01

    La2O3 doped Ni-based coatings have been prepared by electrospark deposition technique. The effect of La2O3 on the microstructure, hardness and wear behavior of the as-prepared Ni-based coatings is investigated by using X-ray diffractometer, scanning electron microscope, wear tribometer and Vickers hardness tester. Results indicates that the microstructure, hardness and wear resistance of La2O3 doped Ni-based coatings are effectively improved as compared to the undoped one, and the coating wit...

  17. One-pot functionalisation of N-substituted tetrahydroisoquinolines by photooxidation and tunable organometallic trapping of iminium intermediates

    Directory of Open Access Journals (Sweden)

    Joshua P. Barham

    2014-12-01

    Full Text Available Nucleophilic trapping of iminium salts generated via oxidative functionalisation of tertiary amines is well established with stabilised carbon nucleophiles. The few reports of organometallic additions have limited scope of substrate and organometallic nucleophile. We report a novel, one-pot methodology that functionalises N-substituted tetrahydroisoquinolines by visible light-assisted photooxidation, followed by trapping of the resultant iminium ions with organometallic nucleophiles. This affords 1,2-disubstituted tetrahydroisoquinolines in moderate to excellent yields.

  18. The synthesis and characterization of organometallic copolymers with Mn-Re binuclear transition-metal group in the side chain

    Institute of Scientific and Technical Information of China (English)

    XU; Zhi; FENG; Gang; BAI; Zhifeng; MA; Yongqiang; CHANG; Weixing; LI; Jing

    2006-01-01

    Novel organometallic copolymers with Mn-Re binuclear transition-metal groups in the side chain are synthesized and characterized. The structure and properties of the copolymers are characterized by GPC, DSC, TG, NMR, FT-IR, UV-Vis spectra and elemental analysis. The glass transition temperature and UV-Vis spectra properties of these three organometallic copolymers are found to be different from the normal polystyrene. New synthetic strategy for the synthesis of organometallic copolymer is developed.

  19. The first organometallic selective estrogen receptor modulators (SERMs) and their relevance to breast cancer.

    Science.gov (United States)

    Jaouen, Gérard; Top, Siden; Vessières, Anne; Leclercq, G; McGlinchey, Michael J

    2004-09-01

    In the overall scheme of the future development of new drugs for the treatment of breast cancer, specially tamoxifen resistant tumours, we have explored the unprecedented use of organometallic SERMs. The initial idea is to enhance the efficacy of the current standard, i.e. tamoxifen, by modifying the structure through judicious incorporation of an organometallic moiety possessing novel properties. Results have been varied, justifying a systematic approach that has proved to be full of surprised. The following differing situations were observed (a) the anti-proliferative effect is due to the vector and the organometallic moiety does not improve the effects of the SERM, no matter what concentration is used. In particular, this is the case for the hydroxytamoxifen derivative bearing a CpRe(CO)3 group, which behaves almost identically to hydroxytamoxifen. These stable species have future promise for use with radionucleides of Re and Tc (b) the effect of the organometallic moiety counteracts the anti-estrogenic behaviour of the vector and leads to species with proliferative activity; this is the case with Cp2TiCl2 entity, which when attached to tamoxifen behaves as a powerful estrogen, probably due to in situ release of Ti(IV) (c) a synergy exists between the cytotoxic organometallic moiety and its organic vector, leading to unique anti-proliferative effects on breast cancer cells classed ER+ and ER-. This result opens a new window on organometallic oncology. It is also clear that the range of possibilities is broad, varied and currently unpredictable. A systematic study combining organometallic chemistry and biology is the only option in the search for new SERMs with novel properties.

  20. Experimental Study on Machining Shape Hole of Ni-based Super-heat-resistant Alloy

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Inconel 718 and Waspaloy, Nickel-based super-heat-resistant alloy, are high-strength, thermal-resistant and corrosion-resistant alloy that are widely used in parts of gas turbines and airplane engines. Due to their extremely tough and thermal-resistant nature, they are well known as materials that are difficult to cut. Shape holes on a disc of an aircraft engine, made of Ni-based super-heat-resistant alloy, are required with good surface integrity and geometric accuracy. This kind of shape hole is produced ...

  1. Phase transformation and liquid density redistribution during solidification of Ni-based superalloy Inconel 718

    Directory of Open Access Journals (Sweden)

    Wang Ling

    2012-08-01

    Full Text Available The influences of chemical segregation and phase transformation on liquid density variation during solidification of Ni-based supperalloy Inconel 718 were investigated using SEM and EDS. It was found that significant segregation in liquid prompts high Nb phase to precipitate directly from liquid, which results in the redistribution of alloy elements and liquid density in their vicinity. The term “inter-precipitate liquid density” is therefore proposed and this concept should be applied to determine the solidification behavior of superalloy Inconel 718.

  2. Effect of Phosphorus on Microstructure and High Temperature Properties of a Cast Ni-base Superalloy

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Effect of phosphorus on the microstructure and high temperature properties of a cast Ni-base superalloy M963 has been investigated. SEM observation and EDS analysis showed that P was mostly enriched in the interdendritic region, and the P-rich phase was formed in the front position of finally solidified eutectics in high P doped alloys. It was found that the P-rich phase, as preferred initiation and propagation site of cracks, could aggravate the fracture process at high temperature in high P doped alloys. Consequently, high P addition would reduce remarkably the ductility and creep life of M963 superalloy at high temperature.

  3. Development of Ni-Based Catalysts for Steam Reforming of Tar Derived from Biomass Pyrolysis

    Institute of Scientific and Technical Information of China (English)

    Dalin LI; Yoshinao NAKAGAWA; Keiichi TOMISHIGE

    2012-01-01

    Nickel catalysts are effective for the steam reforming of tar derived from biomass pyrolysis,but the improvement is needed in terms of activity,stability,suppression of coke deposition and aggregation,and regeneration.Our recent development of Ni-based catalysts for the steam reforming of tar is reviewed including the modification with CeO2 (or MnO),trace Pt,and MgO.The role of additives such as CeO2,MnO,Pt,and MgO is also discussed.

  4. HREM investigation of coherent {gamma}' particles in Ni based superalloys

    Energy Technology Data Exchange (ETDEWEB)

    Calzado, L.; Calderon, H.A. [Dept. de Ciencia de Materiales, ESFM, Apdo., Mexico (Mexico); Mori, T. [Manchester Materials Science Centre, Manchester (United Kingdom); Kisielowski, C. [Lawrence Berkeley Nat. Lab., NCEM, Berkeley, CA (United States); Clement, N. [CEMES-CNRS, Toulouse (France)

    2003-07-01

    The mechanism of coarsening of coherent particles in solids is investigated via high-resolution electron microscopy (HREM). Ni based alloys are used for microscopic observation of interfaces between particles ({gamma}') and matrix ({gamma}). HREM images of neighboring particles are used to ascertain whether or not such particles have the same translation order domain (TOD), and to measure the distance between them. It is found that the distance between particles is influenced by the relationship between their respective TOD. Particles with different TOD show shorter separation distances. (orig.)

  5. Primary and secondary dendrite spacing of Ni-based superalloy single crystals

    Directory of Open Access Journals (Sweden)

    SLOBODANKA KOSTIC

    2009-01-01

    Full Text Available Ni-based superalloy single crystals were grown by different methods (gradient method and Bridgman technique with spontaneous nucleation and with seed. In all crystal growth experiments using the Bridgman technique, the temperature gradient along the vertical furnace axes was constant (G = 33.5 °C/cm. The obtained single crystals were cut, mechanical and chemical polished, and chemically etched. Using a metallographic microscope, the spacing of the primary and secondary dendrites was investigated. The dendrite arm spacing (DAS was determined using a Quantimet 500 MC. The obtained results are discussed and compared with published data.

  6. Microscopic study of the structure of the Steel Ni-based Alloy: Hastelloy G35 Alloy

    Science.gov (United States)

    Sabir, F.; Ben Lenda, O.; Saissi, S.; Marbouh, K.; Tyouke, B.; Zerrouk, L.; Ibnlfassi, A.; Ouzaouit, K.; Elmadani, S.

    2017-03-01

    The study of the influence of heat treatment on changes of mechanical and structural properties of Steel Ni-based Alloy is a highly interdisciplinary topic at the interface of the physical chemistry of metallic materials, which also helps in environmental and economic protection.After heat treatment, the structural and micro-structural studies for the different transformation temperature led to identify phases formed and the morphology. This work has been carried out using different techniques: X-ray diffraction, optical microscopy and scanning electron microscopy.

  7. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth.

    Science.gov (United States)

    Yang, Bin; Keum, Jong; Ovchinnikova, Olga S; Belianinov, Alex; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher M; Geohegan, David B; Xiao, Kai

    2016-04-20

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films, a major unresolved question is the competition between multiple halide species (e.g., I(-), Cl(-), Br(-)) in the formation of the mixed-halide perovskite crystals. Whether Cl(-) ions are successfully incorporated into the perovskite crystal structure or, alternatively, where they are located is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br(-) or Cl(-) ions can promote crystal growth, yet reactive I(-) ions prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl(-) ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performing and cost-effective optoelectronic devices.

  8. Switching on elusive organometallic mechanisms with photoredox catalysis.

    Science.gov (United States)

    Terrett, Jack A; Cuthbertson, James D; Shurtleff, Valerie W; MacMillan, David W C

    2015-08-20

    Transition-metal-catalysed cross-coupling reactions have become one of the most used carbon-carbon and carbon-heteroatom bond-forming reactions in chemical synthesis. Recently, nickel catalysis has been shown to participate in a wide variety of C-C bond-forming reactions, most notably Negishi, Suzuki-Miyaura, Stille, Kumada and Hiyama couplings. Despite the tremendous advances in C-C fragment couplings, the ability to forge C-O bonds in a general fashion via nickel catalysis has been largely unsuccessful. The challenge for nickel-mediated alcohol couplings has been the mechanistic requirement for the critical C-O bond-forming step (formally known as the reductive elimination step) to occur via a Ni(III) alkoxide intermediate. Here we demonstrate that visible-light-excited photoredox catalysts can modulate the preferred oxidation states of nickel alkoxides in an operative catalytic cycle, thereby providing transient access to Ni(III) species that readily participate in reductive elimination. Using this synergistic merger of photoredox and nickel catalysis, we have developed a highly efficient and general carbon-oxygen coupling reaction using abundant alcohols and aryl bromides. More notably, we have developed a general strategy to 'switch on' important yet elusive organometallic mechanisms via oxidation state modulations using only weak light and single-electron-transfer catalysts.

  9. Sweetening ruthenium and osmium: organometallic arene complexes containing aspartame.

    Science.gov (United States)

    Gray, Jennifer C; Habtemariam, Abraha; Winnig, Marcel; Meyerhof, Wolfgang; Sadler, Peter J

    2008-09-01

    The novel organometallic sandwich complexes [(eta(6)-p-cymene)Ru(eta(6)-aspartame)](OTf)(2) (1) (OTf = trifluoromethanesulfonate) and [(eta(6)-p-cymene)Os(eta(6)-aspartame)](OTf)(2) (2) incorporating the artificial sweetener aspartame have been synthesised and characterised. A number of properties of aspartame were found to be altered on binding to either metal. The pK(a) values of both the carboxyl and the amino groups of aspartame are lowered by between 0.35 and 0.57 pH units, causing partial deprotonation of the amino group at pH 7.4 (physiological pH). The rate of degradation of aspartame to 3,6-dioxo-5-phenylmethylpiperazine acetic acid (diketopiperazine) increased over threefold from 0.12 to 0.36 h(-1) for 1, and to 0.43 h(-1) for 2. Furthermore, the reduction potential of the ligand shifted from -1.133 to -0.619 V for 2. For the ruthenium complex 1 the process occurred in two steps, the first (at -0.38 V) within a biologically accessible range. This facilitates reactions with biological reductants such as ascorbate. Binding to and activation of the sweet taste receptor was not observed for these metal complexes up to concentrations of 1 mM. The factors which affect the ability of metal-bound aspartame to interact with the receptor site are discussed.

  10. Record Multiphoton Absorption Cross-Sections by Dendrimer Organometalation.

    Science.gov (United States)

    Simpson, Peter V; Watson, Laurance A; Barlow, Adam; Wang, Genmiao; Cifuentes, Marie P; Humphrey, Mark G

    2016-02-12

    Large increases in molecular two-photon absorption, the onset of measurable molecular three-photon absorption, and record molecular four-photon absorption in organic π-delocalizable frameworks are achieved by incorporation of bis(diphosphine)ruthenium units with alkynyl linkages. The resultant ruthenium alkynyl-containing dendrimers exhibit strong multiphoton absorption activity through the biological and telecommunications windows in the near-infrared region. The ligated ruthenium units significantly enhance solubility and introduce fully reversible redox switchability to the optical properties. Increasing the ruthenium content leads to substantial increases in multiphoton absorption properties without any loss of optical transparency. This significant improvement in multiphoton absorption performance by incorporation of the organometallic units into the organic π-framework is maintained when the relevant parameters are scaled by molecular weights or number of delocalizable π-electrons. The four-photon absorption cross-section of the most metal-rich dendrimer is an order of magnitude greater than the previous record value.

  11. Metallogels from Coordination Complexes, Organometallic, and Coordination Polymers.

    Science.gov (United States)

    Dastidar, Parthasarathi; Ganguly, Sumi; Sarkar, Koushik

    2016-09-20

    A supramolecular gel results from the immobilization of solvent molecules on a 3D network of gelator molecules stabilized by various supramolecular interactions that include hydrogen bonding, π-π stacking, van der Waals interactions, and halogen bonding. In a metallogel, a metal is a part of the gel network as a coordinated metal ion (in a discrete coordination complex), as a cross-linking metal node with a multitopic ligand (in coordination polymer), and as metal nanoparticles adhered to the gel network. Although the field is relatively new, research into metallogels has experienced a considerable upsurge owing to its fundamental importance in supramolecular chemistry and various potential applications. This focus review aims to provide an insight into the development of designing metallogelators. Because of the limited scope, discussions are confined to examples pertaining to metallogelators derived from discrete coordination complexes, organometallic gelators, and coordination polymers. This review is expected to enlighten readers on the current development of designing metallogelators of the abovementioned class of molecules. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Coordination of dibensothiophenes and corannulenes to organometallic ruthenium (II) fragments

    Energy Technology Data Exchange (ETDEWEB)

    Vecchi, Paul Anthony [Iowa State Univ., Ames, IA (United States)

    2005-01-01

    This dissertation contains five papers in the format required for journal publication which describe (in part) my research accomplishments as a graduate student at Iowa State University. This work can be broadly categorized as the binding of weakly-coordinating ligands to cationic organometallic ruthenium fragments, and consists of two main areas of study. Chapters 2-4 are investigations into factors that influence the binding of dibenzothiophenes to [Cp'Ru(CO)2(+ fragments, where Cp' = η5-C5H5 (Cp) and η5-C5Me5 (Cp*). Chapters 5 and 6 present the synthesis and structural characterization of complexes containing corannulene buckybowls that are η6-coordinated to [Cp*Ru(+ fragments. The first chapter contains a brief description of the difficulty in lowering sulfur levels in diesel fuel along with a review of corannulene derivatives and their metal complexes. After the final paper is a short summary of the work herein (Chapter 7). Each chapter is independent, and all equations, schemes, figures, tables, references, and appendices in this dissertation pertain only to the chapter in which they appear.

  13. Lipase active-site-directed anchoring of organometallics: metallopincer/protein hybrids.

    Science.gov (United States)

    Kruithof, Cornelis A; Casado, Miguel A; Guillena, Gabriela; Egmond, Maarten R; van der Kerk-van Hoof, Anca; Heck, Albert J R; Klein Gebbink, Robertus J M; van Koten, Gerard

    2005-11-18

    The work described herein presents a strategy for the regioselective introduction of organometallic complexes into the active site of the lipase cutinase. Nitrophenol phosphonate esters, well known for their lipase inhibitory activity, are used as anchor functionalities and were found to be ideal tools to develop a single-site-directed immobilization method. A small series of phosphonate esters, covalently attached to ECE "pincer"-type d8-metal complexes through a propyl tether (ECE=[C6H3(CH2E)(2)-2,6]-; E=NR2 or SR), were designed and synthesized. Cutinase was treated with these organometallic phosphonate esters and the new metal-complex/protein hybrids were identified as containing exactly one organometallic unit per protein. The organometallic proteins were purified by membrane dialysis and analyzed by ESI-mass spectrometry. The major advantages of this strategy are: 1) one transition metal can be introduced regioselectively and, hence, the metal environment can potentially be fine-tuned; 2) purification procedures are facile due to the use of pre-synthesized metal complexes; and, most importantly, 3) the covalent attachment of robust organometallic pincer complexes to an enzyme is achieved, which will prevent metal leaching from these hybrids. The approach presented herein can be regarded as a tool in the development of regio- and enantioselective catalyst as well as analytical probes for studying enzyme properties (e.g., structure) and, hence, is a "proof-of-principle design" study in enzyme chemistry.

  14. Synthesis, Properties Characterization and Applications of Various Organobismuth Compounds

    Directory of Open Access Journals (Sweden)

    Jingfei Luan

    2011-05-01

    Full Text Available Organobismuth chemistry was emphasized in this review article due to the low price, low toxicity and low radioactivity characteristics of bismuth. As an environmentally-friendly class of organometallic compounds, different types of organobismuth compounds have been used in organic synthesis, catalysis, materials, etc. The synthesis and property characterization of many organobismuth compounds had been summarized. This review article also presented a survey of various applications of organobismuth compounds in organic transformations, as reagents or catalysts. The reactivity, reaction pathways and mechanisms of reactions with organobismuths were discussed. Less common and limiting aspects of organobismuth compounds were also briefly mentioned.

  15. Planar chiral (η6-arene)Cr(CO)3 containing carboxylic acid derivatives: synthesis and use in the preparation of organometallic analogues of the antibiotic platensimycin.

    Science.gov (United States)

    Patra, Malay; Merz, Klaus; Metzler-Nolte, Nils

    2012-01-07

    With more and more organometallic compounds receiving attention for applications in medicinal organometallic chemistry, the need arises for stereoselective syntheses of more complicated structures containing organometallic moieties, for example as isosteric substitutes for organic drug candidates. Herein, the synthesis and characterization of both diastereomers of a planar chiral (η(6)-arene)Cr(CO)(3) containing carboxylic acid derivative, namely, 3-{η(6)-(1, 2, 3, 4-tetrahydro-1-endo/exo-methyl-2-oxonaphthalen-1-yl)-tricarbonylchromium(0)}propanoic acid (7 and 8) is reported. The molecular structures of both were confirmed by single crystal X-ray diffraction. The degree of diastereoselectivity in Cr(CO)(3) complexation with methyl/tert-butyl-3-(1,2,3,4-tetrahydro-1-methyl-2-oxonaphthalen-1-yl)propanoate (4a/4b) vs. the Michael addition of methyl/tert-butyl acrylate to (η(6)-1-methyl-2-tetralone)Cr(CO)(3) (9) was also examined. In the latter case the alkylation was found to be completely diastereoselective and gave methyl/tert-butyl-3-{η(6)-(1, 2, 3, 4-tetrahydro-1-endo-methyl-2-oxonaphthalen-1-yl)-tricarbonylchromium (0)}propanoate (5a and 5b) in excellent yield. Both the carboxylic acids 7 and 8 were coupled with the aminoresorcyclic acid core to achieve diastereomeric bioorganometallics 15a and 15b based on the naturally occurring antibiotic platensimycin lead structure (1a, see Fig. 1). The newly synthesized bioorganometallics were tested against various Gram-positive and Gram-negative bacterial strains but show no promising antibacterial activity.

  16. Effect of inhomogeneous re-oxidation on Ni-based SOFC oxidation resistance

    Science.gov (United States)

    Lou, Kang; Wang, Feng Hui; Lu, Yong Jun; Zhao, Xiang

    2016-09-01

    Inhomogeneous re-oxidation, which causes graded NiO content along anode thickness, has been confirmed to be a key reason for Ni-based cell cracking during redox progress. In this paper, an analytical model is developed to estimate the impact of inhomogeneous re-oxidation on Ni-based solid oxide fuel cell (SOFC) oxidation resistance. And experiments, in which the SOFC was partially re-oxidized, were implemented for model trial. Model results show that electrolyte internal stress can be significantly reduced (from 367 MPa to 135 MPa, when the oxidation degree is 60%), and the electrolyte can remain intact even when the oxidation degree reaches about 70%, if the anode was re-oxidized uniformly. This impact of inhomogeneous re-oxidation on stress in the electrolyte decreases as the anode thickness increases. Scanning electron microscopic (SEM) images of partially oxidized anode cross-sections confirmed that Ni oxidation was inhomogeneous, in which the outer regions of the anode became almost fully oxidized, while the inner regions remained metallic. And the inhomogeneity increases with the redox times. Consequently, it is important to avoid gradients in NiO content during oxidation progress to prevent cell cracking.

  17. Characteristics of high wear resistant Ni-base materials strengthened by precipitation hardening of wolfram silicide

    Energy Technology Data Exchange (ETDEWEB)

    Kiuchi, Kiyoshi; Ide, Hisayuki; Ishiyama, Takashi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1998-12-31

    The practical application of Co-base Stellite and Ni base Inconel for reactor core components with high allowable stress levels is considered to be limited by the formation of radioactive cruds and the susceptibility to IASCC respectively. For this view-point, W-silicide strengthened Cr-W-Si Ni-base high wear resistant alloy so-called HWI alloy was newly developed as an alternative material. The chemical composition and the alloy making process were optimized by applying the electron beam purification process and the thermo-mechanical treatment. The mechanical strength higher than it of above commercial alloys was easily obtained by both solid solution hardening and precipitation hardening, because this alloy has the excellent cold and hot workabilities. The irradiation resistance and the corrosion resistance superior than these of above commercial alloys were verified by several laboratory tests of HWI heats. To maintain austenite phase stability at the practical temperature and to enrich oxide former alloying elements were clarified to be the most important means for this alloy development. (author)

  18. A New Ni-Based Metallic Glass with High Thermal Stability and Hardness

    Directory of Open Access Journals (Sweden)

    Aytekin Hitit

    2015-02-01

    Full Text Available Glass forming ability (GFA, thermal stability and microhardness of Ni51−xCuxW31.6B17.4 (x = 0, 5 metallic glasses have been investigated. For each alloy, thin sheets of samples having thickness of 20 µm and 100 µm were synthesized by piston and anvil method in a vacuum arc furnace. Also, 400 µm thick samples of the alloys were synthesized by suction casting method. The samples were investigated by X-ray diffractometry (XRD and differential scanning calorimetry (DSC. Crystallization temperature of the base alloy, Ni51W31.6B17.4, is found to be 996 K and 5 at.% copper substitution for nickel increases the crystallization temperature to 1063 K, which is the highest value reported for Ni-based metallic glasses up to the present. In addition, critical casting thickness of alloy Ni51W31.6B17.4 is 100 µm and copper substitution does not have any effect on critical casting thickness of the alloys. Also, microhardness of the alloys are found to be around 1200 Hv, which is one of the highest microhardness values reported for a Ni-based metallic glass until now.

  19. Biomass Catalytic Pyrolysis with Ni Based Catalyst to Produce Hydrogen Rich Gas

    Institute of Scientific and Technical Information of China (English)

    WANG Mingfeng; LIU Min; XU Xiwei; LI Bosong; ZHANG Qiang; JIAN Enchen

    2010-01-01

    Hydrogen rich gas was produced using rice husk as biomass material on the continuous biomass pyrolysis apparatus which consisted of continuous pyrolysis reactor and secondary catalytic cracking reactor. Ni based catalysts of different Ni/Al mass ratio and calcined temperature were prepared by impregnating method. The catalysts were characterized by X-ray diffraction (XRD),scan electron microscope (SEM) and FT-IR Spectrometer (FT-IR). Ni based catalyst showed good selectivity for H2 production from biomass. Catalysts prepared under different conditions had little influence on the yields of three states products when used at the same cracking temperature. Ni/Al mass ratio played an important role in products selectivity. However, the content of NiO increased further when Ni/Al mass ratio values reached 0.7 : 10, and the yield of H2 slightly increased. Hydrogen yield was greatly impacted by calcined temperature. Catalyst calcined at 550"C performed best. When the catalyst was calcined at high temperature, NiO in the catalyst transformed into NiAl2O4, and the acid site also changed, which caused the deactivation of the catalyst. The hydrogen yield increased with the cracking temperature. The highest stable yield of hydrogen was about 30% without increasing with the cracking temperature.

  20. A study of microstructural characteristics of Ni-based superalloys at high temperatures

    Science.gov (United States)

    Lal, Ravindra B.; Aggarwal, M. D.

    1990-01-01

    The microstructural characteristics of the Ni-based superalloy MAR-M245(Hf) which is used in manufacturing the components of the Space Shuttle main engine are studied. These superalloys need optimum heat treatment to get the best results. To find out the optimum heat treatment, the techniques of differential thermal analysis (DTA) and the optical photomicrographs were utilized. In the first phase, the existing experimental equipment like cutting, grinding/polishing machines and metallurgical microscope were set up to cut/polish and take the photomicrographs. In the beginning of the project a Perkin Elmer differential thermal analyzer DTA1700 along with a temperature programmed and the needed computer interface was procured and made operational. In the second year a Leitz Metallux-3 hot state research microscope was also procured and installed for in-situ observation of the superalloy samples. The hot stage when tested for the first time alloyed the thermocouple with the Tantalum heating element and has now been installed. Samples of MAR-M246(Hf), MAR-M247, Waspaloy, Udimet-41, CMSX-3, and CMSX-3 (Polycrystalline and single crystals) were studied using a differential thermal analyzer and the results are reported. Photomicrographs of the Ni-based superalloy MAR-M246 (Hf) were recorded before and after heat treatment at certain temperatures. More heat treatments need to be done before a final inference can be reached.

  1. Methodology of Ni-base Superalloy Development for VHTR using Design of Experiments and Thermodynamic Calculation

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sungwoo; Kim, Dongjin [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2013-03-15

    This work is concerning a methodology of Ni-base superalloy development for a very high temperature gas-cooled reactor(VHTR) using design of experiments(DOE) and thermodynamic calculations. Total 32 sets of the Ni-base superalloys with various chemical compositions were formulated based on a fractional factorial design of DOE, and the thermodynamic stability of topologically close-packed(TCP) phases of those alloys was calculated by using the THERMO-CALC software. From the statistical evaluation of the effect of the chemical composition on the formation of TCP phase up to a temperature of 950 .deg. C, which should be suppressed for prolonged service life when it used as the structural components of VHTR, 16 sets were selected for further calculation of the mechanical properties. Considering the yield and ultimate tensile strengths of the selected alloys estimated by using the JMATPRO software, the optimized chemical composition of the alloys for VHTR application, especially intermediate heat exchanger, was proposed for a succeeding experimental study.

  2. Optimization of Ni-Based WC/Co/Cr Composite Coatings Produced by Multilayer Laser Cladding

    Directory of Open Access Journals (Sweden)

    Andrea Angelastro

    2013-01-01

    Full Text Available As a surface coating technique, laser cladding (LC has been developed for improving wear, corrosion, and fatigue properties of mechanical components. The main advantage of this process is the capability of introducing hard particles such as SiC, TiC, and WC as reinforcements in the metallic matrix such as Ni-based alloy, Co-based alloy, and Fe-based alloy to form ceramic-metal composite coatings, which have very high hardness and good wear resistance. In this paper, Ni-based alloy (Colmonoy 227-F and Tungsten Carbides/Cobalt/Chromium (WC/Co/Cr composite coatings were fabricated by the multilayer laser cladding technique (MLC. An optimization procedure was implemented to obtain the combination of process parameters that minimizes the porosity and produces good adhesion to a stainless steel substrate. The optimization procedure was worked out with a mathematical model that was supported by an experimental analysis, which studied the shape of the clad track generated by melting coaxially fed powders with a laser. Microstructural and microhardness analysis completed the set of test performed on the coatings.

  3. CORROSION RESISTANCE OF ORGANOMETALLIC COATING APLICATED IN FUEL TANKS USING ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY IN BIOFUEL – PART I

    Directory of Open Access Journals (Sweden)

    Milene Adriane Luciano

    2014-10-01

    Full Text Available Nowadays, the industry has opted for more sustainable production processes, and the planet has also opted for new energy sources. From this perspective, automotive tanks with organometallic coatings as well as a partial substitution of fossil fuels by biofuels have been developed. These organometallic coated tanks have a zinc layer, deposited by a galvanizing process, formed between the steel and the organometallic coating. This work aims to characterize the organometallic coating used in metal automotive tanks and evaluate their corrosion resistance in contact with hydrated ethyl alcohol fuel (AEHC. For this purpose, the resistance of all layers formed between Zinc and EEP steel and also the tin coated steel, which has been used for over thirty years, were evaluated. The technique chosen was the Electrochemical Impedance Spectroscopy. The results indicated an increase on the corrosion resistance when organometallic coatings are used in AEHC medium. In addition to that, these coatings allow an estimated 25% reduction in tanks production costs.

  4. Design of Multiple Metal Doped Ni Based Catalyst for Hydrogen Generation from Bio-oil Reforming at Mild-temperature

    Institute of Scientific and Technical Information of China (English)

    Li-xia Yuan; Fang Ding; Jian-ming Yao; Xiang-song Chen; Wei-wei Liu; Jin-yong Wu; Fei-yan Gong

    2013-01-01

    A new kind of multiple metal (Cu,Mg,Ce) doped Ni based mixed oxide catalyst,synthesized by the co-precipitation method,was used for efficient production of hydrogen from bio-oil reforming at 250-500 ℃.Two reforming processes,the conventional steam reforming (CSR) and the electrochemical catalytic reforming (ECR),were performed for the bio-oil reforming.The catalyst with an atomic mol ratio of Ni∶Cu∶Mg∶Ce∶Al=5.6∶1.1∶1.9∶1.0∶9.9 exhibited very high reforming activity both in CSR and ECR processes,reaching 82.8% hydrogen yield at 500 ℃ in the CSR,yield of 91.1% at 400 ℃ and 3.1 A in the ECR,respectively.The influences of reforming temperature and the current through the catalyst in the ECR were investigated.It was observed that the reforming and decomposition of the bio-oil were significantly enhanced by the current.The promoting effects of current on the decomposition and reforming processes of bio-oil were further studied by using the model compounds of biooil (acetic acid and ethanol) under 101 kPa or low pressure (0.1 Pa) through the time of flight analysis.The catalyst also shows high water gas shift activity in the range of 300-600 ℃.The catalyst features and alterations in the bio-oil reforming were characterized by the ICP,XRD,XPS and BET measurements.The mechanism of bio-oil reforming was discussed based on the study of the elemental reactions and catalyst characterizations.The research catalyst,potentially,may be a practical catalyst for high efficient production of hydrogen from reforning of bio-oil at mild-temperature.

  5. Molecular metal catalysts on supports: organometallic chemistry meets surface science.

    Science.gov (United States)

    Serna, Pedro; Gates, Bruce C

    2014-08-19

    Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal

  6. Combining organometallic reagents, the sulfur dioxide surrogate DABSO, and amines: a one-pot preparation of sulfonamides, amenable to array synthesis.

    Science.gov (United States)

    Deeming, Alex S; Russell, Claire J; Willis, Michael C

    2015-01-19

    We describe a method for the synthesis of sulfonamides through the combination of an organometallic reagent, a sulfur dioxide equivalent, and an aqueous solution of an amine under oxidative conditions (bleach). This simple reaction protocol avoids the need to employ sulfonyl chloride substrates, thus removing the limitation imposed by the commercial availability of these reagents. The resultant method allows access to new chemical space, and is also tolerant of the polar functional groups needed to impart favorable physiochemical properties required for medicinal chemistry and agrochemistry. The developed chemistry is employed in the synthesis of a targeted 70 compound array, prepared using automated methods. The array achieved a 93% success rate for compounds prepared. Calculated molecular weights, lipophilicities, and polar surface areas are presented, demonstrating the utility of the method for delivering sulfonamides with drug-like properties.

  7. Steam reforming of glycerol into hydrogen over nano-size Ni-based hydrotalcite-like catalysts.

    Science.gov (United States)

    Hur, Eun; Moon, Dong Ju

    2011-08-01

    Steam reforming (SR) of glycerol for the production of hydrogen was investigated over the nano-sized Ni-based catalysts. The Ni-based catalysts were prepared by solid phase crystallization and impregnation methods, and characterized by N2 physisorption, CO chemisorption, XRD, SEM, and TEM techniques. The Ni/gamma-Al2O3 catalyst showed higher conversion and H2 selectivity. However, it was slowly deactivated due to the carbon formation on the surface of catalyst and the sintering. It was found that the Ni based hydrotalcite-like catalyst (spc-Ni/MgAl) showed higher catalytic activity to prevent carbon formation than Ni/gamma-Al2O3 catalyst in the SR of glycerol.

  8. Fabrication kinetics and properties of Ni-based nano-arrays embedded in anodic Al IIO 3 film

    Science.gov (United States)

    Yan, Hao; Zhang, Jiancheng; You, Chenxia; Song, Zhenwei; Yu, Benwei; Shen, Yue

    2008-02-01

    By direct current electrodeposition technique combined with the anodic aluminum oxide films, Ni-based nano-arrays were successfully performed. The structure was studied by X-ray diffraction and high-resolution transmission electron microscopy with selected-area electron diffraction. Energy dispersive spectroscopy was used to prove the composition of the prepared nanowires. The magnetic property curves of Ni-based nano-arrays were measured by a physical property measurement system. According to electrochemical analysis, the growth kinetics of the nanowires was studied by determining the relationship between the current and time under different parameters, such as electrolyte temperature and electrodeposition voltage.

  9. Evaluation of Characteristics of Non-Metallic Inclusions in P/M Ni-Base Superalloy by Automatic Image Analysis

    Institute of Scientific and Technical Information of China (English)

    Li; Xinggang; Ge; Changchun; Shen; Weiping

    2007-01-01

    Non-metallic inclusions,especially the large ones,within P/M Ni-base superalloy have a major influence on fatigue characteristics,but are not directly measurable by routine inspection.In this paper,a method,automatic image analysis,is proposed for estimation of the content,size and amount of non-metallic inclusions in superalloy.The methodology for the practical application of this method is described and the factors affecting the precision of the estimation are discussed.In the experiment,the characteristics of the non-metallic inclusions in Ni-base P/M superalloy are analyzed.

  10. Solidification Behavior and Segregation of Re-containing Cast Ni-base Superalloy with Different Cr Content

    Institute of Scientific and Technical Information of China (English)

    Xiurong Guan; Enze Liu; Zhi Zheng; Yongsi Yu; Jian Tong; Yuchun Zhai

    2011-01-01

    The effect of chromium (Cr) on solidification and segregation behavior of Re-containing cast Ni-base superalloys was investigated by optical microscopy (OM), scanning electron microscopy (SEM) and electronic probe micro analysis (EPMA). The results show that Cr has significant effect on solidification and segregation behavior of Re-containing cast Ni-base superalloys. The liquidus and solidus of alloy decrease with increasing Cr in alloys. The segregation coefficient (K) of Mo increases and that of W and Re decreases gradually with increasing Cr element.

  11. Monotherapy and combined therapy of new potential antitumor compounds: antiproliferative activities and biological targets

    OpenAIRE

    Marques, Mara Lisa Miranda

    2014-01-01

    Review article Martins, P., Marques, M., Coito, L., Pombeiro, A.J.L., Baptista, P.V., Fernandes, A.R. 2014. Organometallic Compounds in Cancer Therapy: Past Lessons and Future Directions. Anti-cancer Agents in Medicinal Chemistry 14. PMID: 25173559

  12. Tensile and fracture behavior of DZ951 Ni-base superalloy

    Institute of Scientific and Technical Information of China (English)

    CHU Zhao-kuang; YU Jin-jiang; SUN Xiao-feng; ZHAO Nai-ren; GUAN Heng-rong; HU Zhuang-qi

    2006-01-01

    The tensile and fracture behavior of DZ951 directionally solidified Ni-base superalloy was studied in the temperature range of 20-1 100 ℃. The fracture mode was examined by scanning electron microscopy. The results show the experimental temperature has no significant effect on the tensile strengths, which are greater than 1 000 MPa from room temperature to 800 ℃. The yield strength reaches its maximum (970 MPa) at 800 ℃. When the experimental temperature is higher than 800 ℃, the tensile and yield strengths decrease evidently and the ductility increases remarkably. The fractograph of fracture surface for the tensile specimen at room temperature shows a dimple-ductile fracture mode. The fractograph from 600 to 800 ℃ shows a slide fracture mode. The fractograph from 900 to 1 100 ℃ exhibits a creep rupture mode with uneven deformation.

  13. Microstructural and Mechanical Properties of Ni-Base Thermal Spray Coatings Deposited by Flame Spraying

    Science.gov (United States)

    Amokrane, Bradai Mohand; Abdelhamid, Sadeddine; Youcef, Mouadji; Abderrahim, Benabbas; Nedjemeddine, Bounar; Ahmed, Mammeri

    2011-10-01

    In this work, two different Ni-base powders, namely, ProXon 21021 (P21) and ProXon 21031 (P31), were sprayed onto a steel substrate 35CrMo4 using a thermal flame spray technique. The morphology and chemical composition of the phases that are present in the powders and coatings were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The hardness and wear resistance of the coatings were investigated. The XRD analysis revealed that the phases present in the coatings are different from the initial powders. In addition, some inhomogeneities such as oxides, porosity, and unmelted particles were observed by SEM. It was found that the P31 spray-coated exhibited higher microhardness, higher wear resistance, and significantly lower friction coefficient in comparison with those of P21 coatings.

  14. The effect of microstructure on the fatigue behavior of Ni base superalloys

    Science.gov (United States)

    Antolovich, S. D.; Jayaraman, N.

    1983-01-01

    Nickel-base superalloys are used in jet engine components such as disks, turbine blades, and vanes. Improvements in the fatigue behavior will allow the life to be extended or the payloads to be increased. The first part of the present investigation deals primarily with the effects of microstructural variations on the fatigue crack propagation (FCP) behavior of nickel-base alloys, while the second part is concerned with low-cycle fatigue (LCF) behavior of Ni base systems. Waspaloy at low temperature is considered, taking into account material heat treatment and test procedures, a composite plot of Waspaloy FCP data, Paris law fatigue crack propagation constants, monotonic tensile data, and overload FCP test results for Waspaloy. It is found that the FCP and overload behavior of nickel-base alloys may be markedly improved by heat treating. Attention is given to effects of cyclic deformation on microstructure and substructure, environmental damage, and an environmental/deformation model of high temperature LCF.

  15. Modeling of Thermal Expansion Coefficients of Ni-Based Superalloys Using Artificial Neural Network

    Science.gov (United States)

    Bano, Nafisa; Nganbe, Michel

    2013-04-01

    The objective of this work is to model the thermal expansion coefficients of various Ni-based superalloys used in gas turbine components. The thermal expansion coefficient is described as a function of temperature, chemical composition including Ni, Cr, Co, Mo, W, Ta, Nb, Al, Ti, B, Zr, and C contents as well as heat treatment including solutionizing and aging. Experimental values are well described and their relative changes well correlated by the model. Because gas turbine engine components operate under severe loading conditions and at high and varying temperatures, the prediction of their thermal expansion coefficient is crucial. The model developed in this work can be useful for design optimizations for minimizing thermo-mechanical stresses between the base alloys and potential protective coatings or adjacent components. It can substantially contribute to improve the performance and service life of gas turbine components.

  16. Isothermal oxidation behavior of cast Ni-base superalloy K44

    Institute of Scientific and Technical Information of China (English)

    LI Yun; LIU Xue-gui; GUO Jian-ting; YUAN Chao; YANG Hong-cai

    2006-01-01

    The oxidation behavior of a cast Ni-base superalloy K44 in air at 850-1 000 ℃ for l00 h was studied. The scales on the surface were determined by SEM and EPMA equipped with an EDXS. The results show that oxidation kinetics obey the parabolic law from which the values of activation energy Qp1=221.1 kJ/mol and Qp2=247.6 kJ/mol are estimated. The oxidation scales are composed of loose outer layer of TiO2/TiO-Cr2O3 and a small amount of NiCr2O4 and NiA12O4, compact intermediate layer Cr2O3, and precipitate of internal oxides A12O3.

  17. Nucleation and growth of precipitates in a Ni-based superalloy

    Energy Technology Data Exchange (ETDEWEB)

    Petkov, M.P.; Lynn, K.G. [Washington State Univ., Pullman, WA (United States). Dept. of Physics; Somoza, A. [IFIMAT, Univ. Nacional del Centro de la Provincia de Buenos Aires, Tandil (Argentina); Comision de Investigaciones Cientificas de la Provincia de Buenos Aires, La Plata (Argentina); Santos, G. [IFIMAT, Univ. Nacional del Centro de la Provincia de Buenos Aires, Tandil (Argentina)

    2001-07-01

    A study of the early stages of precipitation of the {gamma}'-phase in the commercial Ni-base superalloy Inconel X-750 is presented. Precipitation was induced by artificial aging heat treatments at 700 C during different times ranging up to 10{sup 4} min. Positron lifetime spectroscopy experiments, following the microstructural evolution, revealed a very complicated process of nucleation and growth of the second-phase particles, involving solute clustering and solute segregation. ''Frozen frames'' of the evolution process, chosen on the basis of the lifetime results, were studied by coincidence Doppler technique, which sheds information on the electronic and chemical environment around the positron trapping site. (orig.)

  18. Hot corrosion performance of a NiCr coated Ni-based alloy

    Energy Technology Data Exchange (ETDEWEB)

    Sidhu, T.S.; Prakash, S.; Agrawal, R.D. [Indian Institute of Technology, Roorkee (India)

    2006-07-15

    The hot corrosion performance of high velocity oxy-fuel sprayed Ni-20Cr wire coating on a Ni-based superalloy is evaluated for 1000 h at 900{sup o}C under cyclic conditions in a coal-fired boiler. The performance of bare and Ni-20Cr coated Superni 75 is assessed via thermogravimetric data, metal thickness loss corresponding to the corrosion scale formation, scale thickness loss and the depth of internal corrosion attack. The better hot corrosion resistance of the coated alloy is mainly attributed to the formation of a thick band of chromium oxide just above the scale-substrate interface and chromium oxide stringers along the splat boundaries, as well as to the nickel oxide and the dense and uniform fine grain structure of the as sprayed coating.

  19. The influence of mechanical vibrations on microstructure of Ni-based thermally sprayed-fused coatings

    Directory of Open Access Journals (Sweden)

    Jelena ŠKAMAT

    2013-12-01

    Full Text Available The influence of mechanical vibrations on microstructure and properties of Ni-based thermally sprayed and fused coatings deposited on a steel substrate has been studied. Self-fluxing powder with about 73% Ni was used as a sprayed material. As-sprayed coatings were refused using conventional flame technique and with introducing of mechanical vibrations. In result coatings with quite complicated microstructure were obtained. During investigation of coatings by different methods it was found that vibratory treatment really influences the solidified microstructure. It was found that vibrations promote densimetric movement of hard particles up - towards a surface with forming of thicker so-called “hard-inclusions-free” layer near interface. Some tendency was noted that coatings, remelted under vibrations, showed better corrosion and high-temperature oxidation resistance in comparison with coatings created without vibrational treatment during solidification.

  20. Highly selective hydrogenation of halonitroaromatics to aromatic haloamines by ligand modified Ni-based catalysts

    Institute of Scientific and Technical Information of China (English)

    Chun Shan Lu; Jing Hui Lv; Lei Ma; Qun Feng Zhang; Feng Feng; Xiao Nian Li

    2012-01-01

    Ligand modification of Ni-based catalysts by coordination of dicyandiamide to Ni metal leads to enhanced selectivity for the selective hydrogenation of halonitroaromatics.The selectivity of above 99.9% to aromatic haloamines can be achieved at the conversion of 100%.The results of H2-TPD and FT-IR experiments show that Ni-H+ species possessing the properties of Lewis acid site on the surface of Raney Ni could be responsible for the hydrodehalogenation.When Raney Ni was treated by dicyandiamide,Ni-H+ species interacted with N atom from the dicyandiamide.This interaction was stable even at reaction temperature,which reduced the possibility to form the intermediate state of Ar-Cl …H+Ni-.And then C-Cl bond could not be polarized and activated.The hydrodechlorination process was suppressed effectively.

  1. A study of microstructural characteristics and differential thermal analysis of Ni-based superalloys

    Science.gov (United States)

    Aggarwal, M. D.; Lal, R. B.; Oyekenu, Samuel A.; Parr, Richard; Gentz, Stephen

    1989-01-01

    The objective of this work is to correlate the mechanical properties of the Ni-based superalloy MAR M246(Hf) used in the Space Shuttle Main Engine with its structural characteristics by systematic study of optical photomicrographs and differential thermal analysis. The authors developed a method of predicting the liquidus and solidus temperature of various nickel based superalloys (MAR-M247, Waspaloy, Udimet-41, polycrystalline and single crystals of CMSX-2 and CMSX-3) and comparing the predictions with the experimental differential thermal analysis (DTA) curves using Perkin-Elmer DTA 1700. The method of predicting these temperatures is based on the additive effect of the components dissolved in nickel. The results were compared with the experimental values.

  2. Steam reforming of cyclic model compounds of bio-oil over Ni-based catalysts: Product distribution and carbon formation

    DEFF Research Database (Denmark)

    Trane-Restrup, Rasmus; Jensen, Anker Degn

    2015-01-01

    Steam reforming (SR) and oxidative steam reforming (OSR) of furfural, 2-methylfuran, and guaiacol have been investigated in the temperature range 400-800°C at a steam to carbon (S/C)-ratio of 5 and oxygen to carbon (O/C)-ratio of 0.2-1.4 over Ni/CeO2-K/MgAl2O4. Carbon oxides and H2 were the major...... products in the SR of 2-methylfuran and furfural, while the by-products were methane, ethanol, 2-propanol, and acetone. Temperatures of 500°C or above were needed to minimize the formation of by-products in the SR of 2-methylfuran and furfural. Phenolics, like benzenediols and phenol, were produced in high...

  3. Surface and Interface Engineering of Organometallic and Two Dimensional Semiconductor

    Science.gov (United States)

    Park, Jun Hong

    For over half a century, inorganic Si and III-V materials have led the modern semiconductor industry, expanding to logic transistor and optoelectronic applications. However, these inorganic materials have faced two different fundamental limitations, flexibility for wearable applications and scaling limitation as logic transistors. As a result, the organic and two dimensional have been studied intentionally for various fields. In the present dissertation, three different studies will be presented with followed order; (1) the chemical response of organic semiconductor in NO2 exposure. (2) The surface and stability of WSe2 in ambient air. (3) Deposition of dielectric on two dimensional materials using organometallic seeding layer. The organic molecules rely on the van der Waals interaction during growth of thin films, contrast to covalent bond inorganic semiconductors. Therefore, the morphology and electronic property at surface of organic semiconductor in micro scale is more sensitive to change in gaseous conditions. In addition, metal phthalocyanine, which is one of organic semiconductor materials, change their electronic property as reaction with gaseous analytes, suggesting as potential chemical sensing platforms. In the present part, the growth behavior of metal phthalocyanine and surface response to gaseous condition will be elucidated using scanning tunneling microscopy (STM). In second part, the surface of layered transition metal dichalcogenides and their chemical response to exposure ambient air will be investigated, using STM. Layered transition metal dichalcogenides (TMDs) have attracted widespread attention in the scientific community for electronic device applications because improved electrostatic gate control and suppression of short channel leakage resulted from their atomic thin body. To fabricate the transistor based on TMDs, TMDs should be exposed to ambient conditions, while the effect of air exposure has not been understood fully. In this part

  4. Hyperbranched Organometallic Polyynes :Optical and Thermal Properties and Their Transformation into Soft Ferromagnetic Ceramics

    Institute of Scientific and Technical Information of China (English)

    M. H(a)uβler; H. Dong; J. W. Y. Lam; A. Qin; H. Tong; B. Z. Tang

    2005-01-01

    @@ 1Introduction Organometallic polymers have emerged as a group of interesting materials due to their useful catalytic,optical, electrical, sensing, and magnetic properties inaccessible by their pure organic parents. It is therefore highly desirable to utilize this class of high performance macromolecules for the preparation of micro- and nanosized patterns by photolithographic techniques and as precursors for advanced ceramics[1].

  5. Organometallic macromolecules with piano stool coordination repeating units: chain configuration and stimulated solution behaviour.

    Science.gov (United States)

    Cao, Kai; Ward, Jonathan; Amos, Ryan C; Jeong, Moon Gon; Kim, Kyoung Taek; Gauthier, Mario; Foucher, Daniel; Wang, Xiaosong

    2014-09-11

    Theoretical calculations illustrate that organometallic macromolecules with piano stool coordination repeating units (Fe-acyl complex) adopt linear chain configuration with a P-Fe-C backbone surrounded by aromatic groups. The macromolecules show molecular weight-dependent and temperature stimulated solution behaviour in DMSO.

  6. Para-Functionalized NCN-Pincer Palladium and Platinum Complexes as Building Blocks in Organometallic Chemistry

    NARCIS (Netherlands)

    Slagt, Martijn Quico

    2002-01-01

    A rapidly evolving field in chemistry is the application of organometallic and coordination complexes as building blocks or active components for the construction of new materials exhibiting specific catalytic, redox, optical or sensor activities. A central theme in the construction of these inorgan

  7. Smart organometallic polymer platforms for redox sensing and as metal nanoparticle foundry

    NARCIS (Netherlands)

    Feng, Xueling

    2015-01-01

    In this Thesis, we aimed at developing novel tailored architectures and exploring rationally designed systems as redox active platforms for specific functions with organometallic polymer poly(ferrocenylsilane)s (PFSs). The preparation and characterization of various PFSs are described, including vir

  8. Application of olefin cross-metathesis to organometallics. Synthesis of unsaturated ferrocenyl alcohols and ketones

    Science.gov (United States)

    Seshadri; Lovely

    2000-02-10

    [reaction: see text] The application of olefin cross-metathesis to terminally unsaturated alpha-hydroxy- and alpha-ketoferrocenes is reported. Both substrates provided the terminally functionalized olefins in moderate to good yield. These examples represent the first cases of cross-metathesis of substrates containing an organometallic functional group.

  9. Redox-responsive organometallic hydrogels for in situ metal nanoparticle synthesis

    NARCIS (Netherlands)

    Zoetebier, Bram; Hempenius, Mark A.; Vancso, Gyula J.

    2015-01-01

    A new class of redox active hydrogels composed of poly(ferrocenylsilane) polyanion and poly(ethylene glycol) chains was assembled, using a copper-free azide–alkyne Huisgen cycloaddition reaction. These organometallic hydrogels displayed reversible collapse and reswelling upon chemical oxidation and

  10. Para-Functionalized NCN-Pincer Palladium and Platinum Complexes as Building Blocks in Organometallic Chemistry

    NARCIS (Netherlands)

    Slagt, Martijn Quico

    2002-01-01

    A rapidly evolving field in chemistry is the application of organometallic and coordination complexes as building blocks or active components for the construction of new materials exhibiting specific catalytic, redox, optical or sensor activities. A central theme in the construction of these inorgan

  11. Use of organometallic chelates in broiler diet: effect on the performance and bone structure. Preliminary results

    Directory of Open Access Journals (Sweden)

    Biagina Chiofalo

    2010-01-01

    Full Text Available On 26,000 Ross 508 broiler chickens (two groups of 13,000 per pen the effect of dietary substitution with in organic trace minerals or organometallic chelates on performances and bones tructure c trace minerals or organometallic chelates on performances and bone structure was studied. Treatments consisted of a commercial diet integrated with 0.5% of a vitamin-mineral premix containing inorganic trace minerals (CTR or organometallic chelates (MHA using Methionine Hydroxy Analog. Production performance was measured during the 52 d trial period and bone structure was evalu- ated at the slaughter (52 d. Significant (P=0.038 higher values were observed in the finishing period (41 to 52 d for the body weight of the treated group (3560 g vs. 3358 g. The same trend was observed for the ADG (MHA 87.6 g/d vs. CTR 71 g/d; P<0.05. Concerning ash percentage significant higher values were observed in the CTR group for femur (49.01% vs. 51.45%; P<0.01 and tibia (53.87% vs. 49.79%; P<0.001; femur showed also higher values for bone radiopacity (MHA 0.21 px vs. CTR 0.26 px; P=0.035. MHA group showed significant higher value for morphometric measures of the femur and tibia. Results suggest that organometallic chelates can be included in the diet without compromising broiler performance.

  12. Efficient organometallic spin filter between single-wall carbon nanotube or graphene electrodes

    DEFF Research Database (Denmark)

    Koleini, Mohammad; Paulsson, Magnus; Brandbyge, Mads

    2007-01-01

    We present a theoretical study of spin transport in a class of molecular systems consisting of an organometallic benzene-vanadium cluster placed in between graphene or single-wall carbon-nanotube-model contacts. Ab initio modeling is performed by combining spin density functional theory...

  13. Study of the HVOF Ni-Based Coatings' Corrosion Resistance Applied on Municipal Solid-Waste Incinerators

    Science.gov (United States)

    Guilemany, J. M.; Torrell, M.; Miguel, J. R.

    2008-06-01

    Oxidation of exchanger steel tubes causes important problems in Municipal Solid-Waste Incinerator (MSWI) plants. The present paper shows a possible solution for this problem through High-Velocity Oxygen Fuel (HVOF) thermal spray coatings. A comparative study was carried out between powder and wire Ni-based thermal spray coatings (with the same composition). These optimized coatings were compared based on their microstructure, wear properties (ASTM G99-90, ASTM G65-91), and erosion-corrosion (E-C) resistance. An E-C test designed in the Thermal Spray Centre was performed to reproduce the mechanisms that take place in a boiler. Studying the results of this test, the wire HVT Inconel coating sprayed by propylene appears to be the best alternative. A commercial bulk material with a composition similar to Ni-based coatings was tested to find the products of the oxidation reactions. The protective mechanisms of these materials were assessed after studying the results obtained for HVOF coatings and the bulk material where the presence of nickel and chromium oxides as a corrosion product can be seen. Kinetic evolution of the Ni-based coatings can be studied by thermogravimetric analysis. The protection that Inconel coatings give to the tube through the difference of the gain mass can be seen. Ni-based HVOF coatings by both spray conditions are a promising alternative to MSWI protection against chlorine environments, and their structures have a very important role.

  14. Non-vacuum sintering process of WC/W2C reinforced Ni-based coating on steel

    Science.gov (United States)

    Lyu, Yezhe; Sun, Yufu; Yang, Yong

    2016-03-01

    Ni-based composite coatings containing varied contents of tungsten carbides on low carbon steel were fabricated. Effects of sintering temperature and tungsten carbides contents on the surface, interface, microstructure and wear resistance of the coatings were investigated using scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, Vickers microhardness tester, bulk hardness tester and pin-on-disc tribometer. The results indicated that with appropriate sintering temperature (1230 °C), smooth coating surfaces can be achieved. Favorable interfaces about 200 μm can be got that both the chemical composition and property of the interfacial region showed gradual transitions from the substrates to the coatings. Microstructure of the coatings consists of tungsten carbides and M7C3/M23C6 in the matrix. With excessive sintering temperature, tungsten carbides tend to dissolve. Ni-based coatings containing tungsten carbides showed much higher level of bulk hardness and wear resistance than ISO Fe360A and ASTM 1566 steels. With increasing contents of tungsten carbides from 25% to 40%, bulk hardness of Ni-based coatings gradually increased. Ni-based coating with 35% tungsten carbides performed the best wear resistance.

  15. Fatigue-crack-initiation numerical modelling of a Ni-base powder metallurgy alloy

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    A simplified three-dimensional numerical model was presented to simulate the micro-crack nucleation and growth to some predefined dimension(approximately 0.38 mm) on the throat surface of a Ni-base powder metallurgy(PM) specimen.The numerical simulation of micro-crack initiation was based on the Tanaka-Mura micro-crack initiation models,where individual grains of the mesoscopic model were simulated using the Voronoi tessellation.Four improvements were made in the model.(1) Considering crack initiation along with 12 principal slip systems on octahedral slip planes of face centered cubic(FCC) crystal in three-dimensional(3-D) models.(2) Considering the effect of secondary phase precipitate due to impinging slip and dislocation pileup.(3) The Tanaka-Mura theory of fatigue-crack-initiation from notches was applied to simulate the crack initiation from another crack tip.(4) The coalescence of random initiated micro-cracks was simulated once they intersected with each other and a macro-crack was finally formed.The calculated results were in good agreement with the experimental data which verified the rationality of the simulation model.The applicability of the proposed model for treating fatigue-crack-initiation life in engineering structures was preliminarily achieved.%A simplified three-dimensional numerical model was presented to simulate the micro-crack nucleation and growth to some predefined dimension(approximately 0.38 mm) on the throat surface of a Ni-base powder metallurgy(PM) specimen.The numerical simulation of micro-crack initiation was based on the Tanaka-Mura micro-crack initiation models,where individual grains of the mesoscopic model were simulated using the Voronoi tessellation.Four improvements were made in the model.(1) Considering crack initiation along with 12 principal slip systems on octahedral slip planes of face centered cubic(FCC) crystal in three-dimensional(3-D) models.(2) Considering the effect of secondary phase

  16. Grain boundary engineering of powder-processed Ni-base superalloy RR1000

    Science.gov (United States)

    Detrois, Martin

    Grain boundary engineering (GBE) has been used to improve the properties of various polycrystalline materials by optimization of their grain boundary network. Traditional processing routes for GBE often require multiple iterations of cold work followed by short annealing cycles where each iteration imparts a modest increase in the fraction of special grain boundaries. Multiple iterations are then required to achieve sufficiently high fractions (>50%) that result in the improved properties. Thus, this GBE approach is not suitable for the fabrication of large, complex-shaped structures and leads to added manufacturing lead time and cost. In this investigation, the Ni-base superalloy RR1000 used as turbine discs in gas turbine engines manufactured by Rolls-Royce, was considered for GBE using alternative processing routes more suitable to the forging of Ni-base superalloy components. A preliminary study of the effects of hot deformation parameters closer to typical industrial processing revealed that the length fraction of Sigma3 boundaries increased from 35% to 52% following a single deformation/anneal cycle. Deformation parameters that resulted in strain accommodation via superplastic flow did not enhance the formation of Sigma3 boundaries upon annealing. Whereas deformation parameters that resulted in a dominant dislocation-based plasticity flow mechanism promoted the formation of annealing twins. Using misorientation maps and by estimating the stored strain energy from deformation, equations for the length fraction and density of Sigma3 boundaries were generated for high-temperature GBE of RR1000. The grain boundary characters obtained via high-temperature deformation, however, are less ideal than those resulting from traditional cold rolling. The underlying mechanisms responsible for the formation of Sigma3n boundaries during high-temperature GBE were further investigated. A larger starting grain size prior to deformation was found to be unfavorable to the

  17. Morphology and Crystallization of Thin Films of Asymmetric Organic-Organometallic Diblock Copolymers of Isoprene and Ferrocenyldimethylsilane

    NARCIS (Netherlands)

    Lammertink, Rob G.H.; Hempenius, Mark A.; Vancso, G. Julius

    2000-01-01

    The morphology of thin films of asymmetric block copolymers of poly(isoprene-block-ferrocenyldimethylsilane) was studied using atomic force microscopy, transmission electron microscopy, and optical microscopy. Block copolymers with the organometallic (ferrocenylsilane) phase between 20 and 28 vol %

  18. Convergent study of Ru-ligand interactions through QTAIM, ELF, NBO molecular descriptors and TDDFT analysis of organometallic dyes

    Science.gov (United States)

    Sánchez-Coronilla, Antonio; Sánchez-Márquez, Jesús; Zorrilla, David; Martín, Elisa I.; de los Santos, Desireé M.; Navas, Javier; Fernández-Lorenzo, Concha; Alcántara, Rodrigo; Martín-Calleja, Joaquín

    2014-08-01

    We report a theoretical study of a series of Ru complexes of interest in dye-sensitised solar cells, in organic light-emitting diodes, and in the war against cancer. Other metal centres, such as Cr, Co, Ni, Rh, Pd, and Pt, have been included for comparison purposes. The metal-ligand trends in organometallic chemistry for those compounds are shown synergistically by using three molecular descriptors: quantum theory of atoms in molecules (QTAIM), electron localisation function (ELF) and second-order perturbation theory analysis of the natural bond orbital (NBO). The metal-ligand bond order is addressed through both delocalisation index (DI) of QTAIM and fluctuation index (λ) of ELF. Correlation between DI and λ for Ru-N bond in those complexes is introduced for the first time. Electron transfer and stability was also assessed by the second-order perturbation theory analysis of the NBO. Electron transfer from the lone pair NBO of the ligands toward the antibonding lone pair NBO of the metal plays a relevant role in stabilising the complexes, providing useful insights into understanding the effect of the 'expanded ligand' principle in supramolecular chemistry. Finally, absorption wavelengths associated to the metal-to-ligand charge transfer transitions and the highest occupied molecular orbital (HOMO)--lowest unoccupied molecular orbital (LUMO) characteristics were studied by time-dependent density functional theory.

  19. Nanoscaled tin dioxide films processed from organotin-based hybrid materials: an organometallic route toward metal oxide gas sensors.

    Science.gov (United States)

    Renard, Laetitia; Babot, Odile; Saadaoui, Hassan; Fuess, Hartmut; Brötz, Joachim; Gurlo, Aleksander; Arveux, Emmanuel; Klein, Andreas; Toupance, Thierry

    2012-11-07

    Nanocrystalline tin dioxide (SnO(2)) ultra-thin films were obtained employing a straightforward solution-based route that involves the calcination of bridged polystannoxane films processed by the sol-gel process from bis(triprop-1-ynylstannyl)alkylene and -arylene precursors. These films have been thoroughly characterized by FTIR, contact angle measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force (AFM) and scanning electron (SEM) microscopies. Annealing at a high temperature gave 30-35 nm thick cassiterite SnO(2) films with a mean crystallite size ranging from 4 to 7 nm depending on the nature of the organic linker in the distannylated compound used as a precursor. In the presence of H(2) and CO gases, these layers led to highly sensitive, reversible and reproducible responses. The sensing properties were discussed in regard to the crystallinity and porosity of the sensing body that can be tuned by the nature of the precursor employed. Organometallic chemistry combined with the sol-gel process therefore offers new possibilities toward metal oxide nanostructures for the reproducible and sensitive detection of combustible and toxic gases.

  20. Expectation and surprise in group 13 organometallics: molecular vs. polymeric aggregation of Me2Ga and Me2In norcamphor oximates.

    Science.gov (United States)

    Ullrich, Matthias; Berger, Raphael J F; Pape, Tania; Mitzel, Norbert W

    2006-12-07

    Whereas (meso)-[(norcamphor oximato)GaMe2]2 exhibits the dimeric M2O2N2 motif favoured by organo group 13 metal oximates, the Me2In derivative [{(meso)-[(norcamphor oximato)InMe2]2}2]infinity aggregates distinctly different with the In atoms adopting coordination number (CN)=5; compound is the first oximato-based chain-like coordination polymer in group 13 organometallics; it comprises alternating M2O2N2 and M2O2 ring dimers interconnected via two types of a fifth dative bond (O-->In and N-->In) to yield the new {M4O4N4}infinity motif; the calculated energetics of the heteroatom rings involved in and confirm the diverging aggregational behaviour of Ga and In.

  1. Recent Progress on the Photonic Properties of Conjugated Organometallic Polymers Built Upon the trans-Bis(para-ethynylbenzene)bis(phosphine)platinum(II) Chromophore and Related Derivatives.

    Science.gov (United States)

    Wong, Wai-Yeung; Harvey, Pierre D

    2010-04-20

    This review article surveys the electronic and photophysical properties of conjugated organometallic polymers built upon the title compound and its related derivatives focussing primarily on systems investigated in our laboratories. The general structure of the polymers is (trans-bis(para-ethynylbenzene)bis(phosphine)platinum(II)-G)(n) where G is a conjugated group such as thiophene, fluorene, carbazole, substituted silole, quinone derivative, and metalloporphyrin residue, or a non-conjugated main-group moiety. Systems based on substituted phenylene units and other related fused rings are also discussed. The phosphine ligands are generally triethyl- or tri-n-butylphosphine groups. These trans-platinum(II) polymers and the corresponding model compounds are compared to the corresponding ortho-derivatives in the quinone series, and the newly prepared paracyclophane-containing polymers. For the porphyrin series, a comparison of fully conjugated oligomers exhibiting the general structure (trans-bis(para-ethynyl(zinc(porphyrin)))bis(phosphine)platinum(II))(n) (i.e., the C(6) H(4) group is absent from the main chain) will be made. This contribution also includes a description of the properties of the mononuclear chromophore itself, properties that define those of the polymers. Potential applications with regard to electronic and optical devices will be highlighted. These soluble and stable materials feature both the processing advantages of polymers and the functionality provided by the presence of metal centers. These multifunctional organometallic polyyne polymers exhibit convenient structural variability as well as optical and electronic properties, which renders them important for use in different research domains as chemical sensors and sensor protectors, as converters for light/electricity signals, and as patternable precursors to magnetic metal alloy nanoparticles.

  2. Creep deformation behaviour of Rhenium free Ni-based single crystal superalloys LSC-15

    Directory of Open Access Journals (Sweden)

    Tsuno Nobuyasu

    2014-01-01

    Full Text Available In this paper, creep deformation behavior of Ni-based single crystal superalloys LSC-15 were studied. LSC-15 does not include Rhenium and has been developed by IHI Corporation Japan. Creep tests were performed at 1000 and 1050 ∘C under several stress levels. The creep deformation behaviour was different between test temperatures at 1000 ∘C and 1050 ∘C. Moreover, the relationship between the minimum creep rate and stress was different at the various temperatures. The stress exponent values at 1000 ∘C and 1050 ∘C, were n = 6 and 12 respectively. This difference was due to differences in the formation of dislocation network. At 1000 ∘C, when the minimum creep rate, the dislocation network formed completely independent of stress level. On the other hand, at 1050 ∘C, the dislocation network had not developed fully at the minimum creep rate and the formation of dislocation network depended on the stress level. Therefore, stress dependency at 1050 ∘C is higher than that at 1000 ∘C.

  3. Thermomechanical behavior of different Ni-base superalloys during cyclic loading at elevated temperatures

    Directory of Open Access Journals (Sweden)

    Huber Daniel

    2014-01-01

    Full Text Available The material behavior of three Ni-base superalloys (Inconel® 718, Allvac® 718PlusTM and Haynes® 282® during in-phase cyclic mechanical and thermal loading was investigated. Stress controlled thermo-mechanical tests were carried out at temperatures above 700 ∘C and different levels of maximum compressive stress using a Gleeble® 3800 testing system. Microstructure investigations via light optical microscopy (LOM and field emission gun scanning electron microscopy (FEG-SEM as well as numerical precipitation kinetics simulations were performed to interpret the obtained results. For all alloys, the predominant deformation mechanism during deformation up to low plastic strains was identified as dislocation creep. The main softening mechanism causing progressive increase of plastic strain after preceding linear behavior is suggested to be recrystallization facilitated by coarsening of grain boundary precipitates. Furthermore, coarsening and partial transformation of strengthening phases was observed. At all stress levels, Haynes® 282® showed best performance which is attributable to its stable microstructure containing a high phase fraction of small, intermetallic precipitates inside grains and different carbides evenly distributed along grain boundaries.

  4. Control of Interfacial Reactivity Between ZrB2 and Ni-Based Brazing Alloys

    Science.gov (United States)

    Valenza, F.; Muolo, M. L.; Passerone, A.; Cacciamani, G.; Artini, C.

    2012-05-01

    Transition metals diborides (Ti,Zr,Hf)B2 play a key role in applications where stability at extremely high temperatures and damage tolerance are required; however, much research has still to be done to optimize the joining of these materials to themselves or to other high-temperature materials. In this study, the reactivity at the solid-liquid interface between ZrB2 ceramics and Ni-based brazing alloys has been addressed; it is shown how the reactivity and the dissolution of the solid phase can be controlled and even suppressed by adjusting the brazing alloy composition on the basis of thermodynamic calculations. Wetting experiments on ZrB2 ceramics by Ni, Ni-B 17 at.%, and Ni-B 50 at.% were performed at 1500 and 1200 °C by the sessile drop technique. The obtained interfaces were characterized by optical microscopy and SEM-EDS, and interpreted by means of the ad hoc-calculated B-Ni-Zr ternary diagram. A correlation among microstructures, substrate dissolution, shape of the drops, spreading kinetics, and the phase diagram was found. The effect on the interfacial reactivity of Si3Ni4 used as a sintering aid and issues related to Si diffusion into the brazing alloy are discussed as well.

  5. Unexpected δ-Phase Formation in Additive-Manufactured Ni-Based Superalloy

    Science.gov (United States)

    Idell, Y.; Levine, L. E.; Allen, A. J.; Zhang, F.; Campbell, C. E.; Olson, G. B.; Gong, J.; Snyder, D. R.; Deutchman, H. Z.

    2016-03-01

    An as-built and solutionized Ni-based superalloy built by additive manufacturing through a direct metal laser sintering technique is characterized to understand the microstructural differences as compared to the as-wrought alloy. Initially, each layer undergoes rapid solidification as it is melted by the laser; however, as the part is built, the underlying layers experience a variety of heating and cooling cycles that produce significant microsegregation of niobium which allows for the formation of the deleterious δ-phase. The as-built microstructure was characterized through Vickers hardness, optical microscopy, scanning and transmission electron microscopy, electron back-scattering diffraction, x-ray diffraction, and synchrotron x-ray microLaue diffraction. The isothermal formation and growth of the δ-phase were characterized using synchrotron-based in situ small angle and wide angle x-ray scattering experiments. These experimental results are compared with multicomponent diffusion simulations that predict the phase fraction and composition. The high residual stresses and unexpected formation of the δ-phase will require further annealing treatments to be designed so as to remove these deficiencies and obtain an optimized microstructure.

  6. Crystallization behavior of a melt-spun Fe-Ni based steel

    Science.gov (United States)

    Michal, G. M.; Laxmanan, V.; Glasgow, T. K.

    1987-01-01

    Whether Fe-Ni-based alloys solidify with a bcc or fcc structure has been observed by many investigators to be a stronger function of kinetics and undercooling than strictly free-energy minimization. Such behavior has been observed in an Fe(52.8)Ni(28.7)Al(3.4)Ti(6.1)B(9.0) alloy. The alloy was cast as ribbons about 45 microns thick using a dual free-jet variation of chillbock melt spinning against a Cu wheel. Optical, X-ray, and electron analyses of the as-cast and annealed ribbons were performed. A microstructure of at least four layers containing combinations of ecc, bcc, and amorphous phases in differing proportions was observed in the as-cast ribbon. The midthickness layer had the most unusual features, containing fcc grains about 75 nm in size encompassing spherulitic regions as large as 15 microns comprised of fcc grains about 25 nm in size. The crystallization sequence responsible for the as-cast microstructure is discussed in terms of the competition between the formation of bcc and fcc phases as influenced by undercooling, recalescence, and variations in cooling rate experienced by the as-cast ribbon.

  7. Control of equiaxed grains in a complicated Cu-Ni based alloy prepared by centrifugal casting

    Directory of Open Access Journals (Sweden)

    Luo Zongqiang

    2011-02-01

    Full Text Available A complicated Cu-Ni based alloy was developed to fabricate wear-resisting bush for high temperature application. The concern focuses on the control of equiaxed grains in the developed alloy ingot prepared by centrifugal casting. The results show that the equiaxed grains are determined by the pouring temperature of the melt, the cooling rate and the rotation speed of the mold. With the decrease in pouring temperature, the fraction of the equiaxed grains in the transverse section of the ingot increases and the average length of columnar grain decreases. When the pouring temperature is confined below 1,250℃, complete equiaxed grains can be obtained. Based on the optimal centrifugal casting processing, the tensile strength of the developed alloy ingot with complete equiaxed grains reaches to 810 MPa and 435 MPa at room temperature and 500℃, respectively, which is 14% and 110% higher than that of common commercial QAl10-4-4 alloy. The wear rate of the developed alloy is 7.0 × 10-8 and 3.8 × 10-7 mm3•N-1•mm-1 at room temperature and 500℃, respectively, which is 5 times and 39 times lower than that of QAl10-4-4 alloy.

  8. Directional Solidification Microstructure of a Ni-Based Superalloy: Influence of a Weak Transverse Magnetic Field

    Directory of Open Access Journals (Sweden)

    Xu Li

    2015-06-01

    Full Text Available A Ni-based superalloy CMSX-6 was directionally solidified at various drawing speeds (5–20 μm·s−1 and diameters (4 mm, 12 mm under a 0.5 T weak transverse magnetic field. The results show that the application of a weak transverse magnetic field significantly modified the solidification microstructure. It was found that if the drawing speed was lower than 10 μm·s−1, the magnetic field caused extensive macro-segregation in the mushy zone, and a change in the mushy zone length. The magnetic field significantly decreases the size of γ’ and the content of γ-γ’ eutectic. The formation of macro-segregation under a weak magnetic field was attributed to the interdendritic solute transport driven by the thermoelectric magnetic convection (TEMC. The γ’ phase refinement could be attributed to a decrease in nucleation activation energy owing to the magnetic field during solid phase transformation. The change of element segregation is responsible for the content decrease of γ-γ’ eutectic.

  9. Wear Characteristics of Ni-Based Hardfacing Alloy Deposited on Stainless Steel Substrate by Laser Cladding

    Science.gov (United States)

    Awasthi, Reena; Limaye, P. K.; Kumar, Santosh; Kushwaha, Ram P.; Viswanadham, C. S.; Srivastava, Dinesh; Soni, N. L.; Patel, R. J.; Dey, G. K.

    2015-03-01

    In this study, dry sliding wear characteristics of the Ni-based hardfacing alloy (Ni-Mo-Cr-Si) deposited on stainless steel SS316L substrate by laser cladding have been presented. Dry sliding wear behavior of the laser clad layer was evaluated against two different counter bodies, AISI 52100 chromium steel (~850 VHN) and tungsten carbide ball (~2200 VHN) to study both adhesive and abrasive wear characteristics, in comparison with the substrate SS316L using ball on plate reciprocating wear tester. The wear resistance was evaluated as a function of load and sliding speed for a constant sliding amplitude and sliding distance. The wear mechanisms were studied on the basis of wear surface morphology and microchemical analysis of the wear track using SEM-EDS. Laser clad layer of Ni-Mo-Cr-Si on SS316L exhibited much higher hardness (~700 VHN) than that of substrate SS316L (~200 VHN). The laser clad layer exhibited higher wear resistance as compared to SS316L substrate while sliding against both the counterparts. However, the improvement in the wear resistance of the clad layer as compared to the substrate was much higher while sliding against AISI 52100 chromium steel than that while sliding against WC, at the same contact stress intensity.

  10. Molecular dynamics study of mosaic structure in the Ni-based single-crystal superalloy

    Institute of Scientific and Technical Information of China (English)

    Zhu Tao; Wang Chong-Yu

    2006-01-01

    The mosaic structure in a Ni-based single-crystal superalloy is simulated by molecular dynamics using a potential employed in a modified analytic embedded atom method. From the calculated results we find that a closed three dimensional misfit dislocation network, with index of {100} and the side length of the mesh 89.6(A), is formed around a cuboidal γ' precipitate. Comparing the simulation results of the different mosaic models, we find that the side length of the mesh only depends on the lattice parameters of the γ and γ' phases as well as the γ/γ' interface direction, but is independent of the size and number of the cuboidal γ' precipitate. The density of dislocations is inversely proportional to the size of the cuboidal γ' precipitate, i.e. the amount of the dislocation is proportional to the total area of the γ/γ' interface, which may be used to explain the relation between the amount of the fine γ' particles and the creep rupture life of the superalloy. In addition, the closed three-dimensional networks assembled with the misfit dislocations can play a significant role in improving the mechanical properties of superalloys.

  11. Atom probe tomography of Ni-base superalloys Allvac 718Plus and Alloy 718.

    Science.gov (United States)

    Viskari, L; Stiller, K

    2011-05-01

    Atom probe tomography (APT) allows near atomic scale compositional- and morphological studies of, e.g. matrix, precipitates and interfaces in a wide range of materials. In this work two Ni-base superalloys with similar compositions, Alloy 718 and its derivative Allvac 718Plus, are subject for investigation with special emphasis on the latter alloy. The structural and chemical nuances of these alloys are important for their properties. Of special interest are grain boundaries as their structure and chemistry are important for the materials' ability to resist rapid environmentally induced crack propagation. APT has proved to be suitable for analyses of these types of alloys using voltage pulsed APT. However, for investigations of specimens containing grain boundaries and other interfaces the risk for early specimen fracture is high. Analyses using laser pulsing impose lower electrical field on the specimen thereby significantly increasing the success rate of investigations. Here, the effect of laser pulsing was studied and the derived appropriate acquisition parameters were then applied for microstructural studies, from which initial results are shown. Furthermore, the influence of the higher evaporation field experienced by the hardening γ' Ni(3)(Al,Nb) precipitates on the obtained results is discussed.

  12. Mechanisms of High Temperature/Low Stress Creep of Ni-Based Superalloy Single Crystals

    Energy Technology Data Exchange (ETDEWEB)

    Michael J. Mills

    2009-03-05

    Cast nickel-based superalloys are used for blades in land-based, energy conversion and powerplant applications, as well as in aircraft gas turbines operating at temperatures up to 1100 C, where creep is one of the life-limiting factors. Creep of superalloy single crystals has been extensively studied over the last several decades. Surprisingly, only recently has work focused specifically on the dislocation mechanisms that govern high temperature and low stress creep. Nevertheless, the perpetual goal of better engine efficiency demands that the creep mechanisms operative in this regime be fully understood in order to develop alloys and microstructures with improved high temperature capability. At present, the micro-mechanisms controlling creep before and after rafting (the microstructure evolution typical of high temperature creep) has occurred have yet to be identified and modeled, particularly for [001] oriented single crystals. This crystal orientation is most interesting technologically since it exhibits the highest creep strength. The major goal of the program entitled ''Mechanisms of High Temperature/Low Stress Creep of Ni-Based Superalloy Single Crystals'' (DOE Grant DE-FG02-04ER46137) has been to elucidate these creep mechanisms in cast nickel-based superalloys. We have utilized a combination of detailed microstructure and dislocation substructure analysis combined with the development of a novel phase-field model for microstructure evolution.

  13. Microstructure and abrasion wear behavior of Ni-based laser cladding alloy layer at high temperature

    Institute of Scientific and Technical Information of China (English)

    LIU Yong; LIU Su-qin; WANG Shun-xing

    2005-01-01

    Ni-based alloy coating on 21-4-N heat-resistant steel was prepared using CO2 laser, and the high-temperature abrasion wear was tested. The microstructure of this cladding layer and its abrasion wear behavior at high temperature by changing compositions and temperatures were investigated by means of optical microscope and scanning electron microscope. Among the three compositions of cladding layer, i.e. Ni21+20%WC+0.5%CeO2, Ni25+20%WC+0.5%CeO2 and Ni60+20%WC+0.5%CeO2, the experimental results show that Ni21+20%WC+0.5%CeO2 cladding layer is made up of finer grains, and presents the best abrasion wear behavior at high temperature. The wear pattern of laser cladding layer is mainly grain abrasion at lower temperature, and it would be changed to adhesive abrasion and oxide abrasion at higher temperature.

  14. Resistance to sulfur poisoning of Ni-based alloy with coinage (IB) metals

    Science.gov (United States)

    Xu, Xiaopei; Zhang, Yanxing; Yang, Zongxian

    2015-12-01

    The poisoning effects of S atom on the (1 0 0), (1 1 0) and (1 1 1) metal surfaces of pure Ni and Ni-based alloy with IB (coinage) metals (Cu, Ag, Au) are systematically studied. The effects of IB metal dopants on the S poisoning features are analyzed combining the density functional theory (DFT) results with thermodynamics data using the ab initio atomistic thermodynamic method. It is found that introducing IB doping metals into Ni surface can shift the d-band center downward from the Fermi level and weaken the adsorption of S on the (1 0 0) and (1 1 0) surfaces, and the S tolerance ability increases in the order of Ni, Cu/Ni, Ag/Ni and Au/Ni. Nevertheless, on the (1 1 1) surface, the S tolerance ability increases in the order of Ag/Ni (or Cu/Ni), Ni, and Au/Ni. When we increase the coverage of the IB metal dopants, we found that not only Au, but Cu and Ag can increase its S tolerance. We therefore propose that alloying can increase its S tolerance and alloying with Au would be a better way to increase the resistance to sulfur poisoning of the Ni anode as compared with the pure Ni and the Ag- or, Cu-doped Ni materials.

  15. Carbon Deposition Onto Ni-Based Catalysts for Combined Steam/CO2 Reforming of Methane.

    Science.gov (United States)

    Li, Peng; Park, Yoon Hwa; Moon, Dong Ju; Park, Nam Cook; Kim, Young Chul

    2016-02-01

    The present study was performed to suppress carbon deposition by Ce and Fe onto Ni-based catalysts in combined steam/CO2 reforming of methane (CSCRM), which is a process for producing synthesis gas (H2:CO = 2:1) for gas-to-liquids (GTL). The catalytic reaction was evaluated at 900 degrees C and 20 bar with a reactant feed ratio CH4:CO2:H20:Ar = 1:0.8:1.3:1 and gas hourly space velocity GHSV = 25,000 h(-1). The Ce and Fe modified Ni/gamma-A120, catalyst was characterized by BET surface area analysis, X-ray diffraction (XRD), H2 temperature-programmed reduction (TPR), H2 chemisorption, CO2 temperature-programmed desorption (TPD) and SEM. Ce- and Fe-modified Ni/Al2O3 catalysts exhibited remarkable activity and stability during the CSCRM over the course of 50 hours. It suggested that the Ni(12)-Ce(5)-Fe(5)/Al2O3 catalyst shows highly dispersed Ni particles with strong metal-to-support interaction (SMSI) as well as excellent catalytic activity.

  16. MICROMECHANICS OF THE DAMAGE-INDUCED CELLULAR MICROSTRUCTURE IN SINGLE CRYSTAL Ni-BASED SUPERALLOYS

    Institute of Scientific and Technical Information of China (English)

    M.Sakaguchi; M.Okazaki

    2004-01-01

    An analytical method to investigate the morphological evolution of the cellular microstructure is explored and proposed. The method is essentially based on the Eshelby's micromechanics theory, and it is extended so as to be applied for a material system containing inclusions with high volume fraction, by employing the average stress field approximation by Mori and Tanaka. The proposed method enables us to discuss a stable shape of precipitate in the material system, which must be influenced by many factors: e.g., volume fraction of precipitate; Young's modulus ratio and lattice misfit between matrix and precipitate; external stress field in multiaxial state; and heterogeneity of plastic strain between matrix and precipitate. A series of numerical calculations were summarized on stable shape maps. The application of the method to predict the γ' rafting in superalloys during creep showed that the heterogeneity of plastic strain between matrix and precipitates may play a significant role in the shape stability of the precipitate. Furthermore, it was shown that the method was successfully applied to estimate the morphology of the cellular microstructure formed in CMSX-4single crystal Ni-based superalloy.

  17. Burner Rig Hot Corrosion of Five Ni-Base Alloys Including Mar-M247

    Science.gov (United States)

    Nesbitt, James A.; Helmink, R.; Harris, K.; Erickson, G.

    2000-01-01

    The hot corrosion resistance of four new Ni-base superalloys was compared to that of Mar-M247 by testing in a Mach 0.3 burner rig at 900 C for 300 1-hr cycles. While the Al content was held the same as in the Mar-M247, the Cr and Co levels in the four new alloys were decreased while other strengthening elements (Re, Ta) were increased. Surprisingly, despite their lower Cr and Co contents, the hot corrosion behavior of all four new alloys was superior to that of the Mar-M247 alloy. The Mar-M247 alloy began to lose weight almost immediately whereas the other four alloys appeared to undergo an incubation period of 50-150 1-hr cycles. Examination of the cross-sectional microstructures showed regions of rampant corrosion attack (propagation stage) in all five alloys after 300 1-hr cycles . This rampant corrosion morphology was similar for each of the alloys with Ni and Cr sulfides located in an inner subscale region. The morphology of the attack suggests a classic "Type I", or high temperature, hot corrosion attack.

  18. Lanthanide alkyl and silyl compounds: Synthesis, reactivity and catalysts for green

    Energy Technology Data Exchange (ETDEWEB)

    Pindwal, Aradhana [Iowa State Univ., Ames, IA (United States)

    2016-01-01

    The last few decades have witnessed enormous research in the field of organometallic lanthanide chemistry. Our research group has developed a few rare earth alkyl compounds containing tris(dimethylsilyl)methyl ligand and explored their reactivity. This thesis focusses on extending the study of lanthanide alkyl and silyl compounds to develop strategies for their synthesis and explore their reactivity and role as catalysts in processes such as hydrosilylation and cross-dehydrocoupling.

  19. Aromatic Methoxylation and Hydroxylation by Organometallic High-Valent Nickel Complexes.

    Science.gov (United States)

    Zhou, Wen; Schultz, Jason W; Rath, Nigam P; Mirica, Liviu M

    2015-06-24

    Herein we report the synthesis and reactivity of several organometallic Ni(III) complexes stabilized by a modified tetradentate pyridinophane ligand containing one phenyl group. A room temperature stable dicationic Ni(III)-disolvento complex was also isolated, and the presence of two available cis coordination sites in this complex offers an opportunity to probe the C-heteroatom bond formation reactivity of high-valent Ni centers. Interestingly, the Ni(III)-dihydroxide and Ni(III)-dimethoxide species can be synthesized, and they undergo aryl methoxylation and hydroxylation that is favored by addition of oxidant, which also limits the β-hydride elimination side reaction. Overall, these results provide strong evidence for the involvement of high-valent organometallic Ni species, possibly both Ni(III) and Ni(IV) species, in oxidatively induced C-heteroatom bond formation reactions.

  20. Energy and chemicals from the selective electrooxidation of renewable diols by organometallic fuel cells.

    Science.gov (United States)

    Bellini, Marco; Bevilacqua, Manuela; Filippi, Jonathan; Lavacchi, Alessandro; Marchionni, Andrea; Miller, Hamish A; Oberhauser, Werner; Vizza, Francesco; Annen, Samuel P; Grützmacher, H

    2014-09-01

    Organometallic fuel cells catalyze the selective electrooxidation of renewable diols, simultaneously providing high power densities and chemicals of industrial importance. It is shown that the unique organometallic complex [Rh(OTf)(trop2NH)(PPh3)] employed as molecular active site in an anode of an OMFC selectively oxidizes a number of renewable diols, such as ethylene glycol , 1,2-propanediol (1,2-P), 1,3-propanediol (1,3-P), and 1,4-butanediol (1,4-B) to their corresponding mono-carboxylates. The electrochemical performance of this molecular catalyst is discussed, with the aim to achieve cogeneration of electricity and valuable chemicals in a highly selective electrooxidation from diol precursors.

  1. Modular construction of a porous organometallic network based on rhodium olefin complexation.

    Science.gov (United States)

    Stoeck, Ulrich; Nickerl, Georg; Burkhardt, Ulrich; Senkovska, Irena; Kaskel, Stefan

    2012-10-24

    We describe the rational design and synthesis of the first member of a new class of microporous materials. It is built from rhodium and a polyolefinic ligand featuring a rigid tetraphenylsilane backbone via metal olefin complexation, creating a truly organometallic network. The resulting framework, denoted as DUT-37 (Dresden University of Technology no. 37) exhibits considerable porosity and unprecedented stability under ambient conditions. Furthermore, it is catalytically active in transfer hydrogenation.

  2. New Concept of C–H and C–C Bond Activation via Surface Organometallic Chemistry

    KAUST Repository

    Samantaray, Manoja

    2015-08-18

    In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI transition metals in the field of C–H and C–C bond activation. The activation of ubiquitous C–H and C–C bonds of paraffin is a long-standing challenge because of intrinsic low reactivity. There are many concepts derived from surface organometallic chemistry (SOMC): surface organometallic fragments are always intermediates in heterogeneous catalysis. The study of their synthesis and reactivity is a way to rationalize mechanism of heterogeneous catalysis and to achieve structure activity relationship. By surface organometallic chemistry one can enter any catalytic center by a reaction intermediate leading in fine to single site catalysts. With surface organometallic chemistry one can coordinate to the metal which can play a role in different elementary steps leading for example to C–H activation and Olefin metathesis. Because of the development of SOMC there is a lot of space for the improvement of homogeneous catalysis. After the 1997 discovery of alkane metathesis using silica-supported tantalum hydride by Basset et al. at low temperature (150ºC) the focus in this area was shifted to the discovery of more and more challenging surface complexes active in the application of C–H and C–C bond activation. Here we describe the evolution of well-defined metathesis catalyst with time as well as the effect of support on catalysis. We also describe here which metal–ligand combinations are responsible for a variety of C–H and C–C bond activation.

  3. Organometallic NLO Polymers. Accordian Main-Chain NLO Polymers of Ferrocene

    Science.gov (United States)

    1991-12-13

    suggest that the reaction conditions required to carry out the Lewis acid catalyzed transesterification polycondensation are having deleterious effects on...organometallic main-chain NLO polymers. Our research 1"n -U has continued to f--cus on ferrocene based NLO polymers . MFP because of the outstanding results...under rt-ad pressure. The crude product wargood functional group tolerance because of the mild base (i.e. dissolved in chloroform and precipitated in

  4. Organometallic electrodes: modification of electrode surfaces through cathodic reduction of cyclopentadienyldiazonium complexes of cobalt and manganese.

    Science.gov (United States)

    Laws, Derek R; Sheats, John; Rheingold, Arnold L; Geiger, William E

    2010-09-21

    Two organometallic complexes having cyclopentadienyldiazonium ligands have been isolated and characterized by spectroscopy, X-ray crystallography, and electrochemistry. Both CoCp(η(5)-C(5)H(4)N(2))(2+) (2(2+)) and Mn(CO)(3)(η(5)-C(5)H(4)N(2))(+) (3(+)) undergo facile cyclopentadienyldiazonium ligand-based one-electron reductions which liberate dinitrogen and result in strong binding of the cyclopentadienyl ligand to a glassy carbon surface, similar to the processes well established for organic aryldiazonium salts. The organometallic-modified electrodes are robust and have a thickness of approximately one monolayer (Γ = (2-4) × 10(-10) mol cm(-2)). Their voltammetric responses are as expected for a cobaltocenium-modified electrode, [CoCp(η(5)-C(5)H(4)-E)](+), where Cp = cyclopentadienyl and E = electrode, and a "cymantrene"-modified electrode Mn(CO)(3)(η(5)-C(5)H(4)-E). The cobaltocenium electrode has two cathodic surface waves. The first (E(1/2) = -1.34 V vs ferrocene) is highly reversible, whereas the second (E(pc) = -2.4 V) is not, consistent with the known behavior of cobaltocenium. The cymantrene-substituted electrode has a partially chemically reversible anodic wave at E(1/2) = 0.96 V, also consistent with the behavior of its Mn(CO)(3)Cp parent. Many of the properties of aryl-modified electrodes, such as "blockage" of the voltammetric responses of test analytes, are also seen for the organometallic-modified electrodes. Surface-based substitution of a carbonyl group by a phosphite ligand, P(OR)(3), R = Ph or Me, was observed when the cymantrene-modified electrode was anodically oxidized in the presence of a phosphite ligand. The successful grafting of organometallic moieties by direct bonding of a cyclopentadienyl ligand to electrode surfaces expands the chemical and electrochemical dimensions of diazonium-based modified electrodes.

  5. Synthesis of 3,4-disubstituted maleimides by selective cross-coupling reactions using indium organometallics.

    Science.gov (United States)

    Bouissane, Latifa; Pérez Sestelo, José; Sarandeses, Luis A

    2009-03-19

    Unsymmetrical 3,4-disubstituted maleimides have been synthesized by palladium-catalyzed cross-coupling reactions of indium organometallics with 3,4-dihalomaleimides. The synthesis was performed by stepwise or sequential one-pot palladium-catalyzed cross-coupling reactions with various triorganoindium reagents. This method was used to prepare a wide variety of alkyl, aryl, heteroaryl, and alkynyl 3,4-disubstituted maleimides in good yields and with high selectivity and atom economy.

  6. Enhancement of Selectivity of an Organometallic Anticancer Agent by Redox Modulation.

    Science.gov (United States)

    Romero-Canelón, Isolda; Mos, Magdalena; Sadler, Peter J

    2015-10-08

    Combination with redox modulators can potentiate the anticancer activity and maximize the selectivity of organometallic complexes with redox-based mechanisms of action. We show that nontoxic doses of l-buthionine sulfoximine increase the selectivity of organo-Os complex FY26 for human ovarian cancer cells versus normal lung fibroblasts to 63-fold. This increase is not due to changes in the mechanism of action of FY26 but to the decreased response of cancer cells to oxidative stress.

  7. Organometallic halide perovskite single crystals having low deffect density and methods of preparation thereof

    KAUST Repository

    Bakr, Osman M.

    2016-02-18

    The present disclosure presents a method of making a single crystal organometallic halide perovskites, with the formula: AMX3, wherein A is an organic cation, M is selected from the group consisting of: Pb, Sn, Cu, Ni, Co, Fe, Mn, Pd, Cd, Ge, and Eu, and X is a halide. The method comprises the use of two reservoirs containing different precursors and allowing the vapor diffusion from one reservoir to the other one. A solar cell comprising said crystal is also disclosed.

  8. Automated detection and characterization of microstructural features: application to eutectic particles in single crystal Ni-based superalloys

    Science.gov (United States)

    Tschopp, M. A.; Groeber, M. A.; Fahringer, R.; Simmons, J. P.; Rosenberger, A. H.; Woodward, C.

    2010-03-01

    Serial sectioning methods continue to produce an abundant amount of image data for quantifying the three-dimensional nature of material microstructures. Here, we discuss a methodology to automate detecting and characterizing eutectic particles taken from serial images of a production turbine blade made of a heat-treated single crystal Ni-based superalloy (PWA 1484). This method includes two important steps for unassisted eutectic particle characterization: automatically identifying a seed point within each particle and segmenting the particle using a region growing algorithm with an automated stop point. Once detected, the segmented eutectic particles are used to calculate microstructural statistics for characterizing and reconstructing statistically representative synthetic microstructures for single crystal Ni-based superalloys. The significance of this work is its ability to automate characterization for analysing the 3D nature of eutectic particles.

  9. Microstructure and wear behavior of laser cladding Ni-based alloy composite coating reinforced by Ti(C,N) particulates

    Institute of Scientific and Technical Information of China (English)

    Qi Yongtian; Shi Hanchao; Zou Zengda; Hu Liping

    2008-01-01

    In this paper, Ni-based alloy composite coating reinforced by Ti (C,N) particles was fabricated on the mild steel through laser cladding technology. The microstructure of laser cladding layer was analyzed by means of optical microscopy (OM),X-ray diffraction (XRD) and scanning electron microscopy (SEM).The wear resistance test of the coating was evaluated using an M-2000 tester. The results showed that the Ni-based composite coating had an ability of rapid solidification to form dendritic crystals microstructure consisting of Ti (C,N) particulates uniformly distributed in the matrix. It was found that some Ti(C,N) particles are similar to be round in shape, and the others are irregular. Laser cladding layer reinforced by Ti(C,N) particulates was found to possess good wear resistance property.

  10. The halogen effect for Ni-base alloys - A new method for increasing the oxidation protection at high temperatures

    Science.gov (United States)

    Zschau, Hans-Eberhard; Renusch, Daniel; Masset, Patrick J.; Schütze, Michael

    2009-05-01

    A new method for oxidation protection of Ni-base alloys is presented. The method is based on the halogen effect. Thermodynamic calculations show the preferred formation of gaseous Al-halogenides within a certain region of fluorine partial pressures. Ion implantation has been chosen for fluorine treatment. The implantation parameters are defined by using the T-DYN simulation software. Based on these results fluorine implantations of the Ni-base alloy IN 738 are performed to meet the required fluorine content near the surface. The fluorine depth profiles are analyzed by using the PIGE-technique. After oxidation at 1050 °C a dense protecting external alumina scale is formed on the surface.

  11. 2011 Organometallic Chemistry (July 10-15, 2011, Salve Regina University, Newport, RI)

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Emilio Bunel

    2011-07-15

    Organometallic chemistry has played and will continue to play a significant role in helping us understand the way bonds are made or broken in the presence of a transition metal complex. Current challenges range from the efficient exploitation of energy resources to the creative use of natural and artificial enzymes. Most of the new advances in the area are due to our extended understanding of processes at a molecular level due to new mechanistic studies, techniques to detect reaction intermediates and theory. The conference will bring the most recent advances in the field including nanocatalysis, surface organometallic chemistry, characterization techniques, new chemical reactivity and theoretical approaches along with applications to organic synthesis and the discovery of new materials. The Conference will bring together a collection of investigators who are at the forefront of their field, and will provide opportunities for junior scientists and graduate students to present their work in poster format and exchange ideas with leaders in the field. Six outstanding posters will be selected for short talks. The collegial atmosphere of this Conference, with programmed discussion sessions as well as opportunities for informal gatherings in the afternoons and evenings, provides an avenue for scientists from different disciplines to brainstorm and promotes cross-disciplinary collaborations in the various research areas represented. Graduate students and postdoctoral fellows should also consider participating in the Gordon Research Seminar on Organometallic Chemistry (July 9-10, same location) which is specially designed to promote interaction and discussion between junior scientists.

  12. Organometallic copper I, II or III species in an intramolecular dechlorination reaction

    KAUST Repository

    Poater, Albert

    2013-03-15

    The present paper gives insight into an intramolecular dechlorination reaction involving Copper (I) and an ArCH2Cl moiety. The discussion of the presence of a CuIII organometallic intermediate becomes a challenge, and because of the lack of clear experimental detection of this proposed intermediate, and due to the computational evidence that it is less stable than other isomeric species, it can be ruled out for the complex studied here. Our calculations are completely consistent with the key hypothesis of Karlin et al. that TMPA-CuI is the substrate of intramolecular dechlorination reactions as well as the source to generate organometallic species. However the organometallic character of some intermediates has been refused because computationally these species are less stable than other isomers. Thus this study constitutes an additional piece towards the full understanding of a class of reaction of biological relevance. Further, the lack of high energy barriers and deep energy wells along the reaction pathway explains the experimental difficulties to trap other intermediates. © Springer-Verlag Berlin Heidelberg 2013.

  13. Investigation of organometallic reaction mechanisms with one and two dimensional vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cahoon, James Francis [Univ. of California, Berkeley, CA (United States)

    2008-12-01

    One and two dimensional time-resolved vibrational spectroscopy has been used to investigate the elementary reactions of several prototypical organometallic complexes in room temperature solution. The electron transfer and ligand substitution reactions of photogenerated 17-electron organometallic radicals CpW(CO)3 and CpFe(CO)2 have been examined with one dimensional spectroscopy on the picosecond through microsecond time-scales, revealing the importance of caging effects and odd-electron intermediates in these reactions. Similarly, an investigation of the photophysics of the simple Fischer carbene complex Cr(CO)5[CMe(OMe)] showed that this class of molecule undergoes an unusual molecular rearrangement on the picosecond time-scale, briefly forming a metal-ketene complex. Although time-resolved spectroscopy has long been used for these types of photoinitiated reactions, the advent of two dimensional vibrational spectroscopy (2D-IR) opens the possibility to examine the ultrafast dynamics of molecules under thermal equilibrium conditions. Using this method, the picosecond fluxional rearrangements of the model metal carbonyl Fe(CO)5 have been examined, revealing the mechanism, time-scale, and transition state of the fluxional reaction. The success of this experiment demonstrates that 2D-IR is a powerful technique to examine the thermally-driven, ultrafast rearrangements of organometallic molecules in solution.

  14. Atomic layer epitaxy of 3-5 compounds

    Science.gov (United States)

    Dapkus, P. D.; Wittig, C.; Allen, S.

    1986-08-01

    This program is intended to develop a process for the growth of GaAs and related compounds by Atomic Layer Epitaxy (ALE). The program involves fundamental studies of gas phase kinetics of the organometallic and hydrides to be used in the process as well as surface reaction studies to determine the surface of various organometallics. We have chosen in this program to effect ALE growth in a dense H2 atmosphere. We believe that the reactivity of H2 is important to the removal, by hydrogenation, of the alkyl radicals from the growing surface. To better understand the process we are pursuing fundamental information in two areas. First, basic measurements of the reactivity band reaction products of organometallics and hydrides and of photogenerated species with compound semiconductor surfaces are being undertaken that will determine the feasibility of using photoactivation and in thermal catalytic reactions in the gas phase to accomplish ALE. Second, epitaxial growth experiments are being performed to determine the feasibility of an ALE process employing photodecomposition of surface absorbed species as well as thermal catalytic reactions.

  15. The use of TiNi-based endografts in larynx cancer patients

    Directory of Open Access Journals (Sweden)

    Kulbakin Denis

    2015-12-01

    mobile organ when swallowing, speaking etc. Secondly, there are no commercially produced endografts for wide clinical practice. Thirdly, there are high demands regarding the material selection for the replacement. This study aimed to present the new technique of sparing surgery in patients with laryngeal cancer.Methods: Totally 120 patients with laryngeal cancer were observed with stage grouping T2-3N0-1M0 (Т1N0M0 – 14, Т2N0M0 – 40, T3N0M0 – 58, T2N1M0 – 8. Most of them (118, 98.3% were males where patients’ age ranged from 32 to 70 years (Tab. 1. The maximum number of patients (78% was in 40–60 years group. Not all of those in the laryngeal cancer group were newly diagnosed and they received previous treatment. Informed consent was obtained from each patient. The subsites of laryngeal cancer were the glottis in 17 cases, the supraglottic-glottis in 45 cases and the transglottic in 58 cases.The intervention depended on the location and extent of the tumor process. Standard volume of resection, extended resection, combined resection, subtotal resection were basic types of surgery. Most of laryngeal resections were front-lateral (117, 98% and there were only three (2% subtotal ones. Surgeries on the primary focus were combined with cervical lymph node dissection in eight patients (6.6%. The essence of the resection is to remove larynx structures which are affected by neoplastic process as a single unit including mucosa, submucosa layer, muscles, thyroid cartilage with the inner perichondrium into the volume of cut out tissue.Both the creation of laryngeal frame using the endograft made of superelastic TiNi-based alloy mesh and the providing of the inner lining of the recovered larynx is the basis of sparing technique regarding the larynx prosthetics.Producing of original design endograft made of superelastic TiNi-based alloy mesh was performed individually for each patient using the data acquired by helical CT of the larynx, laryngoscopy and volume of

  16. In-situ Raman spectroscopic analysis of interfaces of Ni-base alloy/LAS dissimilar metal weld

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jong Jin; Shin, Sang Hoon; Jung, Ju Ang; Choi, Kyoung Joon; Kim, Ji Hyun [Ulsan National Institute of Science and Technology, Ulsan (Korea, Republic of)

    2012-05-15

    Aging of structural materials in pressurized water reactors (PWRs) has been one of the major issues for plant safety and life extension. While a new alloy (Alloy 690) introduced, some concerns remain unresolved especially deterioration of a dissimilar metal weld. Intergranular stress corrosion cracking (IGSCC) is one of major degradation modes of aging problems that occur in structural materials for steam generators or nozzles in PWRs. The IGSCC of Ni-base alloys in PWR primary water has been extensively studied to establish theoretical and empirical models for predicting the crack initiation in field components. Even though there is no general agreement on the origin of IGSCC, one common assumption of these approaches is that the damage to the alloy substrate can be related to some transport or repair properties of its protective oxide film. Therefore, the oxide film is believed to play a key role in the process of IGSCC on the surface of the Ni-base alloys in the primary water. This study is aimed to characterize the oxide film by in-situ method in order to investigate the effects of aging on the degradation of Ni-base alloy/low alloy steel dissimilar metal weld(DMW). Since the SCC of structural alloys is related to the property of native oxide layers, surface oxides on the aged weld specimens need to be characterized. It is essential to overcome the current limitation of typical ex-situ methods. In this study, therefore, a hydrothermal cell for the in-situ surface oxide analysis using Raman spectroscopy were designed and assembled. It is mainly composed of a water loop for simulated PWR primary water condition, in-situ Raman spectroscopy system, and hydrothermal optical cell for oxide analysis. Using the developed experimental system, the interface region of Ni-base alloy/low alloy steel dissimilar metal weld will be analyzed by acquiring Raman spectrum from DMW specimens exposed to high temperature and high pressure water condition

  17. Magnetic Properties of FeNi-Based Thin Film Materials with Different Additives

    Directory of Open Access Journals (Sweden)

    Cai Liang

    2014-07-01

    Full Text Available This paper presents a study of FeNi-based thin film materials deposited with Mo, Al and B using a co-sputtering process. The existence of soft magnetic properties in combination with strong magneto-mechanical coupling makes these materials attractive for sensor applications. Our findings show that FeNi deposited with Mo or Al yields magnetically soft materials and that depositing with B further increases the softness. The out-of-plane magnetic anisotropy of FeNi thin films is reduced by depositing with Al and completely removed by depositing with B. The effect of depositing with Mo is dependent on the Mo concentration. The coercivity of FeNiMo and FeNiAl is reduced to less than a half of that of FeNi, and a value as low as 40 A/m is obtained for FeNiB. The surfaces of the obtained FeNiMo, FeNiAl and FeNiB thin films reveal very different morphologies. The surface of FeNiMo shows nano-cracks, while the FeNiAl films show large clusters and fewer nano-cracks. When FeNi is deposited with B, a very smooth morphology is obtained. The crystal structure of FeNiMo strongly depends on the depositant concentration and changes into an amorphous structure at a higher Mo level. FeNiAl thin films remain polycrystalline, even at a very high concentration of Al, and FeNiB films are amorphous, even at a very low concentration of B.

  18. Magnetic properties of FeNi-based thin film materials with different additives

    KAUST Repository

    Liang, C.

    2014-07-04

    This paper presents a study of FeNi-based thin film materials deposited with Mo, Al and B using a co-sputtering process. The existence of soft magnetic properties in combination with strong magneto-mechanical coupling makes these materials attractive for sensor applications. Our findings show that FeNi deposited with Mo or Al yields magnetically soft materials and that depositing with B further increases the softness. The out-of-plane magnetic anisotropy of FeNi thin films is reduced by depositing with Al and completely removed by depositing with B. The effect of depositing with Mo is dependent on the Mo concentration. The coercivity of FeNiMo and FeNiAl is reduced to less than a half of that of FeNi, and a value as low as 40 A/m is obtained for FeNiB. The surfaces of the obtained FeNiMo, FeNiAl and FeNiB thin films reveal very different morphologies. The surface of FeNiMo shows nano-cracks, while the FeNiAl films show large clusters and fewer nano-cracks. When FeNi is deposited with B, a very smooth morphology is obtained. The crystal structure of FeNiMo strongly depends on the depositant concentration and changes into an amorphous structure at a higher Mo level. FeNiAl thin films remain polycrystalline, even at a very high concentration of Al, and FeNiB films are amorphous, even at a very low concentration of B. 2014 by the authors.

  19. Ni-based Ni-Fe-B-Si-Ta bulk metallic glasses

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The glass-forming ability and properties of Ni-based Ni-Fe-B-Si-Ta bulk metallic glasses are explored in this work. The alloy compositions are determined by using a combination of the cluster line approach, the multi-alloying strategy and the substitutions of similar elements. Bulk metallic glasses with diameters of 3 mm take shape at compositions formulated under the clus- ter-plus-glue-atom model [M9B]B~[(Ni1-xFex)7.71(Si0.66Ta0.34)1.29B]B0.94=(Ni1-xFex)70.5B17.7Si7.8Ta4, x=0.35–0.45, where the bracketed part is the cluster and the unbracketed part is the glue atoms. These alloys exhibit good magnetic properties. The maximum Is is found in the (Ni0.55Fe0.45)70.5B17.7Si7.8Ta4 alloy which reaches 0.51 T, with its Hc as low as 8.5 A/m. Interestingly, these alloys display dual glass transitions at (Ni0.65Fe0.35)70.5B17.7Si7.8Ta4, (Ni0.60Fe0.4)70.5B17.7Si7.8Ta4 and (Ni0.55Fe0.45)70.5B17.7- Si7.8Ta4 as unveiled by Temperature-Modulated Differential Scanning Calorimetry.

  20. Corrosion behavior of Ni-based structural materials for electrolytic reduction in lithium molten salt

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Soo Haeng, E-mail: nshcho1@kaeri.re.kr [Korea Atomic Energy Research Institute, 1045 Daedeokdaero Yuseong-gu, Daejeon 305-353 (Korea, Republic of); Park, Sung Bin [Korea Atomic Energy Research Institute, 1045 Daedeokdaero Yuseong-gu, Daejeon 305-353 (Korea, Republic of); Lee, Jong Hyeon, E-mail: jonglee@cnu.ac.kr [Graduate School of Green Energy Technology, Chungnam National University, 79 Daehak-ro, Yuseong-gu, Daejeon 305-764 (Korea, Republic of); Hur, Jin Mok; Lee, Han Soo [Korea Atomic Energy Research Institute, 1045 Daedeokdaero Yuseong-gu, Daejeon 305-353 (Korea, Republic of)

    2011-05-01

    In this study, the corrosion behavior of new Ni-based structural materials was studied for electrolytic reduction after exposure to LiCl-Li{sub 2}O molten salt at 650 deg. C for 24-216 h under an oxidizing atmosphere. The new alloys with Ni, Cr, Al, Si, and Nb as the major components were melted at 1700 deg. C under an inert atmosphere. The melt was poured into a preheated metallic mold to prepare an as-cast alloy. The corrosion products and fine structures of the corroded specimens were characterized by scanning electron microscope (SEM), Energy Dispersive X-ray Spectroscope (EDS), and X-ray diffraction (XRD). The corrosion products of as cast and heat treated low Si/high Ti alloys were Cr{sub 2}O{sub 3}, NiCr{sub 2}O{sub 4}, Ni, NiO, and (Al,Nb,Ti)O{sub 2}; those of as cast and heat treated high Si/low Ti alloys were Cr{sub 2}O{sub 3}, NiCr{sub 2}O{sub 4}, Ni, and NiO. The corrosion layers of as cast and heat treated low Si/high Ti alloys were continuous and dense. However, those of as cast and heat treated high Si/low Ti alloys were discontinuous and cracked. Heat treated low Si/high Ti alloy showed the highest corrosion resistance among the examined alloys. The superior corrosion resistance of the heat treated low Si/high Ti alloy was attributed to the addition of an appropriate amount of Si, and the metallurgical evaluations were performed systematically.

  1. Dry friction aspects of Ni-based self-fluxing flame sprayed coatings

    Science.gov (United States)

    Paulin, C.; Chicet, D.; Paleu, V.; Benchea, M.; Lupescu, Ş.; Munteanu, C.

    2017-08-01

    In this paper we present the results tribological obtained in the course of dry wear tests on samples coated with three types of coatings produced from self-fluxing Ni-based powders. In this purpose were used three commercial NiCrBSi powders produced by various manufacturers, which have been sprayed against a low alloyed steel substrate using the flame spray thermal deposition method followed by flame remelting, resulting three different samples, denoted as: A, M and P. The first test was conducted on an Amsler type machine, with rolling motion between tribological contacts of third class. The analysed coating was deposited on the generator of the low alloy steel disc and the shoe was realized from a grindstone. The test was conducted for two situations: (a) constant load of 10 kg and 6 kg applied for 5 hours; (b) progressive load starting from 2 to 10 kg for two different speeds of rotation of the disc. The second test was the one of sliding wear and it was conducted on the UMTR 2M-CTR tribometer. The analysed layers were deposited on the flat surface of a low alloy steel lamella, and the friction was achieved with a conical grinding stone. The working parameters were as follows: 20N constant load, constant speed of 10 mm / s, sliding linear length of 30mm, the test duration being 45 minutes. After conducting the tests and after analysing the results, the following conclusions are drawn: a) during the first test has been obtained a global friction coefficient between 0.3 and 0.4 - typical for dry friction, highlighting some lower values in the case of sample A, in which case there were recorded smaller mass losses; b) at the second test was recorded an approximately linear behaviour of the three samples, with a gradual increase of the friction coefficient and a superficial wear mark revealed both by SEM microscopy and by profilometry.

  2. Microstructure and He desorption behaviors of He charged FeCrNi-based films fabricated by direct current magnetron sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Song, L. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P.O. Box 1129, Hefei 230031 (China); Wang, X.P., E-mail: xpwang@issp.ac.cn [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P.O. Box 1129, Hefei 230031 (China); Liu, F. [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei 230031 (China); Gao, Y.X. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P.O. Box 1129, Hefei 230031 (China); Zhang, T., E-mail: zhangtao@issp.ac.cn [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P.O. Box 1129, Hefei 230031 (China); Luo, G.N. [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei 230031 (China); Fang, Q.F.; Liu, C.S. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P.O. Box 1129, Hefei 230031 (China)

    2015-08-31

    He-charged FeCrNi-based films were prepared at different temperatures in a mixed atmosphere of He and Ar by direct-current magnetron sputtering method. X-ray diffraction and energy dispersive spectrometry analysis confirmed the typical austenitic structure of the deposited FeCrNi films and the compositions were in good accordance with 304 stainless steel target. Cross-sectional scanning electron microscopy images revealed the dense columnar nanocrystalline structure of the fabricated FeCrNi films. Nanoindentation measurements showed that the film fabricated at 300 °C exhibited the highest hardness value of 11.5 GPa. He desorption from FeCrNi-based films was traced by thermal desorption spectroscopy; the relatively low He desorption temperature range (150 °C–450 °C) implied that the charged He atoms were mainly located in interstitial sites of FeCrNi-based films. - Highlights: • He-charged columnar nanocrystalline FeCrNi films were prepared by DC magnetron sputtering. • Substrate temperature of 300 °C and He/Ar ratio 1:1 were the best sputtering parameters. • Compact and uniform microstructure obtained at 300 °C resulted in stable, high hardness. • Two He atoms' absorption/desorption mechanisms were revealed by TDS.

  3. Electrochemical performance and capacity degradation mechanism of single-phase La-Mg-Ni-based hydrogen storage alloys

    Science.gov (United States)

    Liu, Jingjing; Li, Yuan; Han, Da; Yang, Shuqin; Chen, Xiaocui; Zhang, Lu; Han, Shumin

    2015-12-01

    La-Mg-Ni-based hydrogen storage alloys are a promising candidate for the negative electrode materials of nickel metal hydride batteries. However, their fast capacity degradation hinders them from more extensive application. In this study, the electrochemical performance and capacity degradation mechanism of single-phase La2MgNi9, La3MgNi14 and La4MgNi19 alloys are studied from the perspective of their constituent subunits. It is found that the rate capability and cycling stability of the alloy electrodes increase with higher [LaNi5]/[LaMgNi4] subunit ratio, while the discharge capacity shows a reverse trend. Degradation study shows that the inter-molecular strains in the alloys are the main reason that leads to the fast capacity degradation of La-Mg-Ni-based alloys. The strains are caused by the difference in the expansion/contraction properties between [LaNi5] and [LaMgNi4] subunits during charge/discharge which is mainly observed in the H-dissolved solid solution instead of hydride. It is also found that the strains can be relieved by adjusting [LaNi5]/[LaMgNi4] subunit ratio of the alloys, thus achieving less pulverization and oxidation, and better cycling stability. We expect our findings can inspire new thoughts on improving the electrochemical performance of La-Mg-Ni-based alloys by tuning their superlattice structures.

  4. Effect of La2O3 Addition on Microstructure and Wear Behavior of Electrospark Deposited Ni-BASED Coatings

    Science.gov (United States)

    Yuxin, Gao; Jian, Yi

    2013-12-01

    La2O3 doped Ni-based coatings have been prepared by electrospark deposition technique. The effect of La2O3 on the microstructure, hardness and wear behavior of the as-prepared Ni-based coatings is investigated by using X-ray diffractometer, scanning electron microscope, wear tribometer and Vickers hardness tester. Results indicates that the microstructure, hardness and wear resistance of La2O3 doped Ni-based coatings are effectively improved as compared to the undoped one, and the coating with the addition of 2.5 wt.% La2O3 shows the optimal improvement effects. The addition of La2O3 can reduce the defects, refine grains and increase hardness of the coating, which can inhibit the nucleation and propagation of cracking, consequently resist cutting and fracture during the wear process. Moreover, the addition of La2O3 leads to changes in abrasion mechanism of the coatings, and the reasons resulting in different abrasion mechanisms are discussed.

  5. Theoretical study of the structure and reactivity of lanthanide and actinide based organometallic complexes; Etude theorique de la structure et de la reactivite de complexes organometalliques de lanthanides et d'actinides

    Energy Technology Data Exchange (ETDEWEB)

    Barros, N

    2007-06-15

    In this PhD thesis, lanthanide and actinide based organometallic complexes are studied using quantum chemistry methods. In a first part, the catalytic properties of organo-lanthanide compounds are evaluated by studying two types of reactions: the catalytic hydro-functionalization of olefins and the polymerisation of polar monomers. The reaction mechanisms are theoretically determined and validated, and the influence of possible secondary non productive reactions is envisaged. A second part focuses on uranium-based complexes. Firstly, the electronic structure of uranium metallocenes is analysed. An analogy with the uranyl compounds is proposed. In a second chapter, two isoelectronic complexes of uranium IV are studied. After validating the use of DFT methods for describing the electronic structure and the reactivity of these compounds, it is shown that their reactivity difference can be related to a different nature of chemical bonding in these complexes. (author)

  6. Microstructures and mechanical properties of Ti3Al/Ni-based superalloy joints arc welded with Ti–Nb and Ti–Ni–Nb filler alloys

    Directory of Open Access Journals (Sweden)

    Bingqing Chen

    2014-08-01

    Full Text Available Dissimilar joining of Ti3Al-based alloy to Ni-based superalloy has been carried out using gas tungsten arc (GTA welding technology with Ti–Nb and Ti–Ni–Nb filler alloys. The joint welded with the Ti–Nb filler alloy contained much less interfacial brittle phases than the one using the Ti–Ni–Nb filler alloy. The average room-temperature tensile strength of the joint welded with Ti–Nb was 202 MPa and the strength value of the one welded with Ti–Ni–Nb was 128 MPa. For both fillers, the weak links of the dissimilar joints were the weld/In718 interfaces. The presence of TiNi, TiNi3 and Ni3Nb intermetallic compounds in the joint welded with Ti–Ni–Nb induced microcracks at the weld/In718 interface and deteriorated the mechanical properties of the joint. And the adoption of the Ti–Nb filler alloy decreased the formation tendency of interfacial brittle phases to some extent and thus enhanced the tensile strength of the joint.

  7. Enhancing Sulfur Tolerance of Ni-Based Cermet Anodes of Solid Oxide Fuel Cells by Ytterbium-Doped Barium Cerate Infiltration.

    Science.gov (United States)

    Li, Meng; Hua, Bin; Luo, Jing-Li; Jiang, San Ping; Pu, Jian; Chi, Bo; Li, Jian

    2016-04-27

    Conventional anode materials for solid oxide fuel cells (SOFCs) are Ni-based cermets, which are highly susceptible to deactivation by contaminants in hydrocarbon fuels. Hydrogen sulfide is one of the commonly existed contaminants in readily available natural gas and gasification product gases of pyrolysis of biomasses. Development of sulfur tolerant anode materials is thus one of the critical challenges for commercial viability and practical application of SOFC technologies. Here we report a viable approach to enhance substantially the sulfur poisoning resistance of a Ni-gadolinia-doped ceria (Ni-GDC) anode through impregnation of proton conducting perovskite BaCe0.9Yb0.1O3-δ (BCYb). The impregnation of BCYb nanoparticles improves the electrochemical performance of the Ni-GDC anode in both H2 and H2S containing fuels. Moreover, more importantly, the enhanced stability is observed in 500 ppm of H2S/H2. The SEM and XPS analysis indicate that the infiltrated BCYb fine particles inhibit the adsorption of sulfur and facilitate sulfur removal from active sites, thus preventing the detrimental interaction between sulfur and Ni-GDC and the formation of cerium sulfide. The preliminary results of the cell with the BCYb+Ni-GDC anode in methane fuel containing 5000 ppm of H2S show the promising potential of the BCYb infiltration approach in the development of highly active and stable Ni-GDC-based anodes fed with hydrocarbon fuels containing a high concentration of sulfur compounds.

  8. Copper-catalyzed regioselective allylic substitution reactions with indium organometallics.

    Science.gov (United States)

    Rodríguez, David; Sestelo, José Pérez; Sarandeses, Luis A

    2003-03-21

    The first nucleophilic allylic substitution reactions of triorganoindium compounds with allylic halides and phosphates are reported. The reactions of trialkyl- and triarylindium reagents with cinnamyl and geranyl halides and phosphates, with the aid of copper catalysis [Cu(OTf)(2)/P(OEt)(3)], are described. In general, the reaction proceeds efficiently to give good yields and regioselectively to afford the S(N)2' product.

  9. Microstructure and corrosion resistance of Ni-based alloy laser coatings with nanosize CeO2 addition

    Directory of Open Access Journals (Sweden)

    Shi Hong Zhang et al

    2008-01-01

    Full Text Available Micron-size Ni-base alloy (NBA powders were mixed with both 1.5 wt.% (hereinafter % micron-size CeO2 (m-CeO2 and also 1.5% and 3.0% nano-size CeO2 (n- CeO2 powders. These mixtures were coated on low-carbon steel (Q235 by 2.0 kW CO2 laser cladding. The effects on the microstructures, phases and electrochemical corrosion of the coatings upon the addition of m- and n- CeO2 powders to NBA (m- and n- CeO2 /NBA have been investigated. The results showed that a smooth coating was prepared under suitable processing parameters (P= 2.0 kW, V= 180 mm min- 1 by adding 1.5% n- CeO2. In addition to the primary phases of γ-Ni, Cr23 C6 and Ni3 B in the Ni-base alloy coating, CeNi3 was formed in Ni-base alloy coatings with both n- CeO2 and m-CeO2 particles, and CeNi5 appeared in the coating upon decreasing the size of CeO2 particles. Well-developed dendrites were observed in the Ni-base alloy coating; directional dendrites grew at the interface in the coating upon the addition of m-CeO2, whereas fine and multioriented dendrites grew upon decreasing the size of CeO2 particles to the nanoscale. Actinomorphic dendrites and compact equiaxed dendrites grew from the interface to near the surface upon increasing the content of n- CeO2 from 1.5 to 3.0%. In strongly acidic HNO3 solution, the severe corrosion of dendrites occurred and there were many corrosion pits in the Ni-base alloy coating; intercrystalline corrosion also has a dominant role upon the addition of m-CeO2, whereas uniform corrosion occurs in the coating as the size of CeO2 particles is decreased to nanoscale.

  10. Microstructure and corrosion resistance of Ni-based alloy laser coatings with nanosize CeO2 addition.

    Science.gov (United States)

    Hong Zhang, Shi; Xi Li, Ming; Hong Yoon, Jae; Yul Cho, Tong; Zhu He, Yi; Gyu Lee, Chan

    2008-07-01

    Micron-size Ni-base alloy (NBA) powders were mixed with both 1.5 wt.% (hereinafter %) micron-size CeO2 (m-CeO2) and also 1.5% and 3.0% nano-size CeO2 (n- CeO2) powders. These mixtures were coated on low-carbon steel (Q235) by 2.0 kW CO2 laser cladding. The effects on the microstructures, phases and electrochemical corrosion of the coatings upon the addition of m- and n- CeO2 powders to NBA (m- and n- CeO2 /NBA) have been investigated. The results showed that a smooth coating was prepared under suitable processing parameters (P= 2.0 kW, V= 180 mm min(- 1)) by adding 1.5% n- CeO2. In addition to the primary phases of γ-Ni, Cr23C6 and Ni3B in the Ni-base alloy coating, CeNi3 was formed in Ni-base alloy coatings with both n- CeO2 and m-CeO2 particles, and CeNi5 appeared in the coating upon decreasing the size of CeO2 particles. Well-developed dendrites were observed in the Ni-base alloy coating; directional dendrites grew at the interface in the coating upon the addition of m-CeO2, whereas fine and multioriented dendrites grew upon decreasing the size of CeO2 particles to the nanoscale. Actinomorphic dendrites and compact equiaxed dendrites grew from the interface to near the surface upon increasing the content of n- CeO2 from 1.5 to 3.0%. In strongly acidic HNO3 solution, the severe corrosion of dendrites occurred and there were many corrosion pits in the Ni-base alloy coating; intercrystalline corrosion also has a dominant role upon the addition of m-CeO2, whereas uniform corrosion occurs in the coating as the size of CeO2 particles is decreased to nanoscale.

  11. Organometallic Vapor-Phase Epitaxy theory and practice

    CERN Document Server

    Stringfellow, Gerald B

    1999-01-01

    This book describes the operation of a particular technique for the production of compound semiconductor materials. It describes how the technique works, how it can be used for the growth of particular materials and structures, and the application of these materials for specific devices. It contains not only a fundamental description of the operation of the technique but also contains lists of data useful for the everyday operation of OMVPE reactors. It also offers specific recipes that can be used to produce a wide range of specific materials, structures, and devices.Key Features* Updated wit

  12. Room temperature synthesis of Ni-based alloy nanoparticles by radiolysis.

    Energy Technology Data Exchange (ETDEWEB)

    Nenoff, Tina Maria; Berry, Donald T.; Lu, Ping; Leung, Kevin; Provencio, Paula Polyak; Stumpf, Roland Rudolph; Huang, Jian Yu; Zhang, Zhenyuan

    2009-09-01

    Room temperature radiolysis, density functional theory, and various nanoscale characterization methods were used to synthesize and fully describe Ni-based alloy nanoparticles (NPs) that were synthesized at room temperature. These complementary methods provide a strong basis in understanding and describing metastable phase regimes of alloy NPs whose reaction formation is determined by kinetic rather than thermodynamic reaction processes. Four series of NPs, (Ag-Ni, Pd-Ni, Co-Ni, and W-Ni) were analyzed and characterized by a variety of methods, including UV-vis, TEM/HRTEM, HAADF-STEM and EFTEM mapping. In the first focus of research, AgNi and PdNi were studied. Different ratios of Ag{sub x}- Ni{sub 1-x} alloy NPs and Pd{sub 0.5}- Ni{sub 0.5} alloy NP were prepared using a high dose rate from gamma irradiation. Images from high-angle annular dark-field (HAADF) show that the Ag-Ni NPs are not core-shell structure but are homogeneous alloys in composition. Energy filtered transmission electron microscopy (EFTEM) maps show the homogeneity of the metals in each alloy NP. Of particular interest are the normally immiscible Ag-Ni NPs. All evidence confirmed that homogeneous Ag-Ni and Pd-Ni alloy NPs presented here were successfully synthesized by high dose rate radiolytic methodology. A mechanism is provided to explain the homogeneous formation of the alloy NPs. Furthermore, studies of Pd-Ni NPs by in situ TEM (with heated stage) shows the ability to sinter these NPs at temperatures below 800 C. In the second set of work, CoNi and WNi superalloy NPs were attempted at 50/50 concentration ratios using high dose rates from gamma irradiation. Preliminary results on synthesis and characterization have been completed and are presented. As with the earlier alloy NPs, no evidence of core-shell NP formation occurs. Microscopy results seem to indicate alloying occurred with the CoNi alloys. However, there appears to be incomplete reduction of the Na{sub 2}WO{sub 4} to form the W

  13. An Advanced Organometallic Lab Experiment with Biological Implications: Synthesis and Characterization of Fe[subscript 2](µ-S[subscript 2])(C0)[subscript 6

    Science.gov (United States)

    Barrett, Jacob; Spentzos, Ariana; Works, Carmen

    2015-01-01

    The organometallic complex Fe[subscript 2](µ-S[subscript 2])(CO)[subscript 6] has interesting biological implications. The concepts of bio-organometallic chemistry are rarely discussed at the undergraduate level, but this experiment can start such a conversation and, in addition, teach valuable synthetic techniques. The lab experiment takes a…

  14. Orientation and Alloying Effects on Creep Strength in Ni-Based Superalloys

    Science.gov (United States)

    Smith, Timothy Michael, Jr.

    The creep deformation mechanisms present during creep at intermediate stress and temperatures in ME3 were further investigated using diffraction contrast imaging. Both conventional transmission electron microscopy and scanning transmission electron microscopy were utilized. Distinctly different deformation mechanisms become operative during creep at temperatures between 677-815ºC, and at stresses ranging from 274-724MPa. Both polycrystalline and single crystal creep tests were conducted. The single crystal tests provide new insight into grain orientation effects on creep response and deformation mechanisms. Creep at lower temperatures (≤760°C) resulted in the thermally activated shearing modes such as microtwinning, stacking fault ribbons and isolated superlattice extrinsic stacking faults (SESFs). In contrast, these faulting modes occurred much less frequently during creep at 815ºC under lower applied stresses. Instead, the principal deformation mode was dislocation climb bypass. In addition to the difference in creep behavior and creep deformation mechanisms as a function of stress and temperature, it was also observed that microstructural evolution occurs during creep at 760°C and above, where the secondary gamma' coarsened and the tertiary gamma' precipitates dissolved. Based on this work, a creep deformation mechanism map is proposed, emphasizing the influence of stress and temperature on the underlying creep mechanisms. Next, the effects of varying crystal orientation and composition on active deformation modes are explored for two different, commercially used Ni-base disk alloys, ME3 and ME501. Understanding these effects will allow for improved predictive deformation modeling and consequently faster advancements in Ni-base alloy development. In order to investigate these effects, compression creep tests were conducted on [001] and [110] oriented single crystal specimens of the disk alloys ME3 and ME501, at different stress/temperature regimes. At 760

  15. Organo-metallic elements for associative information processing

    Science.gov (United States)

    Potember, Richard S.; Poehler, Theodore O.

    1989-01-01

    In the three years of the program we have: (1) built and tested a 4 bit element matrix device for possible use in high density content-addressable memories systems; (2) established a test and evaluation laboratory to examine optical materials for nonlinear effects, saturable absorption, harmonic generation and photochromism; (3) successfully designed, constructed and operated a codeposition processing system that enables organic materials to be deposited on a variety of substrates to produce optical grade coatings and films. This system is also compatible with other traditional microelectronic techniques; (4) used the sol-gel process with colloidal AgTCNQ to fabricate high speed photochromic switches; (5) develop and applied for patent coverage to make VO2 optical switching materials via the sol-gel processing using vanadium (IV) alkoxide compounds.

  16. Organometallic B12-DNA conjugate: synthesis, structure analysis, and studies of binding to human B12-transporter proteins.

    Science.gov (United States)

    Hunger, Miriam; Mutti, Elena; Rieder, Alexander; Enders, Barbara; Nexo, Ebba; Kräutler, Bernhard

    2014-10-06

    Design, synthesis, and structural characterization of a B12-octadecanucleotide are presented herein, a new organometallic B12-DNA conjugate. In such covalent conjugates, the natural B12 moiety may be a versatile vector for controlled in vivo delivery of oligonucleotides to cellular targets in humans and animals, through the endogenous B12 transport systems. Binding of the organometallic B12 octadecanucleotide to the three important human proteins of B12 transport was studied, to examine its structural suitability for the task of eventual in vivo oligonucleotide delivery. Binding was efficient with transcobalamin (TC), but not so efficient with the homologous glycoproteins intrinsic factor and haptocorrin. Binding of the B12 octadecanucleotide to TC suggests the capacity of the B12 moiety to serve as a natural vector for specific transport of single stranded, organometallic oligonucleotide loads from the blood stream into cells.

  17. Effects of Annealing on the Martensitic Transformation of Ni-Based Ferromagnetic Shape Memory Heusler Alloys and Nanoparticles

    OpenAIRE

    Tina Fichtner; Changhai Wang; Aleksandr A. Levin; Guido Kreiner; Catalina Salazar Mejia; Simone Fabbrici; Franca Albertini; Claudia Felser

    2015-01-01

    We report on the effects of annealing on the martensitic phase transformation in the Ni-based Heusler system: Mn50Ni40Sn10 and Mn50Ni41Sn9 powder and Co50Ni21Ga32 nanoparticles. For the powdered Mn50Ni40Sn10 and Mn50Ni41Sn9 alloys, structural and magnetic measurements reveal that post-annealing decreases the martensitic transformation temperatures and increases the transition hysteresis. This might be associated with a release of stress in the Mn50Ni40Sn10 and Mn50Ni41Sn9 alloys during the an...

  18. Influence of preoxidation on high temperature corrosion of a Ni-based alloy under conditions relevant to biomass firing

    DEFF Research Database (Denmark)

    Okoro, Sunday Chukwudi; Montgomery, Melanie; Jappe Frandsen, Flemming

    2017-01-01

    of preoxidized layers formed on a commercial Cr-Ti-Al-containing Ni-based alloy (Nimonic 80A) to withstand biomass-induced corrosion was investigated. Preoxidation treatments at 900 °C in O2 and O2 + 10 vol% H2O, respectively, were conducted before samples were exposed to conditions that mimicked biomass firing...... attack and formed porous non-protective oxides containing the alloying elements, Ni, Cr, Ti and Al. The influence of the preoxidation layers on the corrosion mechanism is discussed....

  19. Study on Carbon Nanotubes Prepared from Catalytic Decomposition of CH4 over Lanthanum Containing Ni-Base Catalysts

    Institute of Scientific and Technical Information of China (English)

    Wang Minwei; Li Fengyi

    2004-01-01

    A series of lanthanum containing Ni-base catalysts were prepared by citric acid complex method.Carbon nanotubes (CNT) were synthesized bY catalytic decomposing CH4 over these catalysts and characterized by XRD, TEM and TGA.It is found that the addition of lanthanum can not increase the yield of carbon nanotube, but can make the diameter of carbon nanotube thinner and even.The more the lanthanum addsr, the thinner the diameter of CNTs becomes.With the CNTs prepared on Ni-Mg catalyst, the CNTs prepared on Ni-La-Mg catalyst has better crystallinity and thermal stability.

  20. Quantum transport behavior of Ni-based dinuclear complexes in presence of zigzag graphene nanoribbon as electrode

    Science.gov (United States)

    Sarkar, Sunandan; Pramanik, Anup; Sarkar, Pranab

    2016-10-01

    Quantum transport properties of some Ni-based dinuclear complexes with different polydentate organic ligands have been studied by applying abinitio density functional theory along with nonequilibrium Green's function formulations. It is demonstrated that these materials are capable of showing multifunctional spin dependent properties by the influence of edge states of zigzag edged graphene nanoribbons. The current-voltage characteristics of these materials show spin dependent negative differential resistance behavior, spin filtering effect, and also voltage rectifying property. Proper tuning of these materials can alter these effects which may be utilized in various spintronic devices.

  1. Reduced Dwell-Fatigue Resistance in a Ni-Base Superalloy After Short-Term Thermal Exposure

    Science.gov (United States)

    Hörnqvist, Magnus; Viskari, Leif

    2014-06-01

    The effect of short-term thermal exposure on microstructure and dwell-fatigue resistance of Ni-base superalloy 718Plus was investigated. Contrary to previous studies performed after long-term exposure, an increase in the dwell-fatigue crack growth rate was observed, which was connected to a small increase in the size of the hardening precipitates. The proposed controlling mechanism was the stress relaxation rate at the crack tip, and based on this a schematic model for the development of the properties during exposure is presented.

  2. Effect of the cooling rate on microstructure and hardness of MAR-M247 Ni-based superalloy

    OpenAIRE

    Milenkovic, Srdjan; Sabirov, Ilchat; Llorca Martinez, Francisco Javier

    2012-01-01

    The effect of cooling rate on the microstructure of MAR-M247 Ni-based superalloy was investigated via physical simulation of the casting process. Solidification experiments with cooling rates in the range of 0.25–10 K/s showed smooth temperature profiles with measured cooling rates matching the set values. The MAR-M247 showed cellular (0.25 K/s) and dendritic (1, 5 and 10 K/s) microstructures. Microconstituents also varied with cooling rates: γ/γ′ matrix with carbides and γ/γ′ eutectic at 0.2...

  3. Investigation of fragmentation processes following core photoionization of organometallic molecules in the vapor phase

    Science.gov (United States)

    Nagaoka, Shin-ichi; Suzuki, Shinzo; Koyano, Inosuke

    1988-04-01

    Ionic fragmentation processes following ( n - 1)d core level photoionization of organometallic molecules have been studied in the vapor phase using synchrotron radiation. Results on tetramethyllead, tetramethyltin and tetramethylgermanium are reported. The threshold electron spectra and the photoionization efficiency curves of these molecules are presented and discussed. It is concluded that the ( n - 1)d 9 core-hole state of M(CH 3) 4 (M  Pb, Sn or Ge) is split into five sublevels owing to both the spin-orbi and the electrostatic perturbations by the methyl groups, and that the M + ions are predominantly produced following ( n - 1)d photoionization.

  4. Understanding organometallic reaction mechanisms and catalysis experimental and computational tools computational and experimental tools

    CERN Document Server

    Ananikov, Valentin P

    2014-01-01

    Exploring and highlighting the new horizons in the studies of reaction mechanisms that open joint application of experimental studies and theoretical calculations is the goal of this book. The latest insights and developments in the mechanistic studies of organometallic reactions and catalytic processes are presented and reviewed. The book adopts a unique approach, exemplifying how to use experiments, spectroscopy measurements, and computational methods to reveal reaction pathways and molecular structures of catalysts, rather than concentrating solely on one discipline. The result is a deeper

  5. Synthesis and characterization of azo-containing organometallic thin films for all optical switching applications

    Science.gov (United States)

    Gatri, R.; Fillaut, J.-L.; Mysliwiec, J.; Szukalski, A.; Bartkiewicz, S.; El-Ouazzani, H.; Guezguez, I.; Khammar, F.; Sahraoui, B.

    2012-05-01

    Novel photoresponsive materials based on azo-containing bifunctional ruthenium-acetylides have been synthesized. All optical switching based on the Optical Kerr Effect in the organometallic thin films based on ruthenium(II) acetylides containing an azobenzene moiety as a photochromic unit in the main pi-conjugated system dispersed in a poly(methyl methacrylate) matrix has been observed. The excitation beam was delivered from a picosecond laser at wavelength 532 nm while dynamics of induced sample birefringence was probed by a non-absorbed linearly polarized beam of cw He-Ne laser (632.8 nm). The influence of ruthenium part on dynamics of molecular motions has been shown.

  6. Chemoselective Ketone Synthesis by the Addition of Organometallics to N-Acylazetidines.

    Science.gov (United States)

    Liu, Chengwei; Achtenhagen, Marcel; Szostak, Michal

    2016-05-20

    A general and highly chemoselective method for the synthesis of ketones by the addition of organometallics to N-acylazetidines via stable tetrahedral intermediates is reported for the first time. The transformation is characterized by its wide substrate scope and exquisite selectivity for the ketone products even when a large excess of nucleophilic reagents is used. Even of broader interest is the use of N-acylazetidines as bench-stable, readily available amide acylating reagents, in which the reactivity is controlled by amide pyramidalization and strain of the four-membered ring to afford synthetically valuable building blocks.

  7. Supported organometallic complexes: Surface chemistry, spectroscopy, and catalysis. Progress report, February 1, 1991--January 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Marks, T.J.

    1992-02-01

    The long-range goal of this project is to elucidate and understand the surface chemistry and catalytic properties of well-defined, highly-reactive organometallic molecules (principally based upon abundant actinide, lanthanide, and early transition elements) adsorbed on metal oxides and halides. The nature of the adsorbed species is probed by a battery of chemical and physicochemical techniques, to understand the nature of the molecular-surface coordination chemistry and how this can give rise to extremely high catalytic activity. A complementary objective is to delineate the scope and mechanisms of the heterogeneous catalytic reactions, as well as to relate them both conceptually and functionally to model systems generated in solution.

  8. Selective growth of GaAs by organometallic vapor phase epitaxy at atmospheric pressure

    Science.gov (United States)

    Azoulay, R.; Dugrand, L.

    1991-01-01

    Complete selective epitaxy of GaAs by organometallic vapor phase epitaxy at atmospheric pressure was achieved by using TMG, AsH3, and AsCl3 as starting gases. Selectivity was observed at growth temperatures ranging from 650 to 750 °C. The blocking of polycrystal deposition on the mask, Si3N4, or W, is attributed to the adsorption of HCl on the mask, thus preventing the nucleation of GaAs. On the openings, the growth rate may be adjusted by controlling the TMG/AsCl3 ratio. When TMG/AsCl3<1, no growth occurs, but etching is observed.

  9. Phenylethynylcobalamin: a light-stable and thermolysis-resistant organometallic vitamin B(12) derivative prepared by radical synthesis.

    Science.gov (United States)

    Ruetz, Markus; Salchner, Robert; Wurst, Klaus; Fedosov, Sergey; Kräutler, Bernhard

    2013-10-18

    Don't take this antivitamin! 2-Phenylethynylcobalamin was prepared in a newly developed radical reaction using cob(II)alamin and 1-iodo-2-phenylethyne. It has an exceptionally short organometallic bond and is a remarkably light-stable and heat-resistant organometallic cobalamin. It is bound well by two important proteins of the human B12 transport system and has properties that are as expected for a new type of an "antivitamin B12 ". Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Organometallic synthesis, reactivity and catalysis in the solid state using well-defined single-site species

    OpenAIRE

    Pike, Sebastian D.; Weller, Andrew S.

    2015-01-01

    Acting as a bridge between the heterogeneous and homogeneous realms, the use of discrete, well-defined, solid-state organometallic complexes for synthesis and catalysis is a remarkably undeveloped field. Here, we present a review of this topic, focusing on describing the key transformations that can be observed at a transition-metal centre, as well as the use of well-defined organometallic complexes in the solid state as catalysts. There is a particular focus upon gas–solid reactivity/catalys...

  11. Intercalation compounds involving inorganic layered structures

    Directory of Open Access Journals (Sweden)

    CONSTANTINO VERA R. L.

    2000-01-01

    Full Text Available Two-dimensional inorganic networks can shown intracrystalline reactivity, i.e., simple ions, large species as Keggin ions, organic species, coordination compounds or organometallics can be incorporated in the interlayer region. The host-guest interaction usually causes changes in their chemical, catalytic, electronic and optical properties. The isolation of materials with interesting properties and making use of soft chemistry routes have given rise the possibility of industrial and technological applications of these compounds. We have been using several synthetic approaches to intercalate porphyrins and phthalocyanines into inorganic materials: smectite clays, layered double hydroxides and layered niobates. The isolated materials have been characterized by elemental and thermal analysis, X-ray diffraction, surface area measurements, scanning electronic microscopy, electronic and resonance Raman spectroscopies and EPR. The degree of layer stacking and the charge density of the matrices as well their acid-base nature were considered in our studies on the interaction between the macrocycles and inorganic hosts.

  12. In vivo tumour and metastasis reduction and in vitro effects on invasion assays of the ruthenium RM175 and osmium AFAP51 organometallics in the mammary cancer model.

    Science.gov (United States)

    Bergamo, A; Masi, A; Peacock, A F A; Habtemariam, A; Sadler, P J; Sava, G

    2010-01-01

    We have compared the organometallic arene complexes [(eta(6)-biphenyl)M(ethylenediamine)Cl](+) RM175 (M=Ru(II)) and its isostructural osmium(II) analogue AFAP51 (M=Os(II)) for their ability to induce cell detachment resistance from fibronectin, collagen IV and poly-l-lysine, and cell re-adhesion after treatment, their effects on cell migration and cell viability, on matrix metalloproteinases production, and on primary tumour growth of MCa mammary carcinoma, the effect of human serum albumin on their cytotoxicity. There are differences between ruthenium and osmium. The Os complex is up to 6x more potent than RM175 towards highly-invasive breast MDA-MB-231, human breast MCF-7 and human epithelial HBL-100 cancer cells, but whereas RM175 was active against MCa mammary carcinoma in vivo and caused metastasis reduction, AFAP51 was not. Intriguingly the presence of human serum albumin in the growth medium enhanced the cytotoxicity of both compounds. RM175 increased the resistance of MDA-MB-231 cells to detachment from substrates and both compounds inhibited the production of MMP-2. These data confirm the key role of ruthenium itself in anti-metastatic activity. It will be interesting to explore the activity of osmium arene complexes in other tumour models and the possibility of changing the non-arene ligands to tune the anticancer activity of osmium in vivo.

  13. Catalysis by Design Using Surface Organometallic Nitrogen-Containing Fragments

    KAUST Repository

    Hamzaoui, Bilel

    2016-06-14

    The aim of this thesis is to explore the chemistry of well-defined silica-supported group 4 and group 5 complexes that contain one or more multiply-bonded nitrogen atoms. Such species have been recognized as crucial intermediates in many catalytic reactions (e.g. hydroaminoalkylation, olefin hydrogenation, imine metathesis…). The first chapter provided a bibliographic overview of the preparation and the reactivity of group 4 and 5 complexes towards hydroaminoalkylation and imine metathesis catalysis. The second chapter deals with the isolation and the characterization of a series of well-defined group 4 ƞ2-imine complexes surfaces species. 2D solid-state NMR (1H–13C HETCOR, Multiple Quantum) experiments have revealed consistently a unique structural rearrangement, viz azametallacycle occurring on the immobilized metal-amido ligands. Hydrogenolysis of the sole Zr-C bond in such species gives selectively a silica-supported zirconium monohydride that can perform the catalytic hydrogenation of olefins. The third chapter examines the mechanistic studies of the intermolecular hydroaminoalkylation using SOMC to identify the key metallacyclic surface intermediates (silica-supported three-membred and five-membered). The catalyst was regenerated by protonolysis and afforded pure amine. Catalytic testing of a selection of amine compounds with variable electronic properties was carried out. The fourth chapter deals with the generation and the characterization of well-defined silica-supported zirconium-imido complexes. The resulting species effectively catalyzes imine/imine cross-metathesis and thus considered as the first heterogeneous catalysts active for imine metathesis reaction. The fifth chapter studies the reaction of SBA15.1100 ºC with dry aniline and derivatives leading to opening strained siloxane bridges into acid-base paired functionalities (formation of N-phenylsilanamine-silanol pairs). This approach was successfully applied to the design of a series of

  14. Effect of Rare Earth on Microstructure of Vacuum Melting Ni-Based Self-Fluxing Alloy Coatings

    Institute of Scientific and Technical Information of China (English)

    宣天鹏; 闵丹

    2004-01-01

    The Ni-based self-fluxing alloy coating containing RE was acquired by the technique of vacuum melting on the hypoeutectoid steel (Fe-0.45%C) matrix. By X-ray diffraction, SEM and EDX, the microstructure and phase structure of section of coating and the microstructure near the interface between coating and matrix were investigated, and the effect of RE on microstructure of coating was also discussed. The results show that the microstructure of the NiCrBSi alloy coating is composed of Ni-based solid solution and a lot of massive, globular and needle secondary phases CrB, Ni3B, Cr7C3, Cr23C6 among the solid solution. The metallurgical binding between steel matrix and coating is realized. RE makes needle phase of alloy coating vanish. New phases of NiB and Cr6.5Ni2.5Si are precipitated from alloy coating, and secondary phases of alloy coating are sphericized. Consequently, RE also hinders the diffusion of Ni, Cr and Si atoms from coating to matrix and Fe atoms from matrix to coating, holds back the dilution of Fe for NiCrBSi alloy coating, and assures the chemical composition of the alloy coating.

  15. Assessing the Effects of Radiation Damage on Ni-base Alloys for the Prometheus Space Reactor System

    Energy Technology Data Exchange (ETDEWEB)

    T. Angeliu

    2006-01-19

    Ni-base alloys were considered for the Prometheus space reactor pressure vessel with operational parameters of {approx}900 K for 15 years and fluences up to 160 x 10{sup 20} n/cm{sup 2} (E > 0.1 MeV). This paper reviews the effects of irradiation on the behavior of Ni-base alloys and shows that radiation-induced swelling and creep are minor considerations compared to significant embrittlement with neutron ,exposure. While the mechanism responsible for radiation-induced embrittlement is not fully understood, it is likely a combination of helium embrittlement and solute segregation that can be highly dependent on the alloy composition and exposure conditions. Transmutation calculations show that detrimental helium levels would be expected at the end of life for the inner safety rod vessel (thimble) and possibly the outer pressure vessel, primarily from high energy (E > 1 MeV) n,{alpha} reactions with {sup 58}Ni. Helium from {sup 10}B is significant only for the outer vessel due to the proximity of the outer vessel to the Be0 control elements. Recommendations for further assessments of the material behavior and methods to minimize the effects of radiation damage through alloy design are provided.

  16. On the diffusion mechanisms of fine-scale γ′ in an advanced Ni-based superalloy

    Directory of Open Access Journals (Sweden)

    Chen Y.

    2014-01-01

    Full Text Available Size dependent compositional variations for the ordered L12-structure gamma prime (γ′ precipitates in the commercial Ni-based superalloy RR1000 have been investigated using scanning transmission electron microscope (STEM imaging combined with energy-dispersive X-ray (EDX spectroscopy. To address the problem of quantitative compositional determination for nanoscale particles within a metal matrix we have applied a novel electrochemical method to extract individual precipitates. The use of a high-efficiency EDX detector enabled compositional measurements to be obtained for particles with diameters as small as 20 nm with acquisition times of the order of a few minutes. We have studied compositional variations across the different size families of γ′ precipitates within a microstructure generated by slow cooling. Our results demonstrate the importance of kinetic factors for determining the precipitates compositions. In particular, we provide new evidence for the role of aluminium antisite atoms on the low-temperature growth kinetics of fine scale γ′ precipitates. Our findings provide valuable structural data towards improving the accuracy of predicting the microstructural evolution in Ni-based superalloys.

  17. Assessing the Effects of Radiation Damage on Ni-base Alloys for the Prometheus Space Reactor System

    Energy Technology Data Exchange (ETDEWEB)

    T Angeliu; J Ward; J Witter

    2006-04-04

    Ni-base alloys were considered for the Prometheus space reactor pressure vessel with operational parameters of {approx}900 K for 15 years and fluences up to 160 x 10{sup 20} n/cm{sup 2} (E > 0.1 MeV). This paper reviews the effects of irradiation on the behavior of Ni-base alloys and shows that radiation-induced swelling and creep are minor considerations compared to significant embrittlement with neutron exposure. While the mechanism responsible for radiation-induced embrittlement is not fully understood, it is likely a combination of helium embrittlement and solute segregation that can be highly dependent on the alloy composition and exposure conditions. Transmutation calculations show that detrimental helium levels would be expected at the end of life for the inner safety rod vessel (thimble) and possibly the outer pressure vessel, primarily from high energy (E > 1 MeV) n,{alpha} reactions with {sup 58}Ni. Helium from {sup 10}B is significant only for the outer vessel due to the proximity of the outer vessel to the BeO control elements. Recommendations for further assessments of the material behavior and methods to minimize the effects of radiation damage through alloy design are provided.

  18. Microstructural studies on friction surfaced coatings of Ni-based alloys; Gefuegeuntersuchungen an reibgeschweissten Beschichtungen von Ni-Basislegierungen

    Energy Technology Data Exchange (ETDEWEB)

    Akram, Javed; Puli, Ramesh; Kalvala, Prasad Rao; Misra, Mano [Utah Univ., Salt Lake City, UT (United States). Dept. of Metallurgical Engineering

    2015-07-01

    Inconel 625, Inconel 600, Inconel 800H were friction surfaced on steel and Inconel substrates. The interface between steel and Ni-based alloys showed intermixing of two alloys while the interface between two Ni-based alloys showed no such intermixing. The XRD results confirmed that this intermixed zone consisted of mechanical mix two separate metals and no intermetallics were noticed. Friction surfaced Inconel coatings were metallurgically bonded to steel and Inconel substrates with out any physical defects such as voids or cracks. Friction surfaced coatings showed equiaxed fine grained microstructures (4-18 μm) compared with their consumable rod counterparts (12 - 85 μm). Scanning electron microscope electron backscattered diffraction results showed that the coatings consisted of mainly high angle grain boundaries indicative of dynamic recrystallization mechanism. The temperatures recorded using Infra Red camera showed that the temperature attained at the interface between rod and the substrate is about 1100 C. The grain size of the consumable rod was relatively fine near the coating/substrate interface and relatively coarser away from interface indicating the change in strain and temperature the rod experienced at or away from the interface.

  19. An organometallic building block approach to produce a multidecker 4f single-molecule magnet.

    Science.gov (United States)

    Le Roy, Jennifer J; Jeletic, Matthew; Gorelsky, Serge I; Korobkov, Ilia; Ungur, Liviu; Chibotaru, Liviu F; Murugesu, Muralee

    2013-03-06

    An organometallic building block strategy was employed to investigate the magnetic properties of a Ln(III) organometallic single-ion magnet (SIM) and subsequent single-molecule magnet (SMM) after coupling two of the monomeric units. New homoleptic Dy(III)COT″2 and Ln(III)2COT″3 (Ln = Gd, Dy) complexes have been synthesized. DFT calculations of the bimetallic Dy(III) complex indicate strong metal-ligand covalency and uneven donation to the Dy(III) ions by the terminal and internal COT″(2-) (cyclooctatetraenide) rings that correlate with the respective bond distances. Interestingly, the studies also point to a weak covalent interaction between the metal centers, despite a large separation. The ac susceptibility data indicates that both Dy(III)COT″2 and Dy(III)2COT″3 act as an SIM and an SMM, respectively, with complex multiple relaxation mechanisms. Ab initio calculations reveal the direction of the magnetic anisotropic axis is not perpendicular to the planar COT″ rings for both Dy(III)COT″2 and Dy(III)2COT″3 complexes due to the presence of trimethylsilyl groups on the COT″ rings. If these bulky groups are removed, the calculations predict reorientation of the anisotropic axis can be achieved.

  20. Interplay between experiments and calculations for organometallic clusters and caged clusters

    Energy Technology Data Exchange (ETDEWEB)

    Nakajima, Atsushi [Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Yokohama 223-8522 (Japan); Nakajima Designer Nanocluster Assembly Project, ERATO, JST, KSP, 3-2-1 Sakado, Kawasaki 213-0012 (Japan); Keio Institute of Pure and Applied Sciences (KiPAS), Keio University, 3-14-1 Hiyoshi, Yokohama 223-8522 (Japan)

    2015-12-31

    Clusters consisting of 10-1000 atoms exhibit size-dependent electronic and geometric properties. In particular, composite clusters consisting of several elements and/or components provide a promising way for a bottom-up approach for designing functional advanced materials, because the functionality of the composite clusters can be optimized not only by the cluster size but also by their compositions. In the formation of composite clusters, their geometric symmetry and dimensionality are emphasized to control the physical and chemical properties, because selective and anisotropic enhancements for optical, chemical, and magnetic properties can be expected. Organometallic clusters and caged clusters are demonstrated as a representative example of designing the functionality of the composite clusters. Organometallic vanadium-benzene forms a one dimensional sandwich structure showing ferromagnetic behaviors and anomalously large HOMO-LUMO gap differences of two spin orbitals, which can be regarded as spin-filter components for cluster-based spintronic devices. Caged clusters of aluminum (Al) are well stabilized both geometrically and electronically at Al{sub 12}X, behaving as a “superatom”.

  1. A nickel tripeptide as a metallodithiolate ligand anchor for resin-bound organometallics.

    Science.gov (United States)

    Green, Kayla N; Jeffery, Stephen P; Reibenspies, Joseph H; Darensbourg, Marcetta Y

    2006-05-17

    The molecular structure of the acetyl CoA synthase enzyme has clarified the role of individual nickel atoms in the dinickel active site which mediates C-C and C-S coupling reactions. The NiN2S2 portion of the biocatalyst (N2S2 = a cysteine-glycine-cysteine or CGC4- tripeptide ligand) serves as an S-donor ligand comparable to classical bidentate ligands operative in organometallic chemistry, ligating the second nickel which is redox and catalytically active. Inspired by this biological catalyst, the synthesis of NiN2S2 metalloligands, including the solid-phase synthesis of resin-bound Ni(CGC)2-, and sulfur-based derivatization with W(CO)5 and Rh(CO)2+ have been carried out. Through comparison to analogous well-characterized, solution-phase complexes, Attenuated Total Reflectance FTIR spectroscopy establishes the presence of unique heterobimetallic complexes, of the form [Ni(CGC)]M(CO)x, both in solution and immobilized on resin beads. This work provides the initial step toward exploitation of such an evolutionarily optimized nickel peptide as a solid support anchor for hybrid bioinorganic-organometallic catalysts.

  2. Bridging organometallics and quantum chemical topology: Understanding electronic relocalisation during palladium-catalyzed reductive elimination.

    Science.gov (United States)

    de Courcy, Benoit; Derat, Etienne; Piquemal, Jean-Philip

    2015-06-05

    This article proposes to bridge two fields, namely organometallics and quantum chemical topology. To do so, Palladium-catalyzed reductive elimination is studied. Such reaction is a classical elementary step in organometallic chemistry, where the directionality of electrons delocalization is not well understood. New computational evidences highlighting the accepted mechanism are proposed following a strategy coupling quantum theory of atoms in molecules and electron localization function topological analyses and enabling an extended quantification of donated/back-donated electrons fluxes along reaction paths going beyond the usual Dewar-Chatt-Duncanson model. Indeed, if the ligands coordination mode (phosphine, carbene) is commonly described as dative, it appears that ligands lone pairs stay centered on ligands as electrons are shared between metal and ligand with strong delocalization toward the latter. Overall, through strong trans effects coming from the carbon involved in the reductive elimination, palladium delocalizes its valence electrons not only toward phosphines but interestingly also toward the carbene. As back-donation increases during reductive elimination, one of the reaction key components is the palladium ligands ability to accept electrons. The rationalization of such electronic phenomena gives new directions for the design of palladium-catalyzed systems.

  3. The optical characterization of organometallic complex thin films by spectroscopic ellipsometry and photovoltaic diode application

    Energy Technology Data Exchange (ETDEWEB)

    Özaydın, C. [Batman University, Engineering Faculty, Department of Computer Eng., Batman (Turkey); Güllü, Ö., E-mail: omergullu@gmail.com [Batman University, Science and Art Faculty, Department of Physics, Batman (Turkey); Pakma, O. [Batman University, Science and Art Faculty, Department of Physics, Batman (Turkey); Ilhan, S. [Siirt University, Science and Art Faculty, Department of Chemistry, Siirt (Turkey); Akkılıç, K. [Dicle University, Education Faculty, Department of Physics Education, Diyarbakır (Turkey)

    2016-05-15

    Highlights: • Optical properties and thickness of the A novel organometallic complex (OMC) film were investigated by spectroscopic ellipsometry (SE). • Au/OMC/n-Si metal/interlayer/semiconductor (MIS) diode has been fabricated • This paper presents the I–V analysis of Au/OMC/n-Si MIS diode. • Current–voltage and photovoltaic properties of the diode were investigated. - Abstract: In this work, organometallic complex (OMC) films have been deposited onto glass or silicon substrates by spin coating technique and their photovoltaic application potential has been investigated. Optical properties and thickness of the film have been investigated by spectroscopic ellipsometry (SE). Also, transmittance spectrum has been taken by UV/vis spectrophotometer. The optical method has been used to determine the band gap value of the films. Also, Au/OMC/n-Si metal/interlayer/semiconductor (MIS) diode has been fabricated. Current–voltage and photovoltaic properties of the structure were investigated. The ideality factor (n) and barrier height (Φ{sub b}) values of the diode were found to be 2.89 and 0.79 eV, respectively. The device shows photovoltaic behavior with a maximum open-circuit voltage of 396 mV and a short circuit current of 33.8 μA under 300 W light.

  4. Arene control over thiolate to sulfinate oxidation in albumin by organometallic ruthenium anticancer complexes.

    Science.gov (United States)

    Hu, Wenbing; Luo, Qun; Ma, Xiaoyan; Wu, Kui; Liu, Jianan; Chen, Yi; Xiong, Shaoxiang; Wang, Jianping; Sadler, Peter J; Wang, Fuyi

    2009-07-06

    Interactions of organometallic ruthenium anticancer complexes [Ru(eta6-arene)Cl(en)][PF6] (arene=p-cymene (1) or biphenyl (2), en=ethylenediamine) with human serum albumin were investigated by means of mass spectrometry combined with trypsin digestion, specific sidechain modifications and computational modelling. Both complexes were shown to bind to surface histidine (His128, His247, His510) and methionine (Met298) residues in human albumin, but only the p-cymene complex can gain entry to the crevice containing the free cysteine thiolate (Cys34) and induce oxidation to sulfinate. The two complexes exhibit a similar coordination preference for histidine and methionine residues on the protein surface. His128 binding is favoured both kinetically and thermodynamically. At 310 K, six days of incubation of recombinant human albumin (rHA) with complex 1 (rHA:Ru 50:250 microM) led to about 18 % ruthenation of His128 in the protein. However, the extent of ruthenation of albumin by complex 2 was less than that by 1, due to the steric hindrance from the biphenyl ligand. These results imply that the arene ligand in the organometallic ruthenium anticancer complexes plays a crucial role in interactions with proteins.

  5. Synthesis and Microstructural Investigations of Organometallic Pd(II Thiol-Gold Nanoparticles Hybrids

    Directory of Open Access Journals (Sweden)

    Cervellino Antonio

    2008-01-01

    Full Text Available Abstract In this work the synthesis and characterization of gold nanoparticles functionalized by a novel thiol-organometallic complex containing Pd(II centers is presented. Pd(II thiol,trans, trans-[dithiolate-dibis(tributylphosphinedipalladium(II-4,4′-diethynylbiphenyl] was synthesized and linked to Au nanoparticles by the chemical reduction of a metal salt precursor. The new hybrid made of organometallic Pd(II thiol-gold nanoparticles, shows through a single S bridge a direct link between Pd(II and Au nanoparticles. The size-control of the Au nanoparticles (diameter range 2–10 nm was achieved by choosing the suitable AuCl4 −/thiol molar ratio. The size, strain, shape, and crystalline structure of these functionalized nanoparticles were determined by a full-pattern X-ray powder diffraction analysis, high-resolution TEM, and X-ray photoelectron spectroscopy. Photoluminescence spectroscopy measurements of the hybrid system show emission peaks at 418 and 440 nm. The hybrid was exposed to gaseous NO x with the aim to evaluate the suitability for applications in sensor devices; XPS measurements permitted to ascertain and investigate the hybrid –gas interaction.

  6. Dolomite-Derived Ni-Based Catalysts with Fe Modification for Hydrogen Production via Auto-Thermal Reforming of Acetic Acid

    Directory of Open Access Journals (Sweden)

    Xinyan Zhong

    2016-06-01

    Full Text Available Bio-oil can be obtained via fast pyrolysis of biomass, and typically contains acetic acid (~30 mass %. The acetic acid has often been tested as a model compound for hydrogen production via reforming bio-oil, in which catalysts are a key factor for stable hydrogen production. However, deactivation of catalysts by coking and oxidation hinders the application of the reforming process. Dolomite-derived Ni-based catalysts with Fe additive, MgNi0.2Ca0.8−xFexO2±δ (x = 0–0.8, were successfully synthesized by the hydrothermal synthesis method, and then tested in auto-thermal reforming (ATR of acetic acid (AC. The MgNi0.2Ca0.5Fe0.3O2±δ catalyst performed a stable reactivity in ATR: the conversion of AC reached 100%, and the H2 yield remained stable around 2.6 mol-H2/mol-AC. The catalysts were characterized by X-ray diffraction (XRD, N2 physisorption, X-ray photoelectron spectra (XPS, H2-temperature-programmed reduction (TPR, inductively coupled plasma- atomic emission spectroscopy (ICP-AES and Thermogravimetry (TG; the results show that a periclase-like solid solution of Mg(Ni,FeO and lime were formed via the precursors of dolomite and hydrotalcite, and then transformed into Fe-rich Ni-Fe alloy with basic support of MgO-CaO after reduction. The stable Ni0 spices with basic support can explain the stability and resistance to coking during ATR of AC.

  7. Stability of an Electrodeposited Nanocrystalline Ni-Based Alloy Coating in Oil and Gas Wells with the Coexistence of H2S and CO2

    Directory of Open Access Journals (Sweden)

    Yiyong Sui

    2017-06-01

    Full Text Available The stability of an electrodeposited nanocrystalline Ni-based alloy coating in a H2S/CO2 environment was investigated by electrochemical measurements, weight loss method, and surface characterization. The results showed that both the cathodic and anodic processes of the Ni-based alloy coating were simultaneously suppressed, displaying a dramatic decrease of the corrosion current density. The corrosion of the Ni-based alloy coating was controlled by H2S corrosion and showed general corrosion morphology under the test temperatures. The corrosion products, mainly consisting of Ni3S2, NiS, or Ni3S4, had excellent stability in acid solution. The corrosion rate decreased with the rise of temperature, while the adhesive force of the corrosion scale increased. With the rise of temperature, the deposited morphology and composition of corrosion products changed, the NiS content in the corrosion scale increased, and the stability and adhesive strength of the corrosion scale improved. The corrosion scale of the Ni-based alloy coating was stable, compact, had strong adhesion, and caused low weight loss, so the corrosion rates calculated by the weight loss method cannot reveal the actual oxidation rate of the coating. As the corrosion time was prolonged, the Ni-based coating was thinned while the corrosion scale thickened. The corrosion scale was closely combined with the coating, but cannot fully prevent the corrosive reactants from reaching the substrate.

  8. Synthesis of functionalized thiophenes and oligothiophenes by selective and iterative cross-coupling reactions using indium organometallics.

    Science.gov (United States)

    Montserrat Martínez, M; Peña-López, Miguel; Pérez Sestelo, José; Sarandeses, Luis A

    2012-05-21

    The synthesis of unsymmetrical 2,5-disubstituted thiophenes by selective and sequential palladium-catalyzed cross-coupling reactions of indium organometallics with 2,5-dibromothiophene is reported. Following an iterative coupling sequence, α-oligothiophenes were synthesized in good yields and with high atom economy.

  9. Synthesis of organozirconium and -hafnium compounds containing silaneopentyl-type groups

    Energy Technology Data Exchange (ETDEWEB)

    Vdovin, V.M.; Bespalova, N.B.; Ivaschenko, D.A.; Nikitin, V.S.; Sergeeva, M.B.; Strelenko, Y.A.

    1986-01-10

    This paper proposes a new method for the synthesis of organic compounds of zirconium and hafnium containing the group MCH/sub 2/Si, by reacting Zr or Hf tetrachloride with 1,1,3,3-tetramethyl-1,3-disilacyclobutane (I). Using equimolar amounts of the reactants and a temperature of 20 C, cleavage of the disilacyclobutane ring occurs with the formation of the appropriate organometallic compound 2,2,4,4-tetramethyl-4-chloro-2,4-disilabutylzirconium (or hafnium) trichloride (II). The C 13 chemical shifts of compound (II) in C/sub 6/D/sub 6/ solution relative to (CH/sub 3/)/sub 4/Si are presented.

  10. Carburization of W- and Re-rich Ni-based alloys in impure helium at 1000 {sup o}C

    Energy Technology Data Exchange (ETDEWEB)

    Adharapurapu, Raghavendra R., E-mail: araghav@gmail.co [Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109 (United States); Kumar, Deepak; Zhu Jun [Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109 (United States); Pollock, Tresa M. [Materials Department, University of California, Santa Barbara, CA 93106 (United States)

    2011-01-15

    Research highlights: This work investigates the surface and bulk stability of W- and Re-rich Ni-based alloys under carburizing/oxidizing conditions (1000 {sup o}C) in order to understand the fundamental mechanisms of material degradation due to impurities in helium environment of the very high temperature helium-cooled reactor (VHTR). Depending on the alloy composition, carbides of type M{sub 6}C, M{sub 7}C{sub 3} or M{sub 23}C{sub 6} were observed, with a maximum carbon pickup between 0.06 and 0.12 wt.%. Alloys with high W content exhibited M{sub 6}C type carbides, whereas high Cr and low W alloys formed Cr-rich M{sub 23}C{sub 6} carbides. High additions of Re stabilized the M{sub 23}C{sub 6} phase due to its high solubility in these chromium-rich carbides. A continuous film of contiguous carbides (M{sub 6}C and M{sub 23}C{sub 6}) was observed in the grain boundaries; this is likely to be detrimental to the ductility and creep properties. During the first 50 h exposure, carbides were observed on the alloy surface as well as in the bulk with carbides precipitating in the grain interior and on the grain boundary. The (transient) surface carbides oxidized after prolonged exposure (100-225 h) forming stable Cr{sub 2}O{sub 3} oxide on the alloy surface. The work is particularly relevant to the development of strategies towards improvement of Ni-based alloys for intermediate heat exchangers (IHX) for service at 1000 {sup o}C in impure-He environment of the Next Generation Nuclear Plant (NGNP). - Abstract: The surface and microstructure stability of experimental W- and Re-rich Ni-based alloys in an impure-helium environment containing only CO and CO{sub 2} as impurities (ppm level) have been investigated at 1000 {sup o}C. All the alloys carburized during 50 h of exposure, and, depending on the alloy composition, different carbides of the type M{sub 6}C, M{sub 7}C{sub 3} and M{sub 23}C{sub 6} formed on the alloy surface, in grain interiors and at grain boundaries

  11. 10,000-Hour Cyclic Oxidation Behavior at 982 C (1800 F) of 68 High-Temperature Co-, Fe-, and Ni-Base Alloys

    Science.gov (United States)

    Barrett, Charles A.

    1997-01-01

    Sixty-eight high temperature Co-, Fe-, and Ni-base alloys were tested for 10-one thousand hour cycles in static air at 982 C (1800 F). The oxidation behavior of the test samples was evaluated by specific weight change/time data, x-ray diffraction of the post-test samples, and their final appearance. The gravimetric and appearance data were combined into a single modified oxidation parameter, KB4 to rank the cyclic oxidation resistance from excellent to catastrophic. The alloys showing the 'best' resistance with no significant oxidation attack were the alumina/aluminate spinel forming Ni-base turbine alloys: U-700, NASA-VIA and B-1900; the Fe-base ferritic alloys with Al: TRW-Valve, HOS-875, NASA-18T, Thermenol and 18SR; and the Ni-base superalloy IN-702.

  12. Effect of Co on Discontinuous Precipitation Transformation with TCP Phase in Ni-based Alloy Containing Re

    Science.gov (United States)

    Shi, Qianying; An, Ning; Huo, Jiajie; Zheng, Yunrong; Feng, Qiang

    2017-02-01

    The effect of Co on discontinuous precipitation (DP) transformation involving the formation of topologically close-packed (TCP) phase was investigated in three Ni-Cr-Re model alloys containing different levels of Co. One typical TCP phase, σ, was generated within DP cellular colonies along the migrating grain boundaries in experimental alloys during aging treatment. As a result of the increased solubility of Re in the γ matrix and enlarged interlamellar spacing of σ precipitates inside of growing DP colonies, Co addition suppressed the formation of σ phase and associated DP colonies. This study suggests that Co could potentially serve as a microstructural stabilizer in Re-containing Ni-base superalloys, which provides an alternative method for the composition optimization of superalloys.

  13. Lattice specific heat and local density of states of Ni-based dilute alloys at low temperature

    Indian Academy of Sciences (India)

    P D Semlaty; Kapil Dev; P N Ram

    2006-06-01

    A detailed theoretical study of the low-temperature lattice specific heat of Ni-based dilute alloys has been carried out. Lattice Green's function method has been used to calculate the local density of states of substitutional impurities and lattice specific heat in different alloys. The resonance condition has been investigated for possible occurrence of resonance modes. Except in NiCr and NiMn, low-frequency resonance modes have been obtained in all the alloys. However, no localized mode was obtained. The impurity-induced increase in lattice specific heat is explained on the basis of the obtained resonance modes. The calculation shows an excellent agreement with the measured lattice specific heat in these alloys

  14. Kinetics of germanium nanowire growth by the vapor-solid-solid mechanism with a Ni-based catalyst

    Directory of Open Access Journals (Sweden)

    Shruti V. Thombare

    2013-12-01

    Full Text Available The kinetics of vapor-solid-solid (VSS Ge nanowire growth using a Ni-based catalyst were investigated to probe the rate-limiting step for this complex nanoscale crystal growth process. The effects of key parameters such as temperature and precursor partial pressure on the nanowire growth rate were studied in order to gain detailed insights into the growth kinetics. Two different regimes were observed for VSS growth of Ge nanowires as function of temperature. At higher temperatures (345 °C–375 °C, kinetics data suggest that mass transport of germane precursor to the catalyst surface is rate limiting. At lower temperatures (<345 °C, either surface reaction of the GeH4 precursor on the catalyst or incorporation of Ge into the nanowire across the wire/catalyst interface is rate limiting.

  15. Effect of solidification parameters on the microstructures of a single crystal Ni-based superalloy AM3

    Institute of Scientific and Technical Information of China (English)

    Yu Zhuhuan; Liu Lin; Zhao Xinbao; Zhang Weiguo; Zhang Jun; Fu Hengzhi

    2010-01-01

    A single crystal Ni-based superalloy AM3 was processed at withdraw rates of 3.5, 10, 50, 100, 200, and 500 IJm-s-1, respectively. The as-cast microstructures and solidification segregation ratio were characterized with various withdraw rates. The shape and size of carbide microstructuras were determined. As expected, the primary and secondary dendrite arm spacings (PDAS and SDAS) decrease with the increase of withdraw rate. The highest volume fraction of eutectic γ/γ' is observed at the 100 μm·s-1 withdraw rate. The volume fraction of eutectic γ/γ' does not appear to be a strong function of the withdraw rate. With increasing withdraw rate, interface morphologies change in the sequence of planar, cellular, and dendrite. There is a general refinement of the microstructure as the withdraw rate increases. EPMA analysis showed that withdraw rate does not have obvious influence on the segregation of elements.

  16. Hardness and microstructural inhomogeneity at the epitaxial interface of laser 3D-printed Ni-based superalloy

    Science.gov (United States)

    Qian, Dan; Zhang, Anfeng; Zhu, Jianxue; Li, Yao; Zhu, Wenxin; Qi, Baolu; Tamura, Nobumichi; Li, Dichen; Song, Zhongxiao; Chen, Kai

    2016-09-01

    In this letter, microstructural and mechanical inhomogeneities, a great concern for single crystal Ni-based superalloys repaired by laser assisted 3D printing, have been probed near the epitaxial interface. Nanoindentation tests show the hardness to be uniformly lower in the bulk of the substrate and constantly higher in the epitaxial cladding layer. A gradient of hardness through the heat affected zone is also observed, resulting from an increase in dislocation density, as indicated by the broadening of the synchrotron X-ray Laue microdiffraction reflections. The hardening mechanism of the cladding region, on the other hand, is shown to originate not only from high dislocation density but also and more importantly from the fine γ/γ' microstructure.

  17. Three dimensional atom probe study of Ni-base alloy/low alloy steel dissimilar metal weld interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Kyoung Joon; Shin, Sang Hun; Kim, Jong Jin; Jung, Ju Ang; Kim, Ji Hyun [Interdisciplinary School of Green Energy, Ulsan National Institute of Science and Technology, Ulsan (Korea, Republic of)

    2012-08-15

    Three dimensional atom probe tomography (3D APT) is applied to characterize the dissimilar metal joint which was welded between the Ni-based alloy, Alloy 690 and the low alloy steel, A533 Gr. B, with Alloy 152 filler metal. While there is some difficulty in preparing the specimen for the analysis, the 3D APT has a truly quantitative analytical capability to characterize nanometer scale particles in metallic materials, thus its application to the microstructural analysis in multicomponent metallic materials provides critical information on the mechanism of nanoscale microstructural evolution. In this study, the procedure for 3D APT specimen preparation was established, and those for dissimilar metal weld interface were prepared near the fusion boundary by a focused ion beam. The result of the analysis in this study showed the precipitation of chromium carbides near the fusion boundary between A533 Gr. B and Alloy 152.

  18. V-Notched Bar Creep Life Prediction: GH3536 Ni-Based Superalloy Under Multiaxial Stress State

    Science.gov (United States)

    Zhang, D. X.; Wang, J. P.; Wen, Z. X.; Liu, D. S.; Yue, Z. F.

    2016-07-01

    In this study, creep experiments on smooth and circumferential V-type notched round bars were conducted in GH3536 Ni-based superalloy at 750 °C to identify notch strengthening effect in notched specimens. FE analysis was carried out, coupled with continuum damage mechanics (CDM), to analyze stress distribution and damage evolution under multiaxial stress state. The creep deformation of smooth specimens and the rupture life of both smooth and notched specimens showed good agreement between experimental results and FE analysis predictions; the creep rupture life for the notched specimen was successfully predicted via the "skeletal point" concept. Both creep damage analysis and the observed fracture morphology suggest that creep rupture started first at the root in the V-type notched specimens, and shifted to the region close to the notch root when the notch was relatively shallow compared to U-type notched specimens.

  19. Highly efficient growth of vertically aligned carbon nanotubes on Fe-Ni based metal alloy foils for supercapacitors

    Science.gov (United States)

    Amalina Raja Seman, Raja Noor; Asyadi Azam, Mohd; Ambri Mohamed, Mohd

    2016-12-01

    Supercapacitors are highly promising energy devices with superior charge storage performance and a long lifecycle. Construction of the supercapacitor cell, especially electrode fabrication, is critical to ensure good performance in applications. This work demonstrates direct growth of vertically aligned carbon nanotubes (CNTs) on Fe-Ni based metal alloy foils, namely SUS 310S, Inconel 600 and YEF 50, and their use in symmetric vertically aligned CNT supercapacitor electrodes. Alumina and cobalt thin film catalysts were deposited onto the foils, and then CNT growth was performed using alcohol catalytic chemical vapour deposition. By this method, vertically aligned CNTs were successfully grown and used directly as a binder-free supercapacitor electrode to deliver excellent electrochemical performance. The device showed relatively good specific capacitance, a superior rate capability and excellent cycle stability, maintaining about 96% capacitance up to 1000 cycles.

  20. Thermo-Catalytic Methane Decomposition for Hydrogen Production: Effect of Palladium Promoter on Ni-based Catalysts

    Directory of Open Access Journals (Sweden)

    Irene Lock Sow Mei

    2016-08-01

    Full Text Available Hydrogen production from the direct thermo-catalytic decomposition of methane is a promising alternative for clean fuel production. However, thermal decomposition of methane can hardly be of any practical and empirical interest in the industry unless highly efficient and effective catalysts, in terms of both catalytic activity and operational lifetime have been developed. In this study, the effect of palladium (Pd as a promoter onto Ni supported on alumina catalyst has been investigated by using co-precipitation technique. The introduction of Pd promotes better catalytic activity, operational lifetime and thermal stability of the catalyst. As expected, highest methane conversion was achieved at reaction temperature of 800 °C while the bimetallic catalyst (1 wt.% Ni -1wt.% Pd/Al2O3 gave the highest methane conversion of 70% over 15 min of time-on-stream (TOS. Interestingly, the introduction of Pd as promoter onto Ni-based catalyst also has a positive effect on the operational lifetime and thermal stability of the catalyst as the methane conversion has improved significantly over 240 min of TOS. Copyright © 2016 BCREC GROUP. All rights reserved Received: 21st January 2016; Revised: 6th February 2016; Accepted: 6th March 2016 How to Cite: Mei, I.L.S., Lock, S.S.M., Vo, D.V.N., Abdullah, B. (2016. Thermo-Catalytic Methane Decomposition for Hydrogen Production: Effect of Palladium Promoter on Ni-based Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2: 191-199 (doi:10.9767/bcrec.11.2.550.191-199 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.2.550.191-199

  1. Lymphocytotoxicity and immunosuppression by organotin compounds. Suppression of graft-versus-host reactivity, blast transformation, and E-rosette formation by Di-n-butyltindichloride and Di-n-Octyltindichloride

    NARCIS (Netherlands)

    Seinen, W.; Vos, J.G.; Brands, R.; Hooykaas, H.

    1979-01-01

    Di-n-butyltindichloride (DBTC) and di-n-octyltindichloride (DOTC) represent a new group of organometallic compounds with antilymphocytic properties. In rats they induce lymphocyte depletion in thymus and thymus-dependent areas of spleen and peripheral lymph nodes without signs of myelotoxicity or a

  2. Organometallic Polymers.

    Science.gov (United States)

    Carraher, Charles E., Jr.

    1981-01-01

    Reactions utilized to incorporate a metal-containing moiety into a polymer chain (addition, condensation, and coordination) are considered, emphasizing that these reactions also apply to smaller molecules. (JN)

  3. The preparation of highly active antimicrobial silver nanoparticles by an organometallic approach

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, Eduardo J; Garcia-Barrasa, Jorge; Lopez-de-Luzuriaga, Jose M; Monge, Miguel [Departamento de Quimica Grupo de SIntesis Quimica de La Rioja, UA-CSIC, Universidad de La Rioja, Complejo CientIfico-Tecnologico, E-26004 Logrono (Spain); Laguna, Antonio [Departamento de Quimica Inorganica, Instituto de Ciencia de Materiales de Aragon, Universidad de Zaragoza-CSIC, E-50009 Zaragoza (Spain); Torres, Carmen [Departamento de Agricultura y Alimentacion, Universidad de La Rioja, Complejo Cientifico-Tecnologico, E-26004 Logrono (Spain)], E-mail: eduardo.fernandez@unirioja.es

    2008-05-07

    Silver nanoparticles of small size with a high surface to volume ratio have been prepared using an organometallic approach. For this, the complex NBu{sub 4}[Ag(C{sub 6}F{sub 5}){sub 2}] has been treated with AgClO{sub 4} in a 1:1 molar ratio, giving rise to the nanoparticle precursor [Ag(C{sub 6}F{sub 5})] in solution. Addition of one equivalent of hexadecylamine (HDA) and 5 h of reflux in toluene leads to a deep yellow solution containing monodisperse silver nanoparticles (Ag NPs) of ca. 10 nm. This approach leads to nanoparticles with almost uncontaminated surfaces which make them very reactive. Antimicrobial studies show that these nanoparticles are very active as antimicrobial agents. Very low concentrations between 12 and 25 {mu}g ml{sup -1} of Ag NPs are enough to produce bacteriostatic and bactericidal effectiveness.

  4. A spectroscopic study of factors affecting charge transfer at organo-metallic interfaces

    CERN Document Server

    Tucker, C E

    2001-01-01

    polydiacetylene and omega-tricosenoic acid LB films. The resulting analyses have allowed comparison of charge trapping within the different bulk films and also at the film to substrate interface. In addition to DBARS, Fourier Transform Infra-red (FTIR) and Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopies have been used to investigate the factors affecting the carboxylic acid group at the head of the LB molecule and the role this plays in charge transport across the organo-metallic boundary. The properties of organic films produced by the Langmuir-Blodgett (LB) technique have become more widely known in the last few decades, as the variety of organic molecules suitable for this method of production has increased. One class of LB molecule receiving particular attention has been that of conjugated polymers. These organic materials exhibit an anisotropic semi-conductor like behavior along the polymer chain, making them suitable candidate materials for use in molecular electronic devices. However,...

  5. Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

    KAUST Repository

    Pump, Eva

    2016-08-15

    Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an emerging technique that allows access to high-sensitivity NMR spectra from surfaces. However, DNP SENS usually requires the use of radicals as an exogenous source of polarization, which has so far limited applications for organometallic surface species to those that do not react with the radicals. Here we show that reactive surface species can be studied if they are immobilized inside porous materials with suitably small windows, and if bulky nitroxide bi-radicals (here TEKPol) are used as the polarization source and which cannot enter the pores. The method is demonstrated by obtaining significant DNP enhancements from highly reactive complelxes [(equivalent to Si-O-)W(Me)(5)] supported on MCM-41, and effects of pore size (6.0, 3.0 and 2.5 nm) on the performance are discussed.

  6. Synthetic strategies for efficient conjugation of organometallic complexes with pendant protein reactive markers

    KAUST Repository

    Jantke, Dominik

    2013-11-01

    Site-directed conjugation of metal centers to proteins is fundamental for biological and bioinorganic applications of transition metals. However, methods for the site-selective introduction of metal centers remain scarce. Herein, we present broadly applicable synthetic strategies for the conjugation of bioactive molecules with a range of organometallic complexes. Following three different synthetic strategies, we were able to synthesize a small library of metal conjugated protein markers featuring different types of protein reactive sites (epoxides, phenylphosphonates, fluorosulfonates and fluorophosphonate groups) as well as different late transition metals (iron, ruthenium, rhodium, palladium and platinum). The products were isolated in moderate to excellent yields and high purity. Furthermore, X-ray diffraction of the metalated protein markers corroborates structural integrity of the metal complex and the protein reactive site. © 2013 Elsevier B.V. All rights reserved.

  7. Control and Characterization of Titanium Dioxide Morphology: Applications in Surface Organometallic Chemistry

    KAUST Repository

    Jeantelot, Gabriel

    2014-05-01

    Surface Organometallic Chemistry leads to the combination of the high activity and specificity of homogeneous catalysts with the recoverability and practicality of heterogeneous catalysts. Most metal complexes used in this chemistry are grafted on metal oxide supports such as amorphous silica (SiO2) and γ-alumina (Al2O3). In this thesis, we sought to enable the use of titania (TiO2) as a new support for single-site well-defined grafting of metal complexes. This was achieved by synthesizing a special type of anatase-TiO2, bearing a high density of identical hydroxyl groups, through hydrothermal synthesis then post-treatment under high vacuum followed by oxygen flow, and characterized by several analytical techniques including X-ray diffraction, transmission electron microscopy, infrared spectroscopy and nuclear magnetic resonance. Finally, as a proof of concept, the grafting of vanadium oxychloride (VOCl3) was successfully attempted.

  8. Hybrid Organometallic-Inorganic Nanomaterial: Acetyl Ferrocene Schiff base Immobilized on Silica Coated Magnetite Nanoparticles

    Directory of Open Access Journals (Sweden)

    M. Masteri-Farahani

    2015-10-01

    Full Text Available In  this  work,  a  new  hybrid  organometallic-inorganic  hybrid nanomaterial was prepared by immobilization of acetyl ferrocene on the  surface  of magnetite  nanoparticles. Covalent  grafting of silica coated magnetite nanoparticles (SCMNPs with 3-aminopropyl triethoxysilane gave aminopropyl-modified magnetite nanoparticles (AmpSCMNPs. Then, Schiff base condensation  of AmpSCMNPs with acetyl  ferrocene resulted in the preparation of acferro-SCMNPs hybrid nanomaterial. Characterization of the prepared nanomaterial was performed with different physicochemical methods such as Fourier transform infrared spectroscopy (FT-IR, X-ray diffraction (XRD, vibrating sample magnetometry (VSM, thermogravimetric analysis (TGA, scanning electron microscopy (SEM, and transmission electron microscopy (TEM. VSM analysis showed superparamagnetic properties of the prepared nanomaterial and TEM and SEM analyses indicated the relatively spherical nanoparticles with 15 nm average size.

  9. Anisotropic Mo2-phthalocyanine sheet: a new member of the organometallic family.

    Science.gov (United States)

    Zhu, Guizhi; Kan, Min; Sun, Qiang; Jena, Puru

    2014-01-09

    Metal-organic porous sheets, due to their unique atomic configurations and properties, represent a class of materials beyond graphene and BN monolayers. The Mo2-phthalocyanine-based sheet (Mo2Pc) is a new member of this porous organometallic family. Using density functional theory with hybrid functional for exchange-correlation potential, we show that this dimer-based material, unlike conventional organic monolayers that contain isolated metal atoms, possesses unique mechanical, magnetic, electronic, and optical properties due to inherent anisotropy in the structure. Furthermore, it is a semiconductor with a direct band gap of 0.93 eV and is antiferromagnetic with each Mo site carrying a magnetic moment of 0.88 μB. The strong anisotropy in elasticity and infrared light absorption is likely to open new doors for potential applications.

  10. On-Surface Observation of the Formation of Organometallic Complex in a Supramolecular Network

    Science.gov (United States)

    Li, Yibao; Cheng, Linxiu; Liu, Chunhua; Liu, Wei; Fan, Yulan; Fan, Xiaolin; Zeng, Qingdao

    2015-06-01

    The on-surface formation of organometallic monomers or oligomers, especially in supramolecular network, attracts an extensive interest for chemists and material scientist. In this work, we have investigated metal coordination between zinc (II) phthalocyanine (ZnPc) and 1, 3-di (4-pyridyl) propane (dipy-pra) in the 2, 6, 11-tricarboxydecyloxy-3, 7, 10-triundecyloxy triphenylene (asym-TTT) supramolecular template by means of scanning tunneling microscopy (STM) on highly oriented pyrolytic graphite (HOPG) substrate under ambient conditions. The experimental results demonstrate that every two ZnPc molecules in one nano-reactor connect with each other through one dipy-pra molecule by metal-coordination interaction. In this coordinating process, the template of asym-TTT supramolecular networks plays a significant role.

  11. Zigzag-shaped nickel nanowires via organometallic template-free route

    Energy Technology Data Exchange (ETDEWEB)

    Shviro, Meital; Paszternak, Andras [Bar Ilan Institute of Nanotechnology and Advanced Materials (BINA), Bar Ilan University, Department of Chemistry (Israel); Chelly, Avraham [Bar Ilan Institute of Nanotechnology and Advanced Materials (BINA), Bar Ilan University, Department of Engineering (Israel); Zitoun, David, E-mail: david.zitoun@biu.ac.il [Bar Ilan Institute of Nanotechnology and Advanced Materials (BINA), Bar Ilan University, Department of Chemistry (Israel)

    2013-08-15

    In this manuscript, the formation of nickel nanowires of 10-20 nm in diameter (average size: several tens to hundreds of {mu}m long and 1.0-1.5 {mu}m wide) at low temperature is found to be driven by dewetting of liquid organometallic precursors during spin-coating process and by self-assembly of Ni clusters. Elaboration of metallic thin films by low-temperature deposition technique makes the preparation process compatible with most of the substrates. The use of iron and cobalt precursor shows that the process could be extended to other metallic systems. In this work, AFM and SEM are used to follow the assembly of Ni clusters into straight or zigzag lines. The formation of zigzag structure is specific to the Ni precursor at appropriate preparation parameters. This template-free process allows a control of anisotropic structures with homogeneous sizes and angles on the standard Si/SiO{sub 2} surface.

  12. Quasi-one-dimensional spin-orbit-coupled correlated insulator in a multinuclear coordinated organometallic crystal

    Science.gov (United States)

    Merino, J.; Jacko, A. C.; Khosla, A. L.; Powell, B. J.

    2016-11-01

    We show how quasi-one-dimensional correlated insulating states arise at two-thirds filling in organometallic multinuclear coordination complexes described by layered decorated honeycomb lattices. The interplay of spin-orbit coupling and electronic correlations leads to pseudospin-one moments arranged in weakly coupled chains with highly anisotropic exchange and a large trigonal splitting. We show that the in-plane exchange coupling is very different from the interlayer coupling; in particular the latter is much larger, despite the underlying hopping integrals being close to isotropic. Surprisingly, the effective dimensionality of the pseudospin model is strongly dependent on the strength of the electronic correlations: With increasing Hubbard U the pseudospin-one model becomes increasingly one dimensional, even though the crystal is almost isotropic. We predict that the trigonal splitting leads to a quantum phase transition from a Haldane phase to a topologically trivial phase as the relative strength of the spin-orbit coupling increases.

  13. Combustion Synthesis of Fe-Incorporated SnO2 Nanoparticles Using Organometallic Precursor Combination

    Directory of Open Access Journals (Sweden)

    Thomas K. Barkley

    2012-01-01

    Full Text Available Synthesis of nanomaterials within flames has been demonstrated as a highly scalable and versatile approach for obtaining a variety of nanoparticles with respect to their chemistry, composition, size, morphology, and dimensionality. Its applicability can be amplified by exploring new material systems and providing further control over the particle characteristics. This study focused on iron-incorporated SnO2 nanoparticles generated using an inverse coflow diffusion flame burner that supported a near-stoichiometric methane-air combustion. A liquid organometallic precursor solution of Sn(CH34 and Fe(CO5 was used to produce 11–14 nm nanocrystalline particles. Synthesized particles were analyzed using TEM, XRD, and XEDS to characterize for size and composition. A flame temperature field was obtained to map particle evolution within the flame. A range of conditions and parameters were studied to specifically generate targeted particles. The study augments related research towards increasing the production potential of combustion synthesis.

  14. Reactivity of seventeen- and nineteen-valence electron complexes in organometallic chemistry

    Science.gov (United States)

    Stiegman, Albert E.; Tyler, David R.

    1986-01-01

    A guideline to the reactivity of 17- and 19-valence electron species in organometallic chemistry is proposed which the authors believe will supersede all others. The thesis holds that the reactions of 17-electron metal radicals are associatively activated with reactions proceeding through a 19-valence electron species. The disparate reaction chemistry of the 17-electron metal radicals are unified in terms of this associative reaction pathway, and the intermediacy of 19-valence electron complexes in producing the observed products is discussed. It is suggested that related associatively activated pathways need to be considered in some reactions that are thought to occur by more conventional routes involving 16- and 18-electron intermediates. The basic reaction chemistry and electronic structures of these species are briefly discussed.

  15. Organometallic Complexes Anchored to Conductive Carbon for Electrocatalytic Oxidation of Methane at Low Temperature.

    Science.gov (United States)

    Joglekar, Madhura; Nguyen, Vinh; Pylypenko, Svitlana; Ngo, Chilan; Li, Quanning; O'Reilly, Matthew E; Gray, Tristan S; Hubbard, William A; Gunnoe, T Brent; Herring, Andrew M; Trewyn, Brian G

    2016-01-13

    Low-temperature direct methane fuel cells (DMEFCs) offer the opportunity to substantially improve the efficiency of energy production from natural gas. This study focuses on the development of well-defined platinum organometallic complexes covalently anchored to ordered mesoporous carbon (OMC) for electrochemical oxidation of methane in a proton exchange membrane fuel cell at 80 °C. A maximum normalized power of 403 μW/mg Pt was obtained, which was 5 times higher than the power obtained from a modern commercial catalyst and 2 orders of magnitude greater than that from a Pt black catalyst. The observed differences in catalytic activities for oxidation of methane are linked to the chemistry of the tethered catalysts, determined by X-ray photoelectron spectroscopy. The chemistry/activity relationships demonstrate a tangible path for the design of electrocatalytic systems for C-H bond activation that afford superior performance in DMEFC for potential commercial applications.

  16. A Photoferroelectric Perovskite-Type Organometallic Halide with Exceptional Anisotropy of Bulk Photovoltaic Effects.

    Science.gov (United States)

    Sun, Zhihua; Liu, Xitao; Khan, Tariq; Ji, Chengmin; Asghar, Muhammad Adnan; Zhao, Sangen; Li, Lina; Hong, Maochun; Luo, Junhua

    2016-05-23

    Perovskite-type ferroelectrics composed of organometallic halides are emerging as a promising alternative to conventional photovoltaic devices because of their unique photovoltaic effects (PVEs). A new layered perovskite-type photoferroelectric, bis(cyclohexylaminium) tetrabromo lead (1), is presented. The material exhibits an exceptional anisotropy of bulk PVEs. Upon photoexcitation, superior photovoltaic behaviors are created along its inorganic layers, which are composed of corner-sharing PbBr6 octahedra. Semiconducting activity with remarkable photoconductivity is achieved in the vertical direction, showing sizeable on/off current ratios (>10(4) ), which compete with the most active photovoltaic material CH3 NH3 PbI3 . In 1 the temperature-dependence of photovoltage coincides fairly well with that of polarization, confirming the dominant role of ferroelectricity in such highly anisotropic PVEs. This finding sheds light on bulk PVEs in ferroelectric materials, and promotes their application in optoelectronic devices.

  17. Toward new organometallic architectures: synthesis of carbene-centered rhodium and palladium bisphosphine complexes. stability and reactivity of [PC(BIm)PRh(L)][PF6] pincers.

    Science.gov (United States)

    Plikhta, Andriy; Pöthig, Alexander; Herdtweck, Eberhardt; Rieger, Bernhard

    2015-10-05

    In this article, we report the synthesis of a tridentate carbene-centered bisphosphine ligand precursor and its complexes. The developed four-step synthetic strategy of a new PC(BIm)P pincer ligand represents the derivatization of benzimidazole in the first and third positions by (diphenylphosphoryl)methylene synthone, followed by phosphine deprotection and subsequent insertion of a noncoordinating anion. The obtained ligand precursor undergoes complexation, with PdCl2 and [μ-OCH3Rh(COD)]2 smoothly forming the target organometallics [PC(BIm)PPdCl][PF6] and [PC(BIm)PRh(L)][PF6] under mild hydrogenation conditions. A more detailed study of the rhodium complexes [PC(BIm)PRh(L)][PF6] reveals significant thermal stability of the PC(BIm)PRh moiety in the solid state as well as in solution. The chemical behavior of 1,3-bis(diphenylphosphinomethylene)benzimidazol-2-ylrhodium acetonitrile hexafluorophosphate has been screened under decarbonylation, hydrogenation, and hydroboration reaction conditions. Thus, the PC(BIm)PRh(I) complex is a sufficiently stable compound, with the potential to be applied in catalysis.

  18. 1H, 13C, 15N and 195Pt NMR studies of Au(III) and Pt(II) chloride organometallics with 2-phenylpyridine.

    Science.gov (United States)

    Pazderski, Leszek; Pawlak, Tomasz; Sitkowski, Jerzy; Kozerski, Lech; Szłyk, Edward

    2009-11-01

    (1)H, (13)C, (15)N and (195)Pt NMR studies of gold(III) and platinum(II) chloride organometallics with N(1),C(2')-chelated, deprotonated 2-phenylpyridine (2ppy*) of the formulae [Au(2ppy*)Cl(2)], trans(N,N)-[Pt(2ppy*)(2ppy)Cl] and trans(S,N)-[Pt(2ppy*)(DMSO-d(6))Cl] (formed in situ upon dissolving [Pt(2ppy*)(micro-Cl)](2) in DMSO-d(6)) were performed. All signals were unambiguously assigned by HMBC/HSQC methods and the respective (1)H, (13)C and (15)N coordination shifts (i.e. differences between chemical shifts of the same atom in the complex and ligand molecules: Delta(1H)(coord) = delta(1H)(complex) - delta(1H)(ligand), Delta(13C)(coord) = delta(13C)(complex) - delta(13C)(ligand), Delta(15N)(coord) = delta(15N)(complex) - delta(15N)(ligand)), as well as (195)Pt chemical shifts and (1)H-(195)Pt coupling constants discussed in relation to the known molecular structures. Characteristic deshielding of nitrogen-adjacent H(6) protons and metallated C(2') atoms as well as significant shielding of coordinated N(1) nitrogens is discussed in respect to a large set of literature NMR data available for related cyclometallated compounds.

  19. Ruthenium(II) and osmium(II) 1,2,3-triazolylidene organometallics: a preliminary investigation into the biological activity of 'click' carbene complexes.

    Science.gov (United States)

    Kilpin, Kelly J; Crot, Stéphanie; Riedel, Tina; Kitchen, Jonathan A; Dyson, Paul J

    2014-01-21

    Taking advantage of the facile and versatile synthetic properties of 'click' 1,2,3-triazolylidene N-heterocyclic carbenes (tzNHC's), a range of new organometallic Ru(II) and Os(II) arene complexes containing functionalised tzNHC ligands, [M(η(6)-p-cymene)(tzNHC)Cl2] [M = Ru(II), Os(II)], have been synthesised and fully characterised, including the X-ray crystal structure of one of the Os(II) complexes. The tzNHC ligands remain coordinated to the metal centres under relevant physiological conditions, and following binding to the model protein, ubiquitin. The in vitro cytotoxicity of the compounds towards human ovarian cancer cells is dependent on the substituent on the tzNHC ligand but is generally <50 μM and in some cases <1 μM, whilst still retaining a high degree of selectivity towards cancer cells over healthy cells (1.85 μM in A2780 ovarian cancer cells versus 435 μM in human embryonic kidney cells in one case).

  20. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    Energy Technology Data Exchange (ETDEWEB)

    Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-01-01

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

  1. Self-assembled hexanuclear organometallic cages: synthesis, characterization, and host-guest properties.

    Science.gov (United States)

    Han, Ying-Feng; Li, Hao; Zheng, Zhi-Fang; Jin, Guo-Xin

    2012-06-01

    A series of iridium- and rhodium-based hexanuclear organometallic cages containing 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone, 9,10-dihydroxy-1,4-anthraquinone, and 6,11-dihydroxynaphthacene-5,12-dione ligands were synthesized from the self-assembly of the corresponding molecular "clips" and 2,4,6-tri(4-pyridyl)-1,3,5-triazine ligands in good yields. These organometallic cages can form inclusion systems with a wide variety of π-donor substrates, including coronene, pyrene, [Pt(acac)(2)], and hexamethoxytriphenylene. The 1:1 complexation of the resulting supramolecular assemblies was confirmed by (1)H NMR spectroscopy. Large complexation shifts (Δδ>1 ppm) were observed in the (1)H NMR spectra of guests in the presence of cage [Cp*(6)M(6)(μ-DHNA)(3)(tpt)(2)](OTf)(6) (6a; M=Ir, tpt=2,4,6-tri(4-pyridyl)-1,3,5-triazine). The formation of discrete 1:1 donor-acceptor complexes, pyrene⊂6b (M=Rh), coronene⊂6a, coronene⊂6b, and [Pt(acac)(2)]⊂6a was confirmed by their single-crystal X-ray analyses. In these systems, the most important driving force for the formation of guest-host complexes is clearly the donor-acceptor π···π stacking interaction, including charge-transfer interactions between the electron-donating and electron-accepting aromatic components. These structures provide compelling evidence for the existence of strong attractive forces between the electron-deficient triazine core and electron-rich guest. The results presented here may provide useful guidance for designing artificial receptors for functional biomolecules.

  2. Fracture Behavior of TiNi Based Shape Memory Alloy Cold-rolled Tube

    Institute of Scientific and Technical Information of China (English)

    LI Yan-wu; LIU Fu-shun

    2006-01-01

    The microstructures and interfacial characteristics of matrices at the inwalls and the out-walls of the cold-rolled tube with different amounts of deformation were investigated by the scanning electronic microscope (SEM), the optical microscope (OM), and the transmission electronic microscope (TEM) techniques. It was observed that as the amount of deformation increases, the flaws nucleate at the out-walls of the cold rolled tube, the stress-induced martensites change from (11) type Ⅰ twins to (011) type Ⅱ twins and then to (100) compound twins, nanocrystals and bulk amorphisation happen, the high density dislocation causes stress concentration at the out-walls of the Ti50Ni50 cold-rolled tube, and then precipitates its fracture, and the Ti2Ni particles strengthen the grain boundaries and curb the dislocation movements during plastic deformation. The inhomogeneity level of the grains in the Ti50Ni50 alloy plays an important role on the fracture of the Ti50Ni50 cold rolled tube.

  3. The Improvement of Oxidation Resistance of a Re-Based Diffusion Barrier/Ni–Al Coating on the Single-Crystal Ni-Based TMS-82+ Superalloy

    NARCIS (Netherlands)

    Wu, Y.; Wang, Y.M.; Song, G.M.; Li, X.W.

    2011-01-01

    Oxidation behavior of a Re-based diffusion barrier/Ni–Al coated single-crystal (SC) Ni-based TMS-82+ superalloy was studied to compare with those of the base and Ni–Al coated superalloys under cyclic air at 1150 °C for 200 h. The base superalloy showed a negative mass gain due to extensive oxide spa

  4. Improvement of the Oxidation Resistance of the Single-Crystal Ni-Based TMS-82+ Superalloy by Ni–Al Coatings with/without the Diffusion Barrier

    NARCIS (Netherlands)

    Wu, Y.; Li, X.W.; Song, G.M.; Wang, Y.M.; Narita, T.

    2010-01-01

    Oxidation behavior of the uncoated base, Ni–Al coated and Re–Cr-Ni plus Ni–Al coated single-crystal (SC) Ni-based TMS-82+ superalloy is studied under cyclic air at 900ºC for 200 h to assess the oxidation resistance. Regardless of the coating processing, Ni–Al coating is effective in improving the ox

  5. Implantation of Y- and Hf-ions into a F-doped Ni-base superalloy improving the oxidation resistance at high temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Zschau, H.-E. [DECHEMA-Forschungsinstitut, Theodor-Heuss-Allee 25, D-60486 Frankfurt am Main (Germany); King, F. [Goethe-Universität Frankfurt am Main, Institut für Kernphysik, Max-von-Laue-Str. 1, D-60438 Frankfurt am Main (Germany); Galetz, M.C.; Schütze, M. [DECHEMA-Forschungsinstitut, Theodor-Heuss-Allee 25, D-60486 Frankfurt am Main (Germany)

    2015-12-15

    The surface modification of Ni-base alloys with low Al-contents (between 2 and 5 wt.%) with fluorine leads to the formation of a protective alumina scale under high temperature service conditions. The combined implantation of fluorine and reactive elements (Y, Hf) can increase the adherence of this alumina scale needed for technical applications.

  6. Effect of the interface on separation in multicapillary gas chromatography-based hyphenated techniques for speciation analysis of organometallic compounds.

    Science.gov (United States)

    Jitaru, Petru; Birzu, Adrian; Mocanu, Raluca; Adams, Freddy C

    2005-08-01

    This paper reports the effect of transfer line (TL) internal diameter (i.d.) on gas chromatographic separation characteristics such as efficiency and speed, when a multicapillary (MC) column is used for speciation analysis of mercury. Five different TL consisting of fused-silica capillaries with 0.15, 0.20, 0.25, 0.32, and 0.53 mm i.d. are compared. The separation efficiency and total chromatographic run time are critically affected by the i.d. of the TL. Narrow capillaries (i.d. or =35 psig) and wide TL (> or =0.25 mm i.d.).

  7. Alkaline earth organometallic compounds in homogeneous catalysis : Synthesis, characterization and catalytic activity of calcium and magnesium complexes

    NARCIS (Netherlands)

    Penafiel, Johanne

    2016-01-01

    Homogeneous catalysis has been developed mainly through the use of transition metal complexes. However, transition-metal catalysts, often highly toxic, are becoming increasingly rare and consequently more expensive. Therefore, the search for sustainable alternatives is nowadays of great importance.

  8. Reaction of the Anticancer Organometallic Ruthenium Compound, [(η6-p-CymeneRu(ATSCCl]PF6 with Human Serum Albumin

    Directory of Open Access Journals (Sweden)

    Floyd A. Beckford

    2010-01-01

    Full Text Available The reaction of [(η6-p-cymeneRu(ATSCCl]PF6 (ATSC =9-anthraldehyde thiosemicarbazone with human serum albumin was investigated at different temperatures using fluorescence and infrared spectrophotometry. The binding constant, K, for the reaction was determined using a number of different methods. Using a modified Stern-Volmer equation, K was determined to be 9.09×104,12.1×104, and 13.1×104 M−1 at 293 K, 298 K, and 308 K, respectively. A thermodynamic analysis showed that the reaction is spontaneous with ΔG being negative. The enthalpy of reaction ΔH=16.5 kJ mol−1 and the entropy of reaction ΔS=152 Jmol−1K−1. The values of ΔH and ΔS suggest that hydrophobic forces are dominant in the mode of interaction and that the process is mostly entropy driven.

  9. Photonics of a conjugated organometallic Pt-Ir polymer and its model compounds exhibiting hybrid CT excited states.

    Science.gov (United States)

    Soliman, Ahmed M; Fortin, Daniel; Zysman-Colman, Eli; Harvey, Pierre D

    2012-04-13

    Trans- dichlorobis(tri-n-butylphosphine)platinum(II) reacts with bis(2- phenylpyridinato)-(5,5'-diethynyl-2,2'-bipyridine)iridium(III) hexafluorophosphate to form the luminescent conjugated polymer poly[trans-[(5,5'-ethynyl-2,2'-bipyridine)bis(2- phenylpyridinato)-iridium(III)]bis(tri-n-butylphosphine)platinum(II)] hexafluorophosphate ([Pt]-[Ir])n. Gel permeation chromatography indicates a degree of polymerization of 9 inferring the presence of an oligomer. Comparison of the absorption and emission band positions and their temperature dependence, emission quantum yields, and lifetimes with those for models containing only the [Pt] or the [Ir] units indicates hybrid excited states including features from both chromophores.

  10. Photophysical properties of ruthenium(II) polypyridyl-gold(I) ethynyl dyads and triads containing mono- or diethynylphenanthroline incorporated into gold(I) triphenylphosphine organometallics.

    Science.gov (United States)

    Shiotsuka, Michito; Tsuji, Yasushi; Keyaki, Kazutoshi; Nozaki, Koichi

    2010-05-03

    A new ruthenium(II)-gold(I) dyad, [Ru(bpy)(2){5-{(PPh(3))-Au-C[tripe bond]C}-phen}](PF(6))(2) (2), with a different substituted site compared to [Ru(bpy)(2){3-{(PPh(3))-Au-C[triple bond]C}-phen}](PF(6))(2) (1), and a triad, [Ru(bpy)(2){3,6-bis{(PPh(3))-Au-C[triple bond]C}-phen}](PF(6))(2) (3), with an unsymmetric diethynylphenanthroline relative to [Ru(bpy)(2){3,8-bis{(PPh(3))-Au-C[triple bond]C}-phen}](PF(6))(2) (4) have been prepared. These four ruthenium(II)-gold(I) compounds showed typical metal-to-ligand charge-transfer (MLCT) absorption bands in the 400-550 nm region and a lowest energy pi-pi* absorption involved with the gold(I) perturbation in the 300-400 nm region. Broad emission bands assignable to the triplet MLCT transition were definitely observed in all compounds, indicating that the hybrid architecture constructed with Ru(II)-polypyridyl and Au(I)-ethynyl units converts the blue-green gold(I) perturbed pi-pi* phosphorescence into an orange MLCT-based emission. The transient absorption difference spectra of four compounds showed the difference in the electron transfer process between 2 and other compounds 1, 3, and 4 under the excited state. Ru(II)-Au(I) compounds except for 2 receive the supposed charge injection from a ruthenium center to an extended pi-conjugated ethynyl-substituted phenanthroline, which contains one or two gold(I) organometallic unit(s), while 2 undergoes the electron transfer process from the ruthenium center not to the 5-ethynylphenanthroline but to one of the bipyridyl ligands under the excited state. This hypothesis is supported by the deflection of the spots of 2 and [Ru(bpy)(3)](PF(6))(2) from a linear correlation line in a plot of E(0-0) versus DeltaE(1/2), which was based on the electrochemical and emission data of Ru(II)-Au(I) compounds and mononuclear ruthenium(II) polypyridyl complexes.

  11. Preparation of Surface Organometallic Catalysts by Gas-Phase Ligand Stripping and Reactive Landing of Mass-Selected Ions

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Grant E.; Laskin, Julia

    2010-12-27

    Organometallic complexes immobilized on surfaces combine the high selectivity of homogeneous catalysts with the ease of separation of catalyst from products of heterogeneous materials. Here we report a novel approach for the highly controlled preparation of surface organometallic catalysts by gas-phase ligand stripping combined with reactive landing of mass-selected ions onto self assembled monolayer surfaces. Collision induced dissociation is used to generate highly reactive undercoordinated metal complexes in the gas-phase for subsequent surface immobilization. Complexes with an open coordination shell around the metal center are demonstrated to show enhanced activity towards reactive landing in comparison to fully ligated species. In situ TOF-SIMS analysis indicates that the immobilized complexes exhibit behaviour consistent with catalytic activity when exposed to gaseous reagents.

  12. Search for the ground-state electronic configurations of correlated organometallic metallocenes from constraint density functional theory

    Science.gov (United States)

    Nawa, Kenji; Kitaoka, Yukie; Nakamura, Kohji; Imamura, Hiroshi; Akiyama, Toru; Ito, Tomonori; Weinert, M.

    2016-07-01

    The ground-state electronic configurations of the correlated organometallic metallocenes, M Cp2,M =V , Cr, Mn, Fe, Co, and Ni, are investigated using constraint density functional theory combined with nonempirical Ueff parameters determined from linear-response theory. The relative stability of the various d -orbital electronic configurations of these organometallic molecules is found to be sensitive to the amount of correlation. Using nonempirical values of Ueff, the calculated electronic configurations are in agreement with the experiments: 4A2 g ,3E2 g ,6A1 g ,1A1 g ,2E1 g , and 3A2 g for the VCp2,CrCp2,MnCp2,FeCp2,CoCp2 , and NiCp2, respectively.

  13. Stepwise construction of discrete parallelogram- and prism-shaped organometallic architectures based on half-sandwich rhodium fragments.

    Science.gov (United States)

    Gao, Wen-Xi; Lin, Yue-Jian; Jin, Guo-Xin

    2017-08-08

    Herein we describe how to take advantage of a multifunctional ligand to conveniently control the shapes and sizes of different types of discrete organometallic assemblies. Using a versatile ligand 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylate (HL(2-)), which features three kinds of chelating sites, together with half-sandwich rhodium fragments, a series of discrete organometallic complexes with tetranuclear parallelogram and hexanuclear trigonal prism shapes were achieved. The isomerization of the hexanuclear assemblies was confirmed by single-crystal X-ray diffraction analysis. The results also reiterate that pyridyl-substituted imidazole-4,5-dicarboxylate ligands can be used as multifunctional organic scaffolds in the construction of elegant architectures.

  14. Unravelling novel synergies between organometallic and biological partners: a quantum mechanics/molecular mechanics study of an artificial metalloenzyme.

    Science.gov (United States)

    Ortega-Carrasco, Elisabeth; Lledós, Agustí; Maréchal, Jean-Didier

    2014-07-06

    In recent years, the design of artificial metalloenzymes obtained by the insertion of homogeneous catalysts into biological macromolecules has become a major field of research. These hybrids, and the corresponding X-ray structures of several of them, are offering opportunities to better understand the synergy between organometallic and biological subsystems. In this work, we investigate the resting state and activation process of a hybrid inspired by an oxidative haemoenzyme but presenting an unexpected reactivity and structural features. An extensive series of quantum mechanics/molecular mechanics calculations show that the resting state and the activation processes of the novel enzyme differ from naturally occurring haemoenzymes in terms of the electronic state of the metal, participation of the first coordination sphere of the metal and the dynamic process. This study presents novel insights into the sensitivity of the association between organometallic and biological partners and illustrates the molecular challenge that represents the design of efficient enzymes based on this strategy.

  15. Facile synthesis of one-dimensional organometallic-organic hybrid polymers based on a diphosphorus complex and flexible bipyridyl linkers.

    Science.gov (United States)

    Elsayed Moussa, M; Attenberger, B; Peresypkina, E V; Fleischmann, M; Balázs, G; Scheer, M

    2016-08-21

    The selective synthesis of a series of new "ladderlike" one-dimensional organometallic-organic hybrid polymers is shown. The polymers are obtained from the reaction of the diphosphorus ligand complex [Cp2Mo2(CO)4(η(2)-P2)] with the copper salt [Cu(CH3CN)4]BF4 in the presence of flexible organic bipyridyl linkers in high selectivity. This unique behaviour is supported by DFT calculations.

  16. Preparation of tertiary amines by the reaction of iminium ions derived from unsymmetrical aminals with zinc and magnesium organometallics.

    Science.gov (United States)

    Werner, Veronika; Ellwart, Mario; Wagner, Andreas J; Knochel, Paul

    2015-04-17

    We report a convenient one-pot preparation of polyfunctional tertiary amines, including various biorelevant phenethylamines or ephedrine derivatives, via the reaction of new functionalized iminium ions with a variety of zinc and magnesium organometallic reagents. These iminium ions were generated from unsymmetrical aminals, obtained by the in situ addition of various amides to Tietze's iminium salt [Me2NCH2(+)CF3COO(-)]. A functionalized aniline, prepared by this method, was converted to a quinolidine via an intramolecular Heck reaction.

  17. Modification of the adsorption and catalytic properties of micro-and mesoporous materials by reactions with organometallic complexes

    Institute of Scientific and Technical Information of China (English)

    LEFEBVRE; Frédéric; PUTAJ; Piotr; BASSET; Jean-Marie

    2010-01-01

    This review describes the work of two laboratories in the field of the modification of micro-and mesoporous molecular sieves through reactions with organometallic complexes.The modification of zeolites can occur inside the pore channels or on the external surface,depending on the size of the organometallic complex.When the modification occurs on the external surface,it results in a decrease of the pore entrance,which will lead in turn to a modification of the sorption properties of the zeolite,by decreasing the rate of the adsorption(mainly by a kinetic control).Such a material can be also used in catalysis,because the external acid sites,which are responsible for side-reactions,have been removed upon grafting.When small organometallic complexes are used,they can fill the channels and cages of the zeolite and react with internal hydroxyl groups.Due to the high acidity of zeolites,the reaction occurs very easily(for example at-100℃ on faujasite),in contrast to what is observed on the external surface,therefore leading to high metal loadings.In that case,the modification of the sorption properties will be mainly related to a thermodynamic control.The resulting materials can be useful in catalysis,by combining the activity of the organometallic complex and properties(for example shape-selectivity) of the zeolite.Modification of mesoporous molecular sieves occurs always in the pores and results in altering of the sorption properties of the solid,by changing the interaction type between the sorbent and the sorbate.For example the sorption isotherm of alkanes is changed from type II to type III according to the IUPAC nomenclature.

  18. Química organometálica de superfície aplicada à preparação de catalisadores heterogêneos bem definidos Surface organometallic chemistry applied to the preparation of well defined heterogeneous catalysts

    Directory of Open Access Journals (Sweden)

    Silvana I. Wolke

    2002-11-01

    Full Text Available The study of the reactions of organometallic complexes with the surfaces of inorganic oxides, zeolites and metals constitutes the basis of Surface Organometallic Chemistry (SOMC. The basic rules of organometallic chemistry are often valid when applied to surfaces and well-defined surface organometallic complexes can be obtained. These complexes can be used as heterogeneous catalysts or, by controlled reactions, can be transformed in other species useful for a given catalytic reaction. In some cases, these catalysts exhibit higher activity and/or selectivity than their analogous molecular complexes.

  19. Infrared and Raman spectra of inorganic and coordination compounds theory and applications in inorganic chemistry

    CERN Document Server

    Nakamoto, Kazuo

    2008-01-01

    The Sixth Edition of this classic work comprises the most comprehensive and current guide to infrared and Raman spectra of inorganic, organometallic, bioinorganic, and coordination compounds. From fundamental theories of vibrational spectroscopy to applications in a variety of compound types, this has been extensively updated. New topics include the theoretical calculations of vibrational frequencies (DFT method), chemical synthesis by matrix co-condensation reactions, time-resolved Raman spectroscopy, and more. This volume is a core reference for chemists and medical professionals working with infrared or Raman spectroscopies and an excellent textbook for graduate courses.

  20. Viability modulation of cells immobilized in porous TiNi-based alloy scaffold under infrared and ultraviolet radiation

    Directory of Open Access Journals (Sweden)

    С. В. Гюнтер

    2016-01-01

    Full Text Available Cellular response to electromagnetic radiation depends on many factors including the microenvironment of cell. Different cells (spleen, bone marrow, and Ehrlich's adenocarcinoma, respond to the studied types of low-intensity radiation. Exposure to infrared (IR and ultraviolet (UV radiation of low intensity leads to significant change in the number of viable cells. Effects of low-intensity infrared (IR and ultraviolet (UV radiation on the number of viable cells were evaluated against the control group in which cells were exposed to natural daylight. The results showed that IR irradiation led to a 4.6-, 2.5-, and 1.3-fold increase in viable Ehrlich tumor, bone marrow, and spleen cells, respectively, while UV exposure led to a 3.9-, 1.5-, and 1.2-fold increase, respectively. The data show that the extracellular environment of bone marrow, tumor and spleen cell populations affects their viability and proliferative potency in porous TiNi-based scaffolds. IR- and UV irradiation of cell cultures immobilized in the scaffold affects the cell viability in populations of bone marrow, tumor, and spleen cells. In case of IR irradiation, cell viability was significantly improved, at the same time UV irradiation suppressed cell proliferation activity. The effect of IR irradiation can be used to resuscitate the cell area. The effect of UV irradiation can be used to destroy residual tumor lesions or other pathological cell populations.

  1. Effect of heat treatment on microstructure and mechanical properties of laser melting deposited Ni-base superalloy Rene Prime 41

    Energy Technology Data Exchange (ETDEWEB)

    Li, J. [Laboratory of Laser Materials Processing and Manufacturing, Beihang University (formerly Beijing University of Aeronautics and Astronautics), 37 Xueyuan Road, Beijing 100191 (China); Wang, H.M., E-mail: wanghm@buaa.edu.cn [Laboratory of Laser Materials Processing and Manufacturing, Beihang University (formerly Beijing University of Aeronautics and Astronautics), 37 Xueyuan Road, Beijing 100191 (China); Tang, H.B. [Laboratory of Laser Materials Processing and Manufacturing, Beihang University (formerly Beijing University of Aeronautics and Astronautics), 37 Xueyuan Road, Beijing 100191 (China)

    2012-07-30

    Highlights: Black-Right-Pointing-Pointer Extensive precipitation of {gamma} Prime particles resulted in high hardness and ductility. Black-Right-Pointing-Pointer Alignment and coalescence of {gamma} Prime precipitates induced decrease in strength. Black-Right-Pointing-Pointer Standard heat treatment for wrought Rene Prime 41 alloy is not suitable for the LMD alloy. - Abstract: Ni-base superalloy Rene Prime 41 was produced by the laser melting deposition (LMD) manufacturing process. The LMD material was solution treated at 1065 Degree-Sign C for 4 h followed by air quenching and aged at 760 Degree-Sign C for 16 h followed by air cooling. Microstructure of the as-deposited, solution treated and solution-aged alloys were characterized by scanning electron microscopy and transmission electron microscopy, and the tensile properties and hardness were tested. The solution-aged Rene Prime 41 superalloy showed high hardness, low strength and low ductility. The extensive precipitation of {gamma} Prime resulted in high hardness and ductility, and the subsequent alignment and coalescence of {gamma} Prime precipitates induced low strength. The structure-property relationships of the alloy under three different heat treating conditions were studied and results indicated that the standard heat treatment recommended for wrought Rene Prime 41 was not suitable for LMD alloy and had to be modified to realize optimum mechanical properties.

  2. Thin Co/Ni-based bottom pinned spin-transfer torque magnetic random access memory stacks with high annealing tolerance

    Science.gov (United States)

    Tomczak, Y.; Swerts, J.; Mertens, S.; Lin, T.; Couet, S.; Liu, E.; Sankaran, K.; Pourtois, G.; Kim, W.; Souriau, L.; Van Elshocht, S.; Kar, G.; Furnemont, A.

    2016-01-01

    Spin-transfer torque magnetic random access memory (STT-MRAM) is considered as a replacement for next generation embedded and stand-alone memory applications. One of the main challenges in the STT-MRAM stack development is the compatibility of the stack with CMOS process flows in which thermal budgets up to 400 °C are applied. In this letter, we report on a perpendicularly magnetized MgO-based tunnel junction (p-MTJ) on a thin Co/Ni perpendicular synthetic antiferromagnetic layer with high annealing tolerance. Tunnel magneto resistance (TMR) loss after annealing occurs when the reference layer loses its perpendicular magnetic anisotropy due to reduction of the CoFeB/MgO interfacial anisotropy. A stable Co/Ni based p-MTJ stack with TMR values of 130% at resistance-area products of 9 Ω μm2 after 400 °C anneal is achieved via moment control of the Co/Ta/CoFeB reference layer. Thinning of the CoFeB polarizing layer down to 0.8 nm is the key enabler to achieve 400 °C compatibility with limited TMR loss. Thinning the Co below 0.6 nm leads to a loss of the antiferromagnetic interlayer exchange coupling strength through Ru. Insight into the thickness and moment engineering of the reference layer is displayed to obtain the best magnetic properties and high thermal stability for thin Co/Ni SAF-based STT-MRAM stacks.

  3. In- and out-of-phase thermomechanical fatigue of a Ni-based single-crystal superalloy

    Directory of Open Access Journals (Sweden)

    Segersäll Mikael

    2014-01-01

    Full Text Available In this study, the difference between in-phase (IP and out-of-phase (OP thermomechanical fatigue (TMF cycling from 100 to 750 °C has been investigated for the Ni-based single-crystal superalloy MD2. In addition, two different crystal orientations were studied, the ⟨001⟩ and ⟨011⟩ orientations respectively. When comparing IP and OP TMF lives, a strain range dependency is found for the ⟨001⟩ direction. For high strain ranges, IP cycling leads to a higher number of cycles to failure compared to OP. However at lower strain ranges, OP cycling leads to a higher number of cycles to failure compared to IP. Microstructure investigation shows that for the ⟨001⟩ direction, deformation twinning within the γ/γ′-microstructure is much more pronounced during OP conditions compared to IP. However for the ⟨011⟩ direction, the opposite is observed; twinning is more pronounced during IP TMF. From the microstructure investigation it is also visible that intersections between twins seems to trigger formation of TCP phases and recrystallization. These intersections also work as initiation points for TMF damage.

  4. Detached Melt Nucleation during Diffusion Brazing of a Technical Ni-based Superalloy: A Phase-Field Study

    Science.gov (United States)

    Böttger, B.; Apel, M.; Laux, B.; Piegert, S.

    2015-06-01

    Advanced solidification processes like welding, soldering, and brazing are often characterized by their specific solidification conditions. But they also may include different types of melting processes which themselves are strongly influenced by the initial microstructures and compositions of the applied materials and therefore are decisive for the final quality and mechanical properties of the joint. Such melting processes are often not well- understood because - compared to other fields of solidification science - relatively little research has been done on melting by now. Also, regarding microstructure simulation, melting has been strongly neglected in the past, although this process is substantially different from solidification due to the reversed diffusivities of the involved phases. In this paper we present phase-field simulations showing melting, solidification and precipitation of intermetallic phases during diffusion brazing of directionally solidified and heat-treated high-alloyed Ni- based gas turbine blade material using different boron containing braze alloys. Contrary to the common belief, melting of the base material is not always planar and can be further accompanied by detached nucleation and growth of a second liquid phase inside the base material leading to polycrystalline morphologies of the joint after solidification. These findings are consistent with results from brazed laboratory samples, which were characterized by EDX and optical microscopy, and can be explained in terms of specific alloy thermodynamics and inter-diffusion kinetics. Consequences of the gained new understanding for brazing of high- alloyed materials are discussed.

  5. The effect of variations of cobalt content on the cyclic oxidation resistance of selected Ni-base superalloys

    Science.gov (United States)

    Barrett, Charles A.

    1987-01-01

    Cobalt levels were systematically varied in the Ni-base turbine alloys U-700 (cast), U-700m (PM/HIP), Waspaloy, Mar-M-247, In-738, Nimonic-115, U-720, and SX-R-150. the cobalt levels ranged from 0 wt pct to the nominal commercial content in each alloy. the alloys were tested in cyclic oxidation in static air at 1000, 1100 and 1150 C for 500, 200, and 100 hr, respectively. An oxidation attack parameter, Ka, derived from the specific weight change versus time data was used to evaluate the oxidation behavior of the alloys along with X-ray diffraction analysis of the surface oxides. The alloys tend to form either Cr2O3/chromite spinel or Al2O3/aluminate spinel depending on the Cr/Al ratio in the alloys. Alloys with a ratio of 3.5 or higher tend to favor the Cr oxides while those under 3.0 form mostly Al oxides. In general the Al2O3/aluminate spinel forming alloys have the better oxidation resistance. Increased cobalt content lowers the scaling resistance of the higher Cr allys while a 5.0 wt pct Co content is optimum for the Al controlling alloys. The refractory metals, particularly Ta, appear beneficial to both types of oxides, perhaps due to the formation of the omnipresent trirutile Ni(Ta, Cb, Mo, W)2O6. Both scales break down as increasing amounts of NiO are formed.

  6. Real-time microstructure imaging by Laue microdiffraction: A sample application in laser 3D printed Ni-based superalloys

    Science.gov (United States)

    Zhou, Guangni; Zhu, Wenxin; Shen, Hao; Li, Yao; Zhang, Anfeng; Tamura, Nobumichi; Chen, Kai

    2016-06-01

    Synchrotron-based Laue microdiffraction has been widely applied to characterize the local crystal structure, orientation, and defects of inhomogeneous polycrystalline solids by raster scanning them under a micro/nano focused polychromatic X-ray probe. In a typical experiment, a large number of Laue diffraction patterns are collected, requiring novel data reduction and analysis approaches, especially for researchers who do not have access to fast parallel computing capabilities. In this article, a novel approach is developed by plotting the distributions of the average recorded intensity and the average filtered intensity of the Laue patterns. Visualization of the characteristic microstructural features is realized in real time during data collection. As an example, this method is applied to image key features such as microcracks, carbides, heat affected zone, and dendrites in a laser assisted 3D printed Ni-based superalloy, at a speed much faster than data collection. Such analytical approach remains valid for a wide range of crystalline solids, and therefore extends the application range of the Laue microdiffraction technique to problems where real-time decision-making during experiment is crucial (for instance time-resolved non-reversible experiments).

  7. Direct methane solid oxide fuel cells based on catalytic partial oxidation enabling complete coking tolerance of Ni-based anodes

    Science.gov (United States)

    Lee, Daehee; Myung, Jaeha; Tan, Jeiwan; Hyun, Sang-Hoon; Irvine, John T. S.; Kim, Joosun; Moon, Jooho

    2017-03-01

    Solid oxide fuel cells (SOFCs) can oxidize diverse fuels by harnessing oxygen ions. Benefited by this feature, direct utilization of hydrocarbon fuels without external reformers allows for cost-effective realization of SOFC systems. Superior hydrocarbon reforming catalysts such as nickel are required for this application. However, carbon coking on nickel-based anodes and the low efficiency associated with hydrocarbon fueling relegate these systems to immature technologies. Herein, we present methane-fueled SOFCs operated under conditions of catalytic partial oxidation (CPOX). Utilizing CPOX eliminates carbon coking on Ni and facilitates the oxidation of methane. Ni-gadolinium-doped ceria (GDC) anode-based cells exhibit exceptional power densities of 1.35 W cm-2 at 650 °C and 0.74 W cm-2 at 550 °C, with stable operation over 500 h, while the similarly prepared Ni-yttria stabilized zirconia anode-based cells exhibit a power density of 0.27 W cm-2 at 650 °C, showing gradual degradation. Chemical analyses suggest that combining GDC with the Ni anode prevents the oxidation of Ni due to the oxygen exchange ability of GDC. In addition, CPOX operation allows the usage of stainless steel current collectors. Our results demonstrate that high-performance SOFCs utilizing methane CPOX can be realized without deterioration of Ni-based anodes using cost-effective current collectors.

  8. Simulation of oxidation-nitridation-induced microstructural degradation in a cracked Ni-based superalloy at high temperature

    Directory of Open Access Journals (Sweden)

    Yuan Kang

    2014-01-01

    Full Text Available In turbine engines, high temperature components made of superalloys may crack in a creep process during service. With the inward flux of the gases, e.g. oxygen and nitrogen, along those cracks, the microstructure of the superalloy substrate nearby the cracks may degrade by internal oxidation and nitridation. The aim of this study is to investigate and simulate the oxidation-nitridation-induced microstructural degradation in superalloys by taking a variant of Ni-based superalloy IN-792 as a sample. After the creep testing of the superalloy in air, the microstructures on the cross section of the superalloy were analysed in a scanning electron microscope, equipped with energy/wavelength dispersive systems. Internal oxidation and nitridation, presenting by Al/Ti oxides and nitrides, were observed under a porous and even cracked Cr-oxide scale which was formed on the superalloy surface or along the creep cracks connecting the superalloy surface. Meanwhile, the reinforcing γ′ precipitates were depleted. Such oxidation-nitridation-induced microstructural degradation was simulated by using an oxidation-diffusion model, focusing the diffusion of the alloying elements in metallic phases of the superalloy.

  9. Laser clad Ni-base alloy added nano- and micron-size CeO 2 composites

    Science.gov (United States)

    Zhang, Shi Hong; Li, Ming Xi; Cho, Tong Yul; Yoon, Jae Hong; Lee, Chan Gyu; He, Yi Zhu

    2008-07-01

    Micron-size Ni-base alloy (NBA) powders are mixed with both 1.5 wt% (%) micron-CeO 2 (m-CeO 2) and also 1.0-3.0% nano-CeO 2 (n-CeO 2) powders. These mixtures are coated on low carbon steel (Q235) by 2.0 kW CO 2 laser cladding. The effects on microstructures, microhardness and wear resistance of the coating by the addition of m- and n-CeO 2 powders to NBA (m- and n-CeO 2/NBA) have been investigated. Addition to the primary phases of γ-Ni, Cr 23C 6 and Ni 3B of NBA coating, CeNi 3 shows up both in m- and n-CeO 2/NBA coatings and CeNi 5 appears only in n-CeO 2/NBA coating. Directional dendrite and coarse equiaxed dendrite are grown in m-CeO 2/NBA coating from interface to central zone, whereas multi-oriented dendrite and fine equiaxed dendrite growth by addition of n-CeO 2. The microhardness and wear resistance of coatings are greatly improved by CeO 2 powder addition, and compared to the addition of 1.0% and 3.0%, 1.5% n-CeO 2/NBA is the best. Hardness and wear resistance of the coating improves with decreasing CeO 2 size from micron to nano.

  10. Effect of creep and oxidation on reduced fatigue life of Ni-based alloy 617 at 850 °C

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Xiang, E-mail: chenx@ornl.gov [Department of Nuclear, Plasma, and Radiological Engineering, University of Illinois at Urbana-Champaign, 104 South Wright Street, Urbana, IL 61801 (United States); Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN 37831 (United States); Yang, Zhiqing [Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN 37831 (United States); Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 (China); Sokolov, Mikhail A.; Erdman, Donald L. [Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN 37831 (United States); Mo, Kun; Stubbins, James F. [Department of Nuclear, Plasma, and Radiological Engineering, University of Illinois at Urbana-Champaign, 104 South Wright Street, Urbana, IL 61801 (United States)

    2014-01-15

    Low cycle fatigue (LCF) and creep–fatigue testing of Ni-based alloy 617 was carried out at 850 °C. Compared with its LCF life, the material’s creep–fatigue life decreases to different extents depending on test conditions. To elucidate the microstructure-fatigue property relationship for alloy 617 and the effect of creep and oxidation on its fatigue life, systematic microstructural investigations were carried out using scanning electron microscopy, energy-dispersive X-ray spectroscopy, and electron backscatter diffraction (EBSD). In LCF tests, as the total strain range increased, deformations concentrated near high angle grain boundaries (HAGBs). The strain hold period in the creep–fatigue tests introduced additional creep damage to the material, which revealed the detrimental effect of the strain hold time on the material fatigue life in two ways. First, the strain hold time enhanced the localized deformation near HAGBs, resulting in the promotion of intergranular cracking of alloy 617. Second, the strain hold time encouraged grain boundary sliding, which resulted in interior intergranular cracking of the material. Oxidation accelerated the initiation of intergranular cracking in alloy 617. In the crack propagation stage, if oxidation was promoted and the cyclic oxidation damage was greater than the fatigue damage, oxidation-assisted intergranular crack growth resulted in a significant reduction in the material’s fatigue life.

  11. Effect of Creep and Oxidation on Reduced Creep-Fatigue life of Ni-based Alloy 617 at 850 C

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Xiang [ORNL; Yang, Zhiqing [ORNL; Sokolov, Mikhail A [ORNL; ERDMAN III, DONALD L [ORNL; Mo, Kun [ORNL; Stubbins, James [ORNL

    2014-01-01

    Low cycle fatigue (LCF) and creep fatigue testing of Ni-based alloy 617 was carried out at 850 C. Compared with its LCF life, the material s creep fatigue life decreases to different extents depending on test conditions. To elucidate the microstructure-fatigue property relationship for alloy 617 and the effect of creep and oxidation on its fatigue life, systematic microstructural investigations were carried out using scanning electron microscopy, energy-dispersive X-ray spectroscopy, and electron backscatter diffraction (EBSD). In LCF tests, as the total strain range increased, deformations concentrated near high angle grain boundaries (HAGBs). The strain hold period in the creep fatigue tests introduced additional creep damage to the material, which revealed the detrimental effect of the strain hold time on the material fatigue life in two ways. First, the strain hold time enhanced the localized deformation near HAGBs, resulting in the promotion of intergranular cracking of alloy 617. Second, the strain hold time encouraged grain boundary sliding, which resulted in interior intergranular cracking of the material. Oxidation accelerated the initiation of intergranular cracking in alloy 617. In the crack propagation stage, if oxidation was promoted and the cyclic oxidation damage was greater than the fatigue damage, oxidation-assisted intergranular crack growth resulted in a significant reduction in the material s fatigue life.

  12. The precipitation of {eta} phase in an Fe-Ni-based superalloy with different Ti/Al ratios

    Energy Technology Data Exchange (ETDEWEB)

    Seifollahi, Masoumeh; Razavi, Seyed Hossein [Iran Univ. of Science and Technology IUST, Tehran (Iran, Islamic Republic of). School of Metallurgy and Materials Engineering; Kheirandish, Shahram [Iran Univ. of Science and Technology IUST, Tehran (Iran, Islamic Republic of). School of Metallurgy and Materials Engineering; IUST, Tehran (Iran, Islamic Republic of). Centre of Excellence for High Strength Alloys Technology; Abbasi, Seyed Mahdi [K.N. Toosi Univ. of Technology, Tehran (Iran, Islamic Republic of). Metallic Materials Research Center

    2013-04-15

    In this research, the formation and transformation mechanisms of {eta} (Ni{sub 3}Ti) phase in an Fe-Ni-based superalloy at different Ti/Al ratios were investigated. In addition to Ti content, Ti/Al ratio also affects the {eta} phase. So alloys with different Ti/Al ratios were prepared and the microstructures were analysed using optical and scanning electron microscopy and X-ray diffraction. The alloy with lower Ti but higher Ti/Al ratio has a higher {eta} volume fraction. Time-temperature-precipitation diagrams of {eta} phase in the superalloys with different Ti/Al ratios are also presented. Based on the experimental results, when the Ti/Al ratio was decreased from 20 to 3, the time and temperature of {eta} precipitation shifted to longer and higher values, respectively, and the {eta} volume fraction decreased. Ti/Al of 3 could significantly retard the formation of {eta} phase. Depending on the Ti/Al ratio, and the time and temperature of ageing, {eta} was precipitated at twin and grain boundaries or inside the grains, either by {gamma}' {yields} {eta} transformation or directly by formation of austenite. It was also shown that a high Ti/Al ratio in the alloy would reduce the fraction of twin boundaries after solution annealing which affects the {eta} phase nucleation.

  13. Corrosion Resistance of Ni-Based WC/Co Coatings Deposited by Spray and Fuse Process Varying the Oxygen Flow

    Science.gov (United States)

    Jiménez, H.; Olaya, J. J.; Alfonso, J. E.; Mtshali, C. B.; Pineda-Vargas, C. A.

    2017-08-01

    In this work, the effect of oxygen flow variation in the corrosion behavior of Ni-based WC/Co coatings deposited by spray and fuse process was investigated. The coatings were deposited on gray cast iron substrates using a Superjet Eutalloy thermal spraying gun. The morphology of the coatings was analyzed using scanning electron microscopy. The crystallographic phases were registered by x-ray diffraction (XRD), the diffraction patterns show the crystalline phases of the powder components with principal reflections for Ni and WC, the increase in flame temperature, due to the oxygen flow variation, generated amorphization in the nickel and an important crystallization of the planes (111) and (222) of WC as well as the decarburization of WC in W2C and W metallic. The corrosion behavior was investigated at room temperature in a 3.5% w/w aqueous solution of NaCl via potentiodynamic polarization. Electrochemical corrosion test showed that the coatings deposited under neutral flame conditions with an oxygen flow of 12.88 SCFH evidenced higher corrosion resistance. The chemical composition of the coatings and corrosion areas were analyzed by particle-induced x-ray emission, this technique permitting the corroboration of the decarburization process of WC determined by XRD and the formation of Cl structures.

  14. Abrasive Wear Behavior of WC Reinforced Ni-BASED Composite Coating Sprayed and Fused by Oxy-Acetylene Flame

    Science.gov (United States)

    Wang, Qun; Chen, Zhenhua; Ding, Zhang Xiong; Chen, Ding

    Microstructure of WC reinforced Ni-based self-fluxing alloy composite coating sprayed and fused by oxy-acetylene flame was investigated by scanning electron microscopy and energy dispersive X-ray Spectrometry, X-ray diffraction, and transmission electron microscopy. The wear performance of the coating was studied by a MLS-225 wet sand rubber wheel abrasive wear tester at various loads and sizes of abrasive particles. Also, the wear resistance of the coating was compared with uncoated ASTM1020 steel. The results indicated that the coating is bonded metallurgically to the substrate and has a homogeneous microstructure composed of both coarse WC and fine carbide and boride grains such as Cr7C3, Cr23C6, and Ni2B which disperse uniformly in the matrix of γ-Ni solid solution and Ni3B. The worn mass loss of the coating and ASTM1020 steel both increased with the load and size of abrasive particles, also, the coating has exhibited excellent abrasive wear resistance compared with ASTM1020 steel.

  15. Interdiffusion behavior between NiAlHf coating and Ni-based single crystal superalloy with different crystal orientations

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ruili; Gong, Xueyuan [School of Materials Science and Engineering, Beihang University (BUAA), No. 37, Xueyuan Road, Beijing 100191 (China); Peng, Hui [School of Materials Science and Engineering, Beihang University (BUAA), No. 37, Xueyuan Road, Beijing 100191 (China); Beijing Key Laboratory for Advanced Functional Material and Thin Film Technology, Beihang University (BUAA), No. 37, Xueyuan Road, Beijing 100191 (China); Key Laboratory of Aerospace Materials and Performance (Ministry of Education), Beihang University (BUAA), No. 37, Xueyuan Road, Beijing 100191 (China); Ma, Yue, E-mail: mayue@buaa.edu.cn [School of Materials Science and Engineering, Beihang University (BUAA), No. 37, Xueyuan Road, Beijing 100191 (China); Beijing Key Laboratory for Advanced Functional Material and Thin Film Technology, Beihang University (BUAA), No. 37, Xueyuan Road, Beijing 100191 (China); Key Laboratory of Aerospace Materials and Performance (Ministry of Education), Beihang University (BUAA), No. 37, Xueyuan Road, Beijing 100191 (China); Guo, Hongbo, E-mail: guo.hongbo@buaa.edu.cn [School of Materials Science and Engineering, Beihang University (BUAA), No. 37, Xueyuan Road, Beijing 100191 (China); Beijing Key Laboratory for Advanced Functional Material and Thin Film Technology, Beihang University (BUAA), No. 37, Xueyuan Road, Beijing 100191 (China); Key Laboratory of Aerospace Materials and Performance (Ministry of Education), Beihang University (BUAA), No. 37, Xueyuan Road, Beijing 100191 (China)

    2015-01-30

    Highlights: • The interdiffusion behavior between the NiAlHf coating and the superalloy substrate was influenced by the crystal orientation of the substrate alloy. • The structure of TCP phases formed in SRZ and IDZ was studied. • Studying the effect of orientation crystal of substrate on the formation of SRZ. - Abstract: NiAlHf coatings were deposited onto Ni-based single crystal (SC) superalloy with different crystal orientations by electron beam physical vapor deposition (EB-PVD). The effects of the crystal orientations of the superalloy substrate on inter-diffusion behavior between the substrate and the NiAlHf coating were investigated. Substrate diffusion zone (SDZ) containing needle-like μ phases and interdiffusion zone (IDZ) mainly consisting of the ellipsoidal and rod-like μ phases were formed in the SC alloy after heat-treatment 10 h at 1100 °C. The thickness of secondary reaction zone (SRZ) formed in the SC alloy with (0 1 1) crystal orientation is about 14 μm after 50 h heat-treatment at 1100 °C, which is relatively thicker than that in the SC alloy with (0 0 1) crystal orientation, whereas the IDZ revealed similar thickness.

  16. Deactivation mechanisms of Ni-based tar reforming catalysts as monitored by X-ray absorption spectroscopy.

    Science.gov (United States)

    Yung, Matthew M; Kuhn, John N

    2010-11-02

    Deactivation mechanisms of alumina-supported, Ni-based catalysts for tar reforming in biomass-derived syngas were evaluated using extended X-ray absorption fine structure (EXAFS) spectroscopy. Catalysts were characterized before and after catalytic reaction cycles and regeneration procedures, which included oxidation by a mixture of steam and air, and reduction in hydrogen. Qualitative analysis of the EXAFS spectra revealed that oxidation of a portion of the Ni in the catalysts to form an oxide phase and/or a sulfide phase were likely scenarios that led to catalyst deactivation with time-on-stream and with increased reaction cycles. Deactivation through carbon deposition, phosphorus poisoning, or changes in particle size were deemed as unlikely causes. Quantitative analysis of the EXAFS spectra indicated sulfur poisoning occurred with time-on-stream, and the contaminating species could not be completely removed during the regeneration protocols. The results also verified that Ni-containing oxide phases (most likely a spinel also containing Mg and Al) formed and contributed to the deactivation. This study validates the need for developing catalyst systems that will protect Ni from sulfur poisoning and oxide formation at elevated reaction and regeneration temperatures.

  17. Effects of Annealing on the Martensitic Transformation of Ni-Based Ferromagnetic Shape Memory Heusler Alloys and Nanoparticles

    Directory of Open Access Journals (Sweden)

    Tina Fichtner

    2015-03-01

    Full Text Available We report on the effects of annealing on the martensitic phase transformation in the Ni-based Heusler system: Mn50Ni40Sn10 and Mn50Ni41Sn9 powder and Co50Ni21Ga32 nanoparticles. For the powdered Mn50Ni40Sn10 and Mn50Ni41Sn9 alloys, structural and magnetic measurements reveal that post-annealing decreases the martensitic transformation temperatures and increases the transition hysteresis. This might be associated with a release of stress in the Mn50Ni40Sn10 and Mn50Ni41Sn9 alloys during the annealing process. However, in the case of Co50Ni21Ga32 nanoparticles, a reverse phenomenon is observed. X-ray diffraction analysis results reveal that the as-prepared Co50Ni21Ga32 nanoparticles do not show a martensitic phase at room temperature. Post-annealing followed by ice quenching, however, is found to trigger the formation of the martensitic phase. The presence of the martensitic transition is attributed to annealing-induced particle growth and the stress introduced during quenching.

  18. Effects of thermal aging on microstructures of low alloy steel–Ni base alloy dissimilar metal weld interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Kyoung Joon; Kim, Jong Jin [Interdisciplinary School of Green Energy, Ulsan National Institute of Science and Technology (UNIST), 100 Banyeon-ri, Eonyang-eup, Ulju-gun, Ulsan 689-798 (Korea, Republic of); Lee, Bong Ho [National Center for Nanomaterials Technology (NCNT), Pohang University of Science and Technology (POSTECH), 77 Cheongam-ro, Nam-gu, Pohang, Gyeongbuk 790-784 (Korea, Republic of); Bahn, Chi Bum [Argonne National Laboratory, 9700 S. Cass Ave, Lemont, IL 60439 (United States); Kim, Ji Hyun, E-mail: kimjh@unist.ac.kr [Interdisciplinary School of Green Energy, Ulsan National Institute of Science and Technology (UNIST), 100 Banyeon-ri, Eonyang-eup, Ulju-gun, Ulsan 689-798 (Korea, Republic of)

    2013-10-15

    In this study, the advanced instrumental analysis has been performed to investigate the effect of long-term thermal aging on the microstructural evolution in the fusion boundary region between weld metal and low alloy steel in dissimilar metal welds. A representative dissimilar weld mock-up made of Alloy 690-Alloy 152-A533 Gr. B was fabricated and aged at 450 °C for 2750 h. The micro- and nano-scale characterization were conducted mainly near in a weld root region by using optical microscopy, scanning electron microscopy, transmission electron microscopy, and three dimensional atom probe tomography. It was observed that the weld root was generally divided into several regions including dilution zone in the Ni-base alloy weld metal, fusion boundary, and heat-affected zone in the low alloy steel. A steep gradient was shown in the chemical composition profile across the interface between A533 Gr. B and Alloy 152. The precipitation of carbides was also observed along and near the fusion boundary of as-welded and aged dissimilar metal joints. It was also found that the precipitation of Cr carbides was enhanced by the thermal aging near the fusion boundary.

  19. Effects of thermal aging on microstructures of low alloy steel-Ni base alloy dissimilar metal weld interfaces

    Science.gov (United States)

    Choi, Kyoung Joon; Kim, Jong Jin; Lee, Bong Ho; Bahn, Chi Bum; Kim, Ji Hyun

    2013-10-01

    In this study, the advanced instrumental analysis has been performed to investigate the effect of long-term thermal aging on the microstructural evolution in the fusion boundary region between weld metal and low alloy steel in dissimilar metal welds. A representative dissimilar weld mock-up made of Alloy 690-Alloy 152-A533 Gr. B was fabricated and aged at 450 °C for 2750 h. The micro- and nano-scale characterization were conducted mainly near in a weld root region by using optical microscopy, scanning electron microscopy, transmission electron microscopy, and three dimensional atom probe tomography. It was observed that the weld root was generally divided into several regions including dilution zone in the Ni-base alloy weld metal, fusion boundary, and heat-affected zone in the low alloy steel. A steep gradient was shown in the chemical composition profile across the interface between A533 Gr. B and Alloy 152. The precipitation of carbides was also observed along and near the fusion boundary of as-welded and aged dissimilar metal joints. It was also found that the precipitation of Cr carbides was enhanced by the thermal aging near the fusion boundary.

  20. Erosion-corrosion behaviour of Ni-based superalloy Superni-75 in the real service environment of the boiler

    Energy Technology Data Exchange (ETDEWEB)

    Sidhu, T.S.; Prakash, S.; Agrawal, R.D.; Bhagat, R. [Shaheed Bhagat Singh College of Engineering & Technology, Ferozepur (India)

    2009-04-15

    The super-heater and re-heater tubes of the boilers used in thermal power plants are subjected to unacceptable levels of surface degradation by the combined effect of erosion-corrosion mechanism, resulting in the tube wall thinning and premature failure. The nickel-based superalloys can be used as boiler tube materials to increase the service life of the boilers, especially for the new generation ultra-supercritical boilers. The aim of the present investigation is to evaluate the erosion-corrosion behaviour of Ni-based superalloy Superni-75 in the real service environment of the coal-fired boiler of a thermal power plant. The cyclic experimental study was performed for 1000 h in the platen superheater zone of the coal-fired boiler where the temperature was around 900{sup o}C. The corrosion products have been characterized with respect to surface morphology, phase composition and element concentration using the combined techniques of X-ray diffractometry (XRD), scanning electron microscopy/energy-dispersive analysis (SEM/EDAX) and electron probe micro analyser (EPMA). The Superni-75 performed well in the coal-fired boiler environment, which has been attributed mainly to the formation of a thick band of chromium in scale due to selective oxidation of the chromium.

  1. Performance of Ni-based, Fe-based and Co-based Oxygen Carriers in Chemical-Looping Hydrogen Generation

    Institute of Scientific and Technical Information of China (English)

    Liang Hao; Zhang Xiwen; Fang Xiangchen; Yuan Honggang

    2013-01-01

    Ni-based, Fe-based and Co-based oxygen carriers with perovskite oxides used as the supports were prepared by citric acid complexation method. The oxygen carriers were characterized by thermal analysis, H2-temperature-programmed reduction and X-ray diffraction methods. Performance tests were evaluated through Chemical-Looping Hydrogen Genera-tion in a ifxed-bed reactor operating at atmospheric pressure. The characterization results showed that all samples were composed of metal oxides and perovskite oxides. Performance results indicated that CH4 conversion over the oxygen car-riers decreased in the following order:NiO/LaNiO3>Co2O3/LaCoO3>Fe2O3/LaFeO3. The ability of NiO/LaNiO3 and Fe2O3/LaFeO3 to decompose water was stronger than that of Co2O3/LaCoO3 as evidenced by our experiments. H2 amounting to 80 mL upon reacting on methane in every cycle could be completely oxidized by NiO/LaNiO3 at 900℃in the period from the third cycle to the eighth cycle.

  2. Effect of La2O3 on High-Temperature Oxidation Resistance of Electrospark Deposited Ni-BASED Coatings

    Science.gov (United States)

    Gao, Yuxin; Yi, Jian; Fang, Zhigang; Cheng, Hu

    2014-08-01

    The oxidation tests of electrospark deposited Ni-based coatings without and with 2.5 wt.% La2O3 were conducted at 960°C in air for 100 h. The oxidation kinetic of the coatings was studied by testing the weight gain. The phase structures and morphologies of the oxidized coatings were investigated by XRD and SEM. The experimental results show that the coatings with 2.5 wt.% La2O3 exhibits excellent high-temperature oxidation resistance including low oxidation rate and improved spallation resistance, due to the formation of a denser and more adherent oxide scale compared with that without La2O3. The effects of La2O3 on the oxidation resistance include the following two aspects: First, refinement of the coating grains promotes the selective oxidation of Cr, leading to the formation of protective chromia scale in a short time, and second, refinement of the oxide grains enhances the high-temperature creep rate, resulting in decrease of inner stress and improvement of spallation resistance of the oxide layer.

  3. Erosion–corrosion behaviour of Ni-based superalloy Superni-75 in the real service environment of the boiler

    Indian Academy of Sciences (India)

    T S Sidhu; S Prakash; R D Agrawal; Ramesh Bhagat

    2009-04-01

    The super-heater and re-heater tubes of the boilers used in thermal power plants are subjected to unacceptable levels of surface degradation by the combined effect of erosion–corrosion mechanism, resulting in the tube wall thinning and premature failure. The nickel-based superalloys can be used as boiler tube materials to increase the service life of the boilers, especially for the new generation tra-supercritical boilers. The aim of the present investigation is to evaluate the erosion–corrosion behaviour of Ni-based superalloy Superni-75 in the real service environment of the coal-fired boiler of a thermal power plant. The cyclic experimental study was performed for 1000 h in the platen superheater zone of the coal-fired boiler where the temperature was around 900°C. The corrosion products have been characterized with respect to surface morphology, phase composition and element concentration using the combined techniques of X-ray diffractometry (XRD), scanning electron microscopy/energy-dispersive analysis (SEM/EDAX) and electron probe micro analyser (EPMA). The Superni-75 performed well in the coal-fired boiler environment, which has been attributed mainly to the formation of a thick band of chromium in scale due to selective oxidation of the chromium.

  4. Effect of solution cooling rate on the γ' precipitation behaviors of a Ni-base P/M superalloy

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The effect of cooling rate on the cooling "/' precipitation behaviors was investigated in a Ni-base powder/metallurgy (P/M)superalioy (FGH4096).The empirical equations were established between the cooling rate and the average sizes of secondary and tertiary γ' precipitates within grains and tertiary γ' precipitates at grain boundaries,as well as the apparent width of grain boundaries.The results show that the average sizes of secondary or tertiary γ' precipitates are inversely correlated with the cooling rate.The shape of secondary γ' precipitates within grains changes from butterfly-like to spherical with the increase of cooling rate,but all the tertiary γ' precipitates formed are spherical in shape.It is also found that tertiary γ' may be precipitated in the latter part of the cooling cycle only if the cooling rate is not faster than 4.3℃/s,and the apparent width of grain boundaries decreases linearly with the increase of cooling rate.

  5. Investigation of the effects of Ni-based alloy K465 on the normal spectral emissivity during oxidation

    Science.gov (United States)

    Zhao, Shunan; Li, Xunfeng; Zhou, Xiaoming; Cheng, Keyong; Huai, Xiulan

    2016-09-01

    The normal spectral emissivity of Ni-based alloy K465 during oxidation is experimentally measured at 810, 914 and 998 °C for 12 h in air over the wavelength from 1.3 to 2.4 μm. The combined standard uncertainty of the normal spectral emissivity is less than 3%. The oscillations of the emissivity and the effects of oxidation temperature, heating time and wavelength on the emissivity are investigated. The oscillations of the emissivity are formed by the interference effect between the radiation from the surfaces of the substrate and the oxidation film. The oscillation extremums of the emissivity shift towards larger wavelengths as the oxidation process proceeds. The results show that the normal spectral emissivity increases as the temperature increases at the initial time. The normal spectral emissivity decreases as wavelength increases except for the occurrence of the oscillations of the emissivity. The normal spectral emissivity increases rapidly at the initial heating time, and the change of emissivity becomes slow when the oxidation tends to be saturated gradually. Besides, the emissivity fitting models versus heating time and wavelength are established, which fit the experimental results very well. The emissivity relative errors of the fitting models are less than 4%.

  6. Effect of impregnation phases on the performance of Ni-based anodes for low temperature solid oxide fuel cells

    Science.gov (United States)

    Liu, Zhangbo; Ding, Dong; Liu, Beibei; Guo, Weiwei; Wang, Wendong; Xia, Changrong

    2011-10-01

    Impregnated nanoparticles are very effective in improving the electrochemical performance of solid oxide fuel cell (SOFC) anodes possibly due to the extension of reaction sites and/or the enhancement of catalytic activity. In this work, samaria-doped ceria (SDC), pure ceria, samaria, and alumina oxides impregnated Ni-based anodes are fabricated to compare the site extending and the catalytic effects. Except for alumina, the impregnation of the other three nano-sized oxides could substantially enhance the performance of the anodes for the hydrogen oxidation reactions. Moreover, single cells with CeO2 and Sm2O3 impregnated anodes could exhibit as great performance as those with SDC impregnated anodes. When the impregnation loading reached the optimal value, 1.7 mmol cm-3, these cells exhibit very high performance, with peak power densities around 750 mW cm-2. The high performance of CeO2 and Sm2O3 impregnated anodes demonstrates that the improved performance are mainly attributed to the significantly improved electrochemical activities of the anodes, but not to the extension of triple-phase-boundary, and wet impregnation is indeed an alternative and effective technique to introduce these nano-sized catalytic active oxides into the anode configuration of SOFCs to enhance cell performance, stability and reliability.

  7. Determination of the mechanism and extent of surface degradation in Ni-based cathode materials after repeated electrochemical cycling

    Directory of Open Access Journals (Sweden)

    Sooyeon Hwang

    2016-09-01

    Full Text Available We take advantage of scanning transmission electron microscopy and electron energy loss spectroscopy to investigate the changes in near-surface electronic structure and quantify the degree of local degradation of Ni-based cathode materials with the layered structure (LiNi0.8Mn0.1Co0.1O2 and LiNi0.4Mn0.3Co0.3O2 after 20 cycles of delithiation and lithiation. Reduction of transition metals occurs in the near-surface region of cathode materials: Mn is the major element to be reduced in the case of relatively Mn-rich composition, while reduction of Ni ions is dominant in Ni-rich materials. The valences of Ni and Mn ions are complementary, i.e., when one is reduced, the other is oxidized in order to maintain charge neutrality. The depth of degradation zone is found to be much deeper in Ni-rich materials. This comparative analysis provides important insights needed for the devising of new cathode materials with high capacity as well as long lifetime.

  8. Influences of synthesis methods and modifier addition on the properties of Ni-based catalysts supported on reticulated ceramic foams

    Institute of Scientific and Technical Information of China (English)

    Vesna Nikoli; eljko Kamberovi; Zoran Ani; Marija Kora; Miroslav Soki; Vesna Maksimovi

    2014-01-01

    A method of synthesizing Ni-based catalysts supported onα-Al2O3-based foams was developed. The foams were impregnated with aqueous solutions of metal chlorides under an air atmosphere using an aerosol route. Separate procedures involved calcination to form oxides and drying to obtain chlorides on the foam surface. The synthesized samples were subsequently reduced with hydrogen. With respect to the Ni/Al2O3 catalysts, the chloride reduction route enabled the formation of a Ni coating without agglomerates or cracks. Further research included catalyst modification by the addition of Pd, Cu, and Fe. The influences of the additives on the degree of reduction and on the low-temperature reduction effectiveness (533 and 633 K) were examined and compared for the catalysts obtained from oxides and chlorides. Greater degrees of reduction were achieved with chlorides, whereas Pd was the most effective modifier among those investigated. The reduc-tion process was nearly complete at 533 K in the sample that contained 0.1wt%Pd. A lower reduction temperature was utilized, and the cal-cination step was avoided, which may enhance the economical and technological aspects of the developed catalyst production method.

  9. Redox responsive nanotubes from organometallic polymers by template assisted layer by layer fabrication

    Science.gov (United States)

    Song, Jing; Jańczewski, Dominik; Guo, Yuanyuan; Xu, Jianwei; Vancso, G. Julius

    2013-11-01

    Redox responsive nanotubes were fabricated by the template assisted layer-by-layer (LbL) assembly method and employed as platforms for molecular payload release. Positively and negatively charged organometallic poly(ferrocenylsilane)s (PFS) were used to construct the nanotubes, in combination with other polyions. During fabrication, multilayers of these polyions were deposited onto the inner pores of template porous membranes, followed by subsequent removal of the template. Anodized porous alumina and track-etched polycarbonate membranes were used as templates. The morphology, electrochemistry, composition and other properties of the obtained tubular structure were characterized by fluorescence microscopy, scanning (SEM) and transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) spectroscopy. Composite nanotubes, consisting of poly(acrylic acid) anions with PFS+ and nanoparticles including fluorophore labelled dextran and decorated quantum dots, with PFS polyelectrolytes were also fabricated, broadening the scope of the structures. Cyclic voltammograms of PFS containing nanotubes showed similar redox responsive behaviour to thin LbL assembled films. Redox triggered release of labelled macromolecules from these tubular structures demonstrated application potential in controlled molecular delivery.Redox responsive nanotubes were fabricated by the template assisted layer-by-layer (LbL) assembly method and employed as platforms for molecular payload release. Positively and negatively charged organometallic poly(ferrocenylsilane)s (PFS) were used to construct the nanotubes, in combination with other polyions. During fabrication, multilayers of these polyions were deposited onto the inner pores of template porous membranes, followed by subsequent removal of the template. Anodized porous alumina and track-etched polycarbonate membranes were used as templates. The morphology, electrochemistry, composition and other properties of the obtained tubular

  10. Gas phase studies of the Pesci decarboxylation reaction: synthesis, structure, and unimolecular and bimolecular reactivity of organometallic ions.

    Science.gov (United States)

    O'Hair, Richard A J; Rijs, Nicole J

    2015-02-17

    CONSPECTUS: Decarboxylation chemistry has a rich history, and in more recent times, it has been recruited in the quest to develop cheaper, cleaner, and more efficient bond-coupling reactions. Thus, over the past two decades, there has been intense investigation into new metal-catalyzed reactions of carboxylic substrates. Understanding the elementary steps of metal-mediated transformations is at the heart of inventing new reactions and improving the performance of existing ones. Fortunately, during the same time period, there has been a convergence in mass spectrometry (MS) techniques, which allows these catalytic processes to be examined efficiently in the gas phase. Thus, electrospray ionization (ESI) sources have been combined with ion-trap mass spectrometers, which in turn have been modified to either accept radiation from tunable OPO lasers for spectroscopy based structural assignment of ions or to allow the study of ion-molecule reactions (IMR). The resultant "complete" gas-phase chemical laboratories provide a platform to study the elementary steps of metal-catalyzed decarboxylation reactions in exquisite detail. In this Account, we illustrate how the powerful combination of ion trap mass spectrometry experiments and DFT calculations can be systematically used to examine the formation of organometallic ions and their chemical transformations. Specifically, ESI-MS allows the transfer of inorganic carboxylate complexes, [RCO2M(L)n](x), (x = charge) from the condensed to the gas phase. These mass selected ions serve as precursors to organometallic ions [RM(L)n](x) via neutral extrusion of CO2, accessible by slow heating in the ion trap using collision induced dissociation (CID). This approach provides access to an array of organometallic ions with well-defined stoichiometry. In terms of understanding the decarboxylation process, we highlight the role of the metal center (M), the organic group (R), and the auxiliary ligand (L), along with cluster nuclearity, in

  11. Photophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophore

    KAUST Repository

    Goswami, Subhadip

    2014-12-18

    A pair of diketopyrrolopyrrole (DPP) chromophores that are end-functionalized with platinum containing "auxochromes" were subjected to electrochemical and photophysical study. The chromophores contain either platinum acetylide or ortho-metalated 2-thienylpyridinyl(platinum) end-groups (DPP-Pt(CC) and DPP-Pt(acac), respectively). The ground state redox potentials of the chromophores were determined by solution electrochemistry, and the HOMO and LUMO levels were estimated. The chromophores\\' photophysical properties were characterized by absorption, photoluminescence, and time-resolved absorption spectroscopy on time scales from sub-picoseconds to microseconds. Density functional theory (DFT) computations were performed to understand the molecular orbitals involved in both the singlet and triplet excited state photophysics. The results reveal that in both platinum DPP derivatives the organometallic auxochromes have a significant effect on the chromophores\\' photophysics. The most profound effect is a reduction in the fluorescence yields accompanied by enhanced triplet yields due to spin-orbit coupling induced by the metal centers. The effects are most pronounced in DPP-Pt(acac), indicating that the orthometalated platinum auxochrome is able to induce spin-orbital coupling to a greater extent compared to the platinum acetylide units. (Figure Presented).

  12. Atmospheric pressure synthesis of photoluminescent hybrid materials by sequential organometallic vapor infiltration into polyethylene terephthalate fibers

    Energy Technology Data Exchange (ETDEWEB)

    Akyildiz, Halil I. [Department of Textile Engineering, Chemistry and Science, North Carolina State University, Raleigh, North Carolina 27695 (United States); Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695 (United States); Mousa, Moataz Bellah M. [Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, North Carolina 27695 (United States); Jur, Jesse S., E-mail: jsjur@ncsu.edu [Department of Textile Engineering, Chemistry and Science, North Carolina State University, Raleigh, North Carolina 27695 (United States)

    2015-01-28

    Exposing a polymer to sequential organometallic vapor infiltration (SVI) under low pressure conditions can significantly modify the polymer's chemical, mechanical, and optical properties. We demonstrate that SVI of trimethylaluminum into polyethylene terephthalate (PET) can also proceed readily at atmospheric pressure, and at 60 °C the extent of reaction determined by mass uptake is independent of pressure between 2.5 Torr and 760 Torr. At 120 °C, however, the mass gain is 50% larger at 2.5 Torr relative to that at 760 Torr, indicating that the precursor diffusion in the chamber and fiber matrix decreases at higher source pressure. Mass gain decreases, in general, as the SVI process temperature increases both at 2.5 Torr and 760 Torr attributed to the faster reaction kinetics forming a barrier layer, which prevents further diffusion of the reactive species. The resulting PET/Al-O{sub x} product shows high photoluminescence compared to untreated fibers. A physical mask on the polymer during infiltration at 760 Torr is replicated in the underlying polymer, producing an image in the polymer that is visible under UV illumination. Because of the reduced precursor diffusivity during exposure at 760 Torr, the image shows improved resolution compared to SVI performed under typical 2.5 Torr conditions.

  13. Study of surface relief gratings on azo organometallic films in picosecond regime.

    Science.gov (United States)

    Luc, J; Bouchouit, K; Czaplicki, R; Fillaut, J-L; Sahraoui, B

    2008-09-29

    Materials for optical data storage and optical information processing must exhibit good holographic properties. Many materials for these applications have been already proposed. Here we describe a grating inscription process characterized by short inscription time and long-time stability. A series of ruthenium-acetylide organometallic complexes containing an azobenzene fragment were synthesized. Photo-induced gratings were produced by short pulse (16 ps, 532 nm) laser irradiation. The surface relief gratings formed at the same time were observed by atomic force microscope. In this work, we highlight the short inscription times brought into play as well as the good temporal stability of these gratings stored at room temperature. We study the influence of the polarization states and the light intensity of writing beams on the dynamics of the surface relief gratings formation and we compare these results with those of a known representative of azobenzene derivative (Disperse Red 1). Lastly, we show that it is possible to write two-dimensional surface relief gratings.

  14. Low-Temperature Wet Conformal Nickel Silicide Deposition for Transistor Technology through an Organometallic Approach.

    Science.gov (United States)

    Lin, Tsung-Han; Margossian, Tigran; De Marchi, Michele; Thammasack, Maxime; Zemlyanov, Dmitry; Kumar, Sudhir; Jagielski, Jakub; Zheng, Li-Qing; Shih, Chih-Jen; Zenobi, Renato; De Micheli, Giovanni; Baudouin, David; Gaillardon, Pierre-Emmanuel; Copéret, Christophe

    2017-02-08

    The race for performance of integrated circuits is nowadays facing a downscale limitation. To overpass this nanoscale limit, modern transistors with complex geometries have flourished, allowing higher performance and energy efficiency. Accompanying this breakthrough, challenges toward high-performance devices have emerged on each significant step, such as the inhomogeneous coverage issue and thermal-induced short circuit issue of metal silicide formation. In this respect, we developed a two-step organometallic approach for nickel silicide formation under near-ambient temperature. Transmission electron and atomic force microscopy show the formation of a homogeneous and conformal layer of NiSix on pristine silicon surface. Post-treatment decreases the carbon content to a level similar to what is found for the original wafer (∼6%). X-ray photoelectron spectroscopy also reveals an increasing ratio of Si content in the layer after annealing, which is shown to be NiSi2 according to X-ray absorption spectroscopy investigation on a Si nanoparticle model. I-V characteristic fitting reveals that this NiSi2 layer exhibits a competitive Schottky barrier height of 0.41 eV and series resistance of 8.5 Ω, thus opening an alternative low-temperature route for metal silicide formation on advanced devices.

  15. Time resolved infrared studies of C-H bond activation by organometallics

    Energy Technology Data Exchange (ETDEWEB)

    Asplund, M.C. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley National Lab., CA (United States). Chemical Sciences Div.

    1998-06-01

    This work describes how step-scan Fourier Transform Infrared spectroscopy and visible and near infrared ultrafast lasers have been applied to the study of the photochemical activation of C-H bonds in organometallic systems, which allow for the selective breaking of C-H bonds in alkanes. The author has established the photochemical mechanism of C-H activation by Tp{sup *}Rh(CO){sub 2}(Tp{sup *} = HB-Pz{sup *}{sub 3}, Pz = 3,5-dimethylpyrazolyl) in alkane solution. The initially formed monocarbonyl forms a weak solvent complex, which undergoes a change in Tp{sup *} ligand connectivity. The final C-H bond breaking step occurs at different time scales depending on the structure of the alkane. In linear solvents, the time scale is <50 ns and cyclic alkanes is {approximately}200 ps. The reactivity of the Tp{sup *}Rh(CO){sub 2} system has also been studied in aromatic solvents. Here the reaction proceeds through two different pathways, with very different time scales. The first proceeds in a manner analogous to alkanes and takes <50 ns. The second proceeds through a Rh-C-C complex, and takes place on a time scale of 1.8 {micro}s.

  16. Active photonic devices based on colloidal semiconductor nanocrystals and organometallic halide perovskites

    Science.gov (United States)

    Suárez Alvarez, Isaac

    2016-10-01

    Semiconductor nanocrystals have arisen as outstanding materials to develop a new generation of optoelectronic devices. Their fabrication under simple and low cost colloidal chemistry methods results in cheap nanostructures able to provide a wide range of optical functionalities. Their attractive optical properties include a high absorption cross section below the band gap, a high quantum yield emission at room temperature, or the capability of tuning the band-gap with the size or the base material. In addition, their solution process nature enables an easy integration on several substrates and photonic structures. As a consequence, these nanoparticles have been extensively proposed to develop several photonic applications, such as detection of light, optical gain, generation of light or sensing. This manuscript reviews the great effort undertaken by the scientific community to construct active photonic devices based on these nanoparticles. The conditions to demonstrate stimulated emission are carefully studied by comparing the dependence of the optical properties of the nanocrystals with their size, shape and composition. In addition, this paper describes the design of different photonic architectures (waveguides and cavities) to enhance the generation of photoluminescence, and hence to reduce the threshold of optical gain. Finally, semiconductor nanocrystals are compared to organometallic halide perovskites, as this novel material has emerged as an alternative to colloidal nanoparticles.

  17. Binding and interaction of di- and tri-substituted organometallic triptycene palladium complexes with DNA.

    Science.gov (United States)

    Kumari, Rina; Bhowmick, Sourav; Das, Neeladri; Das, Prolay

    2014-10-01

    Two triptycene-based ligands with pendant bromophenyl units have been prepared. These triptycene derivatives have been used as synthons for the synthesis of di and tri nuclear palladium complexes. The organic molecules and their corresponding organometallic complexes have been fully characterized using nuclear magnetic resonance (NMR), infrared (IR) spectroscopy and mass spectrometry. The mode of binding and effect of the complexes on pUC19 plasmid, calf thymus DNA and oligomer duplex DNA have been investigated by a host of analytical methods. The complexes brought about unwinding of supercoiled plasmid and the unwinding angle was found to be related to the binding affinity of the complexes with DNA, where both these parameters were guided by the structure of the complexes. Concentration-dependent inhibition of endonuclease activity of SspI and BamHI by the complexes indicates preference for G/C sequence for binding to DNA. However, neither the complexes did not introduce any cleavage at abasic site in oligomer duplex DNA, nor they created linear form of the plasmid upon co-incubation with the DNA samples. The interactions of the complexes with DNA were found to be strongly guided by the structure of the complexes, where intercalation as well as groove binding was observed, without inflicting any damage to the DNA. The mode of interaction of the complexes with DNA was further confirmed by isothermal calorimetry.

  18. Formation of Organometallic Intermediate States in On-Surface Ullmann Couplings.

    Science.gov (United States)

    Barton, Dennis; Gao, Hong-Ying; Held, Philipp Alexander; Studer, Armido; Fuchs, Harald; Doltsinis, Nikos L; Neugebauer, Johannes

    2017-02-17

    Possible origins of the formation of organometallic intermediates in on-surface Ullmann couplings have been investigated by surface tunneling microscopy (STM) and density functional theory (DFT) calculations. We consider the case of iodobenzenes on the coinage metals Au, Ag and Cu. We found experimental evidence for the formation of surface vacancies and the presence of metal adatoms in these coupling reactions, which are taken as a hint for the reactive extraction of surface atoms by adsorbates. In a second step, we demonstrate by ab initio molecular dynamics calculations for aryl-iodides on copper that metal atoms can be pulled out of the surface to form metalorganic species. By contrast, a thermally activated provision of a metal atom from the surface to form an adatom is energetically unfavourable. Finally, we investigate the mechanism and energetics of the reactive extraction of surface metal atoms by means of (climbing-image) nudged-elastic-band density-functional theory calculations for iodobenzene on copper, silver and gold, and analyze our results in the light of the experimental findings.

  19. New organometallic salts as precursors for the functionalization of carbon nanotubes with metallic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Alonso-Nunez, G., E-mail: galonso@cnyn.unam.mx; Garza, L. Morales de la; Rogel-Hernandez, E.; Reynoso, E. [Universidad Nacional Autonoma de Mexico, Centro de Nanociencias y Nanotecnologia (Mexico); Licea-Claverie, A.; Felix-Navarro, R. M. [Instituto Tecnologico de Tijuana, Centro de Graduados e Investigacion (Mexico); Berhault, G. [UMR 5256 CNRS-Universite de Lyon, Institut de Recherches sur la Catalyse et l' Environnement de Lyon (France); Paraguay-Delgado, F. [Centro de Investigacion en Materiales Avanzados S. C. (Mexico)

    2011-09-15

    New organometallic salts were synthesized in aqueous solution and were used as precursors for the functionalization of carbon nanotubes (CNT) by metallic nanoparticles. The precursors were obtained by reaction between HAuCl{sub 4}, (NH{sub 4}){sub 2}PtCl{sub 6}, (NH{sub 4}){sub 2}PdCl{sub 6}, or (NH{sub 4}){sub 3}RhCl{sub 6} with cetyltrimethylammonium bromide (CTAB). The as-obtained (CTA){sub n}Me{sub x}Cl{sub y} salts (with Me = Au, Pt, Pd, Rh) were characterized by Fourier-transform infra-red (FTIR) spectroscopy, {sup 1}H nuclear magnetic resonance (NMR) spectroscopy, and thermogravimetric analysis. These precursors were then used to synthesize metallic nanoparticles of Au, Pt, Pd, and Rh over multiwalled carbon nanotubes (MWCNT). Characterization by scanning transmission electron microscopy (STEM) and thermogravimetric analysis under air reveals that the CNT-supported catalysts exhibit high loading and good dispersion of the metallic nanoparticles with small average particle sizes. The present preparation procedure therefore allows obtaining high densities of small metallic nanoparticles at the surface of MWCNT.

  20. Ligand exchange synthesis of organometallic Rh nanoparticles and application in explosive sensing

    Science.gov (United States)

    Srivastav, Amit K.; Agrawal, Bhavesh; Swami, Bhavya; Agrawal, Yadvendra K.; Maity, Prasenjit

    2017-06-01

    Alkyne {phenyl acetylene (PA) and 9-ethynylphenanthrene (EPT)}-ligated Rh nanoparticles ( 1 and 2, respectively) with mean diameter of 1.5 ± 0.2 nm were synthesized via a facile and high-yield biphasic ligand exchange protocol using similar sized ethylene glycol (EG)-stabilized Rh nanoparticles as precursors (EG:Rh). The synthesized organometallic Rh nanoparticles were convincingly characterized using several spectroscopic and microscopic techniques, e.g., Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1H NMR), optical absorption spectroscopy (UV-Vis), photoluminescence spectroscopy (PL), powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscope (TEM). We propose that the syntheses mechanism relies on catalytic acetylenic (≡C-H, carbon-hydrogen) bond breaking by EG:Rh followed by strong metal-carbon bond formation with a vinyldiene (>C═C═M) motif. The obtained 1 and 2 showed luminescence property, which arises from ligand structure through intraparticle conjugation. Electron-rich phenanthrene-ligated Rh nanoparticles ( 2) showed good sensing performance for detection of electron deficient nitro-aromatic explosive molecules (NA) in solution phase through luminescence quenching method.

  1. Organometallic halide perovskite/barium di-silicide thin-film double-junction solar cells

    Science.gov (United States)

    Vismara, R.; Isabella, O.; Zeman, M.

    2016-04-01

    Barium di-silicide (BaSi2) is an abundant and inexpensive semiconductor with appealing opto-electrical properties. In this work we show that a 2-μm thick BaSi2-based thin-film solar cell can exhibit an implied photo-current density equal to 41.1 mA/cm2, which is higher than that of a state-of-the-art wafer-based c-Si hetero-junction solar cell. This performance makes BaSi2 an attractive absorber for high-performing thin-film and multi-junction solar cells. In particular, to assess the potential of barium di-silicide, we propose a thin-film double-junction solar cell based on organometallic halide perovskite (CH3NH3PbI3) as top absorber and BaSi2 as bottom absorber. The resulting modelled ultra-thin double-junction CH3NH3PbI3 / BaSi2 (< 2 μm) exhibits an implied total photo-current density equal to 38.65 mA/cm2 (19.84 mA/cm2 top cell, 18.81 mA/cm2 bottom cell) and conversion efficiencies up to 28%.

  2. Long-term creep rupture strength of weldment of Fe-Ni based alloy as candidate tube and pipe for advanced USC boilers

    Energy Technology Data Exchange (ETDEWEB)

    Bao, Gang; Sato, Takashi [Babcok-Hitachi K.K., Hiroshima (Japan). Kure Research Laboratory; Marumoto, Yoshihide [Babcok-Hitachi K.K., Hiroshima (Japan). Kure Div.

    2010-07-01

    A lot of works have been going to develop 700C USC power plant in Europe and Japan. High strength Ni based alloys such as Alloy 617, Alloy 740 and Alloy 263 were the candidates for boiler tube and pipe in Europe, and Fe-Ni based alloy HR6W (45Ni-24Fe-23Cr-7W-Ti) is also a candidate for tube and pipe in Japan. One of the Key issues to achieve 700 C boilers is the welding process of these alloys. Authors investigated the weldability and the long-term creep rupture strength of HR6W tube. The weldments were investigated metallurgically to find proper welding procedure and creep rupture tests are ongoing exceed 38,000 hours. The long-term creep rupture strengths of the HST weld joints are similar to those of parent metals and integrity of the weldments was confirmed based on with other mechanical testing results. (orig.)

  3. The Effect of CeO2 Addition on the Microstructure and Properties of Ni-Based Flame-Spray Coatings

    Science.gov (United States)

    Zhang, Zhenyu; Liang, Bunv; Guo, Hongjian

    2014-04-01

    Ni-based alloy with different amount of CeO2 powders were flame sprayed and melted onto 1045 carbon steel substrate. Microstructure and properties of the coatings were studied by XRD, field emission gun scanning electron microscope (FEGSEM) and SEM analyses. The wear behavior of the coatings was investigated under dry sliding wear conditions, and was compared with that of the coatings without CeO2, The results show that the microstructure of the coating with CeO2 differs widely from the coating without CeO2, the novel microstructure is beneficial for wear resistance. Abrasive wear tests without lubricant and analysis of the worn surfaces revealed that the Ni-based alloy coatings with the addition of 0.8% CeO2 exhibit higher wear resistance.

  4. Effect of solid-solution temperature on the microstructure of Fe-Ni based high strength low thermal expansion (HSLTE) alloy

    Institute of Scientific and Technical Information of China (English)

    Yifan Tu; Jin Xu; Jianfu Zhang; Boping Zhang; Dongliang Zhao

    2007-01-01

    The influence of solid-solution temperature on the dissolution of carbide precipitates,the average grain size and the microhardness of the austenite matrix in an Fe-Ni based high strength low thermal expansion (HSLTE) alloy was investigated to obtain the proper temperature range of the solid-solution process.The XRD analysis,microstructure observations,and the theoretical calculations showed that the Mo-rich M2C-type precipitates in the Fe-Ni based HSLTE alloy dissolve completely at about 1100 ℃.The average grain size of the studied alloys increases from 14 to 46 μm in the temperature range of 1050 to 1200 ℃.The microhardness of the matrix decreases first for the sake of solid-solution treatment,but then increases later with increasing solution temperature because of the solution strengthening effect.

  5. Nano-structureal and nano-chemical analysis of Ni-based alloy/low alloy steel dissimilar metal weld interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Kyoung Joon; Shin, Sang Hun; Kim, Jong Jin; Jung, Ju Ang; Kim, Ji Hyun [Interdisciplinary School of Green Energy, Ulsan National Institute of Science and Technology (UNIST), Ulsan (Korea, Republic of)

    2012-06-15

    The dissimilar metal joints welded between Ni-based alloy, Alloy 690 and low alloy steel, A533 Gr. B with Alloy 152 filler metal were characterized by using optical microscope, scanning electron microscope, transmission electron microscope, secondary ion mass spectrometry and 3-dimensional atom probe tomography. It was found that in the weld root region, the weld was divided into several regions including unmixed zone in Ni-base alloy, fusion boundary, and heat-affected zone in the low alloy steel. The result of nanostructural and nanochemical analyses in this study showed the non-homogeneous distribution of elements with higher Fe but lower Mn, Ni and Cr in A533 Gr. B compared with Alloy 152, and the precipitation of carbides near the fusion boundary.

  6. Development of a High Chromium Ni-Base Filler Metal Resistant to Ductility Dip Cracking and Solidification Cracking

    Science.gov (United States)

    Hope, Adam T.

    Many nuclear reactor components previously constructed with Ni-based alloys containing 20 wt% Cr have been found to be susceptible to stress corrosion cracking. The nuclear power industry now uses high chromium (˜30wt%) Ni-based filler metals to mitigate stress corrosion cracking. Current alloys are plagued with weldability issues, either solidification cracking or ductility dip cracking (DDC). Solidification cracking is related to solidification temperature range and the DDC is related to the fraction eutectic present in the microstructure. It was determined that an optimal alloy should have a solidification temperature range less than 150°C and at least 2% volume fraction eutectic. Due to the nature of the Nb rich eutectic that forms, it is difficult to avoid both cracking types simultaneously. Through computational modeling, alternative eutectic forming elements, Hf and Ta, have been identified as replacements for Nb in such alloys. Compositions have been optimized through a combination of computational and experimental techniques combined with a design of experiment methodology. Small buttons were melted using commercially pure materials in a copper hearth to obtain the desired compositions. These buttons were then subjected to a gas tungsten arc spot weld. A type C thermocouple was used to acquire the cooling history during the solidification process. The cooling curves were processed using Single Sensor Differential Thermal Analysis to determine the solidification temperature range, and indicator of solidification cracking susceptibility. Metallography was performed to determine the fraction eutectic present, an indicator of DDC resistance. The optimal level of Hf to resist cracking was found to be 0.25 wt%. The optimal level of Ta was found to be 4 wt%. gamma/MC type eutectics were found to form first in all Nb, Ta, and Hf-bearing compositions. Depending on Fe and Cr content, gamma/Laves eutectic was sometimes found in Nb and Ta-bearing compositions, while

  7. Effect of Mo content on microstructure and stress-rupture properties of a Ni-base single crystal superalloy

    Directory of Open Access Journals (Sweden)

    Yunfei Liang

    2016-02-01

    Full Text Available The additional 1.5 wt% Mo was added in a Ni-base single crystal (SC alloy with the composition of Ni–6.5Al–8.0Mo–2.4Cr–6.2Ta–4.9Co–1.5Re–(0.01–0.05Y (wt% to study the effect of Mo content on the microstructure and stress-rupture properties. The creep and stress-rupture tests under the conditions of 850 °C/500 MPa and 1100 °C/130 MPa were conducted, and the microstructure of as-cast, heat treated and stress ruptured specimens were analyzed. It was found that the 1.5 wt% Mo addition enhanced the stress-rupture lives at both intermediate (850 °C and high (1100 °C temperatures. The microstructure analysis showed that adding 1.5 wt% Mo in the basic alloy affected the microstructure dramatically, i.e., the Mo-rich phases formed in the specimens of as-cast and stress-ruptured specimens. It is considered that the improvement of the stress-rupture lives is duo to the strengthening effect of Mo to both γ and γ′ phases and the decrease of stacking fault energy, diffusion constant and dislocation spacing. The Mo-rich phases precipitated under condition of 1100 °C/130 MPa did not affect the creep and stress-rupture properties obviously in the present study.

  8. The Effects of Strain-Annealing on Tuning Permeability and Lowering Losses in Fe-Ni-Based Metal Amorphous Nanocomposites

    Science.gov (United States)

    Aronhime, Natan; DeGeorge, Vincent; Keylin, Vladimir; Ohodnicki, Paul; McHenry, Michael E.

    2017-07-01

    Fe-Ni-based metal amorphous nanocomposites with a range of compositions (Fe100-x Ni x )80Nb4Si2B14 (30 ≤ x ≤ 70) are investigated for motor and transformer applications, where it is beneficial to have tunable permeability. It is shown that strain annealing offers an effective method for tuning permeability in these alloys. For an Fe-rich alloy, permeability increased from 4000 to 16,000 with a positive magnetostriction. In a Ni-rich alloy, permeability decreased from 290 to 40 with a negative magnetostriction. Significant elongations (above 60%) are observed during strain annealing at high stress. Crystallization products have been determined in all alloys heated to 480°C. γ-FeNi is formed in all alloys, while (Fe30Ni70)80Nb4Si2B14 also undergoes secondary crystallization at temperatures of approximately 480°C to form a phase with the Cr23C6-type structure and a likely composition of Fe21Nb2B6. Toroidal losses have been measured for (Fe70Ni30)80Nb4Si y B16-y (0 ≤ y ≤ 3) at various annealing temperatures. At an induction of 1 T and frequency of 400 Hz and 1 kHz, the toroidal losses obtained are W1.0T, 400 Hz = 0.9 W/kg and W1.0T, 1 kHz = 2.3 W/kg, respectively. These losses are lower than losses recently reported for state of the art 3.0% and 6.5% silicon steels, a Metglas Fe-based amorphous alloy, and some Fe-based nanocomposites.

  9. Thin Co/Ni-based bottom pinned spin-transfer torque magnetic random access memory stacks with high annealing tolerance

    Energy Technology Data Exchange (ETDEWEB)

    Tomczak, Y., E-mail: Yoann.Tomczak@imec.be [IMEC Kapeldreef 75, B-3001 Leuven (Belgium); Department of Chemistry, KU Leuven (University of Leuven), Celestijnenlaan 200F, B-3001 Leuven (Belgium); Swerts, J.; Mertens, S.; Lin, T.; Couet, S.; Sankaran, K.; Pourtois, G.; Kim, W.; Souriau, L.; Van Elshocht, S.; Kar, G.; Furnemont, A. [IMEC Kapeldreef 75, B-3001 Leuven (Belgium); Liu, E. [Department of Chemistry, KU Leuven (University of Leuven), Celestijnenlaan 200F, B-3001 Leuven (Belgium)

    2016-01-25

    Spin-transfer torque magnetic random access memory (STT-MRAM) is considered as a replacement for next generation embedded and stand-alone memory applications. One of the main challenges in the STT-MRAM stack development is the compatibility of the stack with CMOS process flows in which thermal budgets up to 400 °C are applied. In this letter, we report on a perpendicularly magnetized MgO-based tunnel junction (p-MTJ) on a thin Co/Ni perpendicular synthetic antiferromagnetic layer with high annealing tolerance. Tunnel magneto resistance (TMR) loss after annealing occurs when the reference layer loses its perpendicular magnetic anisotropy due to reduction of the CoFeB/MgO interfacial anisotropy. A stable Co/Ni based p-MTJ stack with TMR values of 130% at resistance-area products of 9 Ω μm{sup 2} after 400 °C anneal is achieved via moment control of the Co/Ta/CoFeB reference layer. Thinning of the CoFeB polarizing layer down to 0.8 nm is the key enabler to achieve 400 °C compatibility with limited TMR loss. Thinning the Co below 0.6 nm leads to a loss of the antiferromagnetic interlayer exchange coupling strength through Ru. Insight into the thickness and moment engineering of the reference layer is displayed to obtain the best magnetic properties and high thermal stability for thin Co/Ni SAF-based STT-MRAM stacks.

  10. Hydrodeoxygenation of prairie cordgrass bio-oil over Ni based activated carbon synergistic catalysts combined with different metals.

    Science.gov (United States)

    Cheng, Shouyun; Wei, Lin; Zhao, Xianhui; Kadis, Ethan; Cao, Yuhe; Julson, James; Gu, Zhengrong

    2016-06-25

    Bio-oil can be upgraded through hydrodeoxygenation (HDO). Low-cost and effective catalysts are crucial for the HDO process. In this study, four inexpensive combinations of Ni based activated carbon synergistic catalysts including Ni/AC, Ni-Fe/AC, Ni-Mo/AC and Ni-Cu/AC were evaluated for HDO of prairie cordgrass (PCG) bio-oil. The tests were carried out in the autoclave under mild operating conditions with 500psig of H2 pressure and 350°C temperature. The catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and transmission electron microscope (TEM). The results show that all synergistic catalysts had significant improvements on the physicochemical properties (water content, pH, oxygen content, higher heating value and chemical compositions) of the upgraded PCG bio-oil. The higher heating value of the upgraded bio-oil (ranging from 29.65MJ/kg to 31.61MJ/kg) improved significantly in comparison with the raw bio-oil (11.33MJ/kg), while the oxygen content reduced to only 21.70-25.88% from 68.81% of the raw bio-oil. Compared to raw bio-oil (8.78% hydrocarbons and no alkyl-phenols), the Ni/AC catalysts produced the highest content of gasoline range hydrocarbons (C6-C12) at 32.63% in the upgraded bio-oil, while Ni-Mo/AC generated the upgraded bio-oil with the highest content of gasoline blending alkyl-phenols at 38.41%.

  11. Effects of alloying element and temperature on the stacking fault energies of dilute Ni-base superalloys.

    Science.gov (United States)

    Shang, S L; Zacherl, C L; Fang, H Z; Wang, Y; Du, Y; Liu, Z K

    2012-12-19

    A systematic study of stacking fault energy (γ(SF)) resulting from induced alias shear deformation has been performed by means of first-principles calculations for dilute Ni-base superalloys (Ni(23)X and Ni(71)X) for various alloying elements (X) as a function of temperature. Twenty-six alloying elements are considered, i.e., Al, Co, Cr, Cu, Fe, Hf, Ir, Mn, Mo, Nb, Os, Pd, Pt, Re, Rh, Ru, Sc, Si, Ta, Tc, Ti, V, W, Y, Zn, and Zr. The temperature dependence of γ(SF) is computed using the proposed quasistatic approach based on a predicted γ(SF)-volume-temperature relationship. Besides γ(SF), equilibrium volume and the normalized stacking fault energy (Γ(SF) = γ(SF)/Gb, with G the shear modulus and b the Burgers vector) are also studied as a function of temperature for the 26 alloying elements. The following conclusions are obtained: all alloying elements X studied herein decrease the γ(SF) of fcc Ni, approximately the further the alloying element X is from Ni on the periodic table, the larger the decrease of γ(SF) for the dilute Ni-X alloy, and roughly the γ(SF) of Ni-X decreases with increasing equilibrium volume. In addition, the values of γ(SF) for all Ni-X systems decrease with increasing temperature (except for Ni-Cr at higher Cr content), and the largest decrease is observed for pure Ni. Similar to the case of the shear modulus, the variation of γ(SF) for Ni-X systems due to various alloying elements is traceable from the distribution of (magnetization) charge density: the spherical distribution of charge density around a Ni atom, especially a smaller sphere, results in a lower value of γ(SF) due to the facility of redistribution of charges. Computed stacking fault energies and the related properties are in favorable accord with available experimental and theoretical data.

  12. Ni-Based Catalysts for Low Temperature Methane Steam Reforming: Recent Results on Ni-Au and Comparison with Other Bi-Metallic Systems

    Directory of Open Access Journals (Sweden)

    Anna M. Venezia

    2013-06-01

    Full Text Available Steam reforming of light hydrocarbons provides a promising method for hydrogen production. Ni-based catalysts are so far the best and the most commonly used catalysts for steam reforming because of their acceptably high activity and significantly lower cost in comparison with alternative precious metal-based catalysts. However, nickel catalysts are susceptible to deactivation from the deposition of carbon, even when operating at steam-to-carbon ratios predicted to be thermodynamically outside of the carbon-forming regime. Reactivity and deactivation by carbon formation can be tuned by modifying Ni surfaces with a second metal, such as Au through alloy formation. In the present review, we summarize the very recent progress in the design, synthesis, and characterization of supported bimetallic Ni-based catalysts for steam reforming. The progress in the modification of Ni with noble metals (such as Au and Ag is discussed in terms of preparation, characterization and pretreatment methods. Moreover, the comparison with the effects of other metals (such as Sn, Cu, Co, Mo, Fe, Gd and B is addressed. The differences of catalytic activity, thermal stability and carbon species between bimetallic and monometallic Ni-based catalysts are also briefly shown.

  13. Synergic effects of ion irradiations (La, Ce) and alkaline pretreatment (KOH) on hydriding kinetic property of a Mm–Ni based alloy

    Energy Technology Data Exchange (ETDEWEB)

    Abe, H., E-mail: abe.hiroshi10@jaea.go.jp [Quantum Beam Science Directorate, Japan Atomic Energy Agency, 1233 Watanuki, Takasaki, Gunma 370-1292 (Japan); Aone, S.; Morimoto, R.; Uchida, H. [Course of Applied Science, Graduate School of Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka, Kanagawa 259-1292 (Japan)

    2013-12-15

    Highlights: •Ion irradiations by various ions onto a Mm–Ni based hydrogen storage alloy. •The generation of vacancy type defects by ion irradiations in the surface of a Mm–Ni based alloy. •The enhancement of the initial rate by the ion irradiations of the Mm surface. •The enhancement of the initial rate by an alkaline treatment of the Mm surface. -- Abstract: The ion beam irradiation is known to produce a high density of vacancy type defects in the surface region of a metal and found to be an effective method as a surface modification in order to enhance the hydriding rate of a metal. In this study, we examined synergic effects of both surface modifications of ion irradiations and alkaline treatment on the initial hydriding rate of a Mm–Ni based alloy. In this study, the irradiations by lanthanum (La) and cerium (Ce) ions combined with an alkaline KOH pretreatment were found much more effective in the enhancement of the initial hydriding rate compared with irradiations with other ions. This study reports the synergic effects of the surface modifications by the both the surface irradiations with rare earth ions of La and Ce, and an alkaline surface treatment on the hydriding kinetics.

  14. Coordination Chemistry of [Co(acac)2 ] with N-Doped Graphene: Implications for Oxygen Reduction Reaction Reactivity of Organometallic Co-O4 -N Species.

    Science.gov (United States)

    Han, Jongwoo; Sa, Young Jin; Shim, Yeonjun; Choi, Min; Park, Noejung; Joo, Sang Hoon; Park, Sungjin

    2015-10-19

    Hybridization of organometallic complexes with graphene-based materials can give rise to enhanced catalytic performance. Understanding the chemical structures within hybrid materials is of primary importance. In this work, archetypical hybrid materials are synthesized by the reaction of an organometallic complex, [Co(II) (acac)2 ] (acac=acetylacetonate), with N-doped graphene-based materials at room temperature. Experimental characterization of the hybrid materials and theoretical calculations reveal that the organometallic cobalt-containing species is coordinated to heterocyclic groups in N-doped graphene as well as to its parental acac ligands. The hybrid material shows high electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media, and superior durability and methanol tolerance to a Pt/C catalyst. Based on the chemical structures and ORR experiments, the catalytically active species is identified as a Co-O4 -N structure.

  15. Mechanistic Studies at the Interface Between Organometallic Chemistry and Homogeneous Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Casey, Charles P

    2012-11-14

    Mechanistic Studies at the Interface Between Organometallic Chemistry and Homogeneous Catalysis Charles P. Casey, Principal Investigator Department of Chemistry, University of Wisconsin - Madison, Madison, Wisconsin 53706 Phone 608-262-0584 FAX: 608-262-7144 Email: casey@chem.wisc.edu http://www.chem.wisc.edu/main/people/faculty/casey.html Executive Summary. Our goal was to learn the intimate mechanistic details of reactions involved in homogeneous catalysis and to use the insight we gain to develop new and improved catalysts. Our work centered on the hydrogenation of polar functional groups such as aldehydes and ketones and on hydroformylation. Specifically, we concentrated on catalysts capable of simultaneously transferring hydride from a metal center and a proton from an acidic oxygen or nitrogen center to an aldehyde or ketone. An economical iron based catalyst was developed and patented. Better understanding of fundamental organometallic reactions and catalytic processes enabled design of energy and material efficient chemical processes. Our work contributed to the development of catalysts for the selective and mild hydrogenation of ketones and aldehydes; this will provide a modern green alternative to reductions by LiAlH4 and NaBH4, which require extensive work-up procedures and produce waste streams. (C5R4OH)Ru(CO)2H Hydrogenation Catalysts. Youval Shvo described a remarkable catalytic system in which the key intermediate (C5R4OH)Ru(CO)2H (1) has an electronically coupled acidic OH unit and a hydridic RuH unit. Our efforts centered on understanding and improving upon this important catalyst for reduction of aldehydes and ketones. Our mechanistic studies established that the reduction of aldehydes by 1 to produce alcohols and a diruthenium bridging hydride species occurs much more rapidly than regeneration of the ruthenium hydride from the diruthenium bridging hydride species. Our mechanistic studies require simultaneous transfer of hydride from ruthenium to

  16. Highly electrophilic organometallics for carbocationic polymerizations: from anion engineering to new polymer materials.

    Science.gov (United States)

    Bochmann, Manfred

    2010-09-21

    Ion-ion interactions are a crucial but often overlooked aspect of many polymerization reactions. The precise nature of cation-anion binding is as yet poorly understood, and little is known of the extent of ionic interactions in the typically nonaqueous, low-polarity reaction media of most polymerizations. Nevertheless, adequate control of cation-anion interactions can greatly enhance the productivity and efficiency of chemical processes and can provide low-energy alternatives to current methods. This is illustrated here with the carbocationic polymerization of isoalkenes. Carbocationic polymerizations involve, as the name implies, carbocations as propagating species. Of the various types of substrates that can be polymerized cationically, the copolymerization of isobutene to isobutene-isoprene rubber stands out as the only large-scale, industrially important implementation of this reaction type. The products, elastomers with controlled degrees of unsaturation for subsequent cross-linking, have excellent gas barrier and mechanical dampening properties that make them indispensable components in polymer composites. For such applications, the polymer molecular weight has to be high, ∼5 × 10(5) g/mol, with 1-2 mol % isoprene. Cationic polymerizations are however notoriously difficult to control. As a means of suppressing chain transfer, the process is carried out at temperatures as low as -100 °C, with aluminum chloride initiators in chloromethane. Current industrial production of isobutene-isoprene butyl rubber is thus highly energy intensive and produces aluminum and chloride effluent. This Account summarizes how highly electrophilic organometallics coupled with new types of very weakly coordinating counteranions can provide the basis for a more environmentally friendly, lower energy alternative. Because any copolymerization of two monomers, here primarily isobutene and isoprene, leads to two different propagating species, each of which is characterized by

  17. Transferrin serves as a mediator to deliver organometallic ruthenium(II) anticancer complexes into cells.

    Science.gov (United States)

    Guo, Wei; Zheng, Wei; Luo, Qun; Li, Xianchan; Zhao, Yao; Xiong, Shaoxiang; Wang, Fuyi

    2013-05-06

    We report herein a systematic study on interactions of organometallic ruthenium(II) anticancer complex [(η(6)-arene)Ru(en)Cl](+) (arene = p-cymene (1) or biphenyl (2), en = ethylenediamine) with human transferrin (hTf) and the effects of the hTf-ligation on the bioavailability of these complexes with cisplatin as a reference. Incubated with a 5-fold excess of complex 1, 2, or cisplatin, 1 mol of diferric hTf (holo-hTf) attached 0.62 mol of 1, 1.01 mol of 2, or 2.14 mol of cisplatin. Mass spectrometry revealed that both ruthenium complexes coordinated to N-donors His242, His273, His578, and His606, whereas cisplatin bound to O donors Tyr136 and Tyr317 and S-donor Met256 in addition to His273 and His578 on the surface of both apo- and holo-hTf. Moreover, cisplatin could bind to Thr457 within the C-lobe iron binding cleft of apo-hTf. Neither ruthenium nor platinum binding interfered with the recognition of holo-hTf by the transferrin receptor (TfR). The ruthenated/platinated holo-hTf complexes could be internalized via TfR-mediated endocytosis at a similar rate to that of holo-hTf itself. Moreover, the binding to holo-hTf well preserved the bioavailability of the ruthenium complexes, and the hTf-bound 1 and 2 showed a similar cytotoxicity toward the human breast cancer cell line MCF-7 to those of the complexes themselves. However, the conjugation with holo-hTf significantly reduced the cellular uptake of cisplatin and the amount of platinated DNA adducts formed intracellularly, leading to dramatic reduction of cisplatin cytotoxicity toward MCF-7. These findings suggest that hTf can serve as a mediator for the targeting delivery of Ru(arene) anticancer complexes while deactivating cisplatin.

  18. Probing the chemistry, electronic structure and redox energetics in pentavalent organometallic actinide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Graves, Christopher R [Los Alamos National Laboratory; Vaughn, Anthony E [Los Alamos National Laboratory; Morris, David E [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory

    2008-01-01

    Complexes of the early actinides (Th-Pu) have gained considerable prominence in organometallic chemistry as they have been shown to undergo chemistries not observed with their transition- or lanthanide metal counterparts. Further, while bonding in f-element complexes has historically been considered to be ionic, the issue of covalence remains a subject of debate in the area of actinide science, and studies aimed at elucidating key bonding interactions with 5f-orbitals continue to garner attention. Towards this end, our interests have focused on the role that metal oxidation state plays in the structure, reactivity and spectral properties of organouranium complexes. We report our progress in the synthesis of substituted U{sup V}-imido complexes using various routes: (1) Direct oxidation of U{sup IV}-imido complexes with copper(I) salts; (2) Salt metathesis with U{sup V}-imido halides; (3) Protonolysis and insertion of an U{sup V}-imido alkyl or aryl complex with H-N{double_bond}CPh{sub 2} or N{triple_bond}C-Ph, respectively, to form a U{sup V}-imido ketimide complex. Further, we report and compare the crystallographic, electrochemical, spectroscopic and magnetic characterization of the pentavalent uranium (C{sub 5}Me{sub 5}){sub 2}U({double_bond}N-Ar)(Y) series (Y = OTf, SPh, C{triple_bond}C-Ph, NPh{sub 2}, OPh, N{double_bond}CPh{sub 2}) to further interrogate the molecular, electronic, and magnetic structures of this new class of uranium complexes.

  19. Decarboxylative-coupling of allyl acetate catalyzed by group 10 organometallics, [(phen)M(CH3)]+.

    Science.gov (United States)

    Woolley, Matthew; Ariafard, Alireza; Khairallah, George N; Kwan, Kim Hong-Yin; Donnelly, Paul S; White, Jonathan M; Canty, Allan J; Yates, Brian F; O'Hair, Richard A J

    2014-12-19

    Gas-phase carbon-carbon bond forming reactions, catalyzed by group 10 metal acetate cations [(phen)M(O2CCH3)](+) (where M = Ni, Pd or Pt) formed via electrospray ionization of metal acetate complexes [(phen)M(O2CCH3)2], were examined using an ion trap mass spectrometer and density functional theory (DFT) calculations. In step 1 of the catalytic cycle, collision induced dissociation (CID) of [(phen)M(O2CCH3)](+) yields the organometallic complex, [(phen)M(CH3)](+), via decarboxylation. [(phen)M(CH3)](+) reacts with allyl acetate via three competing reactions, with reactivity orders (% reaction efficiencies) established via kinetic modeling. In step 2a, allylic alkylation occurs to give 1-butene and reform metal acetate, [(phen)M(O2CCH3)](+), with Ni (36%) > Pd (28%) > Pt (2%). Adduct formation, [(phen)M(C6H11O2)](+), occurs with Pt (24%) > Pd (21%) > Ni(11%). The major losses upon CID on the adduct, [(phen)M(C6H11O2)](+), are 1-butene for M = Ni and Pd and methane for Pt. Loss of methane only occurs for Pt (10%) to give [(phen)Pt(C5H7O2)](+). The sequences of steps 1 and 2a close a catalytic cycle for decarboxylative carbon-carbon bond coupling. DFT calculations suggest that carbon-carbon bond formation occurs via alkene insertion as the initial step for all three metals, without involving higher oxidation states for the metal centers.

  20. Organometallic synthesis of ZnO nanoparticles for gas sensing: towards selectivity through nanoparticles morphology

    Energy Technology Data Exchange (ETDEWEB)

    Ryzhikov, Andrey; Jońca, Justyna; Kahn, Myrtil; Fajerwerg, Katia [Laboratoire de Chimie de Coordination (LCC), CNRS (France); Chaudret, Bruno [Laboratoire de Physique et de Chimie de Nano-objets (LPCNO), INSA, UPS, CNRS (France); Chapelle, Audrey [Laboratoire d’Analyse et d’Architecture des Systèmes (LAAS), CNRS (France); Ménini, Philippe [Université Toulouse III, Paul Sabatier (France); Shim, Chang Hyun [Laboratoire d’Analyse et d’Architecture des Systèmes (LAAS), CNRS (France); Gaudon, Alain [Alpha M.O.S. SA (France); Fau, Pierre, E-mail: pierre.fau@lcc-toulouse.fr [Laboratoire de Chimie de Coordination (LCC), CNRS (France)

    2015-07-15

    ZnO nanoparticles (NP) with different morphologies such as nanorods (NR), isotropic NP, and cloud-like (CL) structures have been synthesized by an organometallic route. The prepared ZnO nanostructures have been deposited on miniaturized silicon gas sensor substrates by an inkjet method, and their responses to CO, C{sub 3}H{sub 8}, and NH{sub 3} gases have been studied at different operating temperatures (340–500 °C) and relative humidity of 50 %. It is noteworthy that the morphology of the nanostructure of the sensitive layer is maintained after thermal treatment. The morphology of ZnO NP significantly influences the sensor response level and their selectivity properties to reducing gases. Among the three different ZnO types, sensors prepared with NR show the highest response to both CO and C{sub 3}H{sub 8}. Sensors made of isotropic NP and CL structures show a lower but similar response to CO. From all investigated nanostructures, sensors made of CL structures show the weakest response to C{sub 3}H{sub 8}. With NH{sub 3} gas, no effect of the morphology of the ZnO sensitive layer has been evidenced. These different responses highlight the important role of the nanostructure of the ZnO sensitive layer and the nature of the target gas on the detection properties of the sensors. Graphical Abstract: Three different ZnO nanoparticles morphologies (cloud-like, dots, rods) have been employed as sensitive layers in chemoresistive sensors for the selective detection of CO, C{sub 3}H{sub 8} and NH{sub 3}.