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Sample records for ni-based organometallic compounds

  1. Organometallic compounds: an opportunity for chemical biology?

    PubMed

    Patra, Malay; Gasser, Gilles

    2012-06-18

    Organometallic compounds are renowned for their remarkable applications in the field of catalysis, but much less is known about their potential in chemical biology. Indeed, such compounds have long been considered to be either unstable under physiological conditions or cytotoxic. As a consequence, little attention has been paid to their possible utilisation for biological purposes. Because of their outstanding physicochemical properties, which include chemical stability, structural diversity and unique photo- and electrochemical properties, however, organometallic compounds have the ability to play a leading role in the field of chemical biology. Indeed, remarkable examples of the use of such compounds-notably as enzyme inhibitors and as luminescent agents-have recently been reported. Here we summarise recent advances in the use of organometallic compounds for chemical biology purposes, an area that we define as "organometallic chemical biology". We also demonstrate that these recent discoveries are only a beginning and that many other organometallic complexes are likely to be found useful in this field of research in the near future.

  2. Synthesis of organometallic compounds: Final technical report

    SciTech Connect

    Parker, J.

    1987-01-28

    The object of this project is the establishment of procedures which would allow the practical production of solutions of organometallic compounds suitable for the deposition of conductive metal films at temperatures below 250/sup 0/C. Purdue University's Turner Laboratory developed the basic chemistry for the synthesis of these ''oxygen bridge'' organometallic compounds. A solution of a metal salt is combined with a solution of an ammonium (or amine) soap of an appropriate organic acid. The resulting product precipitate is cleaned, dried and dissolved in xylene. Control of reaction pH and reagent purity was essential in producing useful quantities of the organometallic compounds in better than 75% yields and at reasonable costs. Processes were developed for silver, bismuth, platinum, nickel, and gold organometallic products. The processes for the gold and platinum products remained difficult, giving low yields and evidence of poor product stability. It is anticipated that improvement in the removal of inorganic impurities from the product would enhance its stability. Thermal analyses were applied to the products to determine their decomposition characteristics, and rough cost studies were made to aid in comparisons with conventional metallization methods.

  3. Bioremediation of organometallic compounds by bacterial degradation.

    PubMed

    Shah, Jay; Dahanukar, Neelesh

    2012-06-01

    The use of organometallic compounds in the environment is constantly increasing with increased technology and progress in scientific research. But since these compounds are fairly stable, as metallic bonds are stable, they are difficult to degrade or decompose naturally. The aim of this work was to isolate and characterize heterotrophic bacteria that can degrade organometallic compounds (in this case 'ferrocene' and its derivatives). A Gram-negative coccobacillus was isolated from a rusting iron pipe draining into a freshwater lake, which could utilize ferrocene as a sole source of carbon. Phylogenetic analysis based on 16S rDNA sequence suggested that the isolated organism resembled an environmental isolate of Bordetella. Ferrocene degradation was confirmed by plotting the growth curve of the bacterium in a medium with ferrocene as the sole source of carbon. Further confirmation of degradation of ferrocene and its derivatives was done using Gas Chromatography Mass Spectroscopy. Since the bacterium degraded organometallic compounds and released the metal in liquid medium, it could be suggested that this organism can also be used for extracting metal ions from organo-metal containing wastes.

  4. Small organometallic compounds as antibacterial agents.

    PubMed

    Patra, Malay; Gasser, Gilles; Metzler-Nolte, Nils

    2012-06-07

    The emergence of bacterial resistance to commercial antibiotics is an issue of global importance. During the last two decades, the number of antibacterial agents that have been discovered and introduced into the market has steadily declined and failed to meet the challenges posed by rapidly increasing resistance of the pathogens against common antibacterial drugs. The development of new classes of compounds to control the virulence of the pathogens is therefore urgently required. This perspective describes the historical development in brief and recent advances on the preparation of small organometallic compounds as new classes of antibacterial agents with potential for clinical development.

  5. Progress towards bioorthogonal catalysis with organometallic compounds.

    PubMed

    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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Detection of Metal and Organometallic Compounds with Bioluminescent Bacterial Bioassays.

    PubMed

    Durand, M J; Hua, A; Jouanneau, S; Cregut, M; Thouand, G

    2015-10-17

    Chemical detection of metal and organometallic compounds is very specific and sensitive, but these techniques are time consuming and expensive. Although these techniques provide information about the concentrations of compounds, they fail to inform us about the toxicity of a sample. Because the toxic effects of metals and organometallic compounds are influenced by a multitude of environmental factors, such as pH, the presence of chelating agents, speciation, and organic matter, bioassays have been developed for ecotoxicological studies. Among these bioassays, recombinant luminescent bacteria have been developed over the past 20 years, and many of them are specific for the detection of metals and metalloids. These bioassays are simple to use, are inexpensive, and provide information on the bioavailable fraction of metals and organometals. Thus, they are an essential complementary tool for providing information beyond chemical analysis. In this chapter, we propose to investigate the detection of metals and organometallic compounds with bioluminescent bacterial bioassays and the applications of these bioassays to environmental samples. Graphical Abstract.

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

    EPA Science Inventory

    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...

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

    EPA Science Inventory

    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.

    PubMed

    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.

    PubMed

    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. 40 CFR 721.10414 - Polycyclic polyamine diester organometallic compound (generic) (P-10-358).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Polycyclic polyamine diester organometallic compound (generic) (P-10-358). 721.10414 Section 721.10414 Protection of Environment ENVIRONMENTAL... compound (generic) (P-10-358). (a) Chemical substance and significant new uses subject to reporting....

  12. 40 CFR 721.10414 - Polycyclic polyamine diester organometallic compound (generic) (P-10-358).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Polycyclic polyamine diester organometallic compound (generic) (P-10-358). 721.10414 Section 721.10414 Protection of Environment ENVIRONMENTAL... compound (generic) (P-10-358). (a) Chemical substance and significant new uses subject to reporting....

  13. 40 CFR 721.10414 - Polycyclic polyamine diester organometallic compound (generic) (P-10-358).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polycyclic polyamine diester organometallic compound (generic) (P-10-358). 721.10414 Section 721.10414 Protection of Environment ENVIRONMENTAL... compound (generic) (P-10-358). (a) Chemical substance and significant new uses subject to reporting....

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

    PubMed Central

    Nxumalo, Edward N.; Coville, Neil J.

    2010-01-01

    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(CO)5. 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.

  15. Organometallic Chemical Vapor Deposition Growth of Antimony Compounds

    NASA Astrophysics Data System (ADS)

    Chiang, Peng-Kuen

    This research is motivated by the desire to synthesize Sb III-V materials, including GaAs(,1-x)Sb(,x), InSb, and InAs(,1-x)Sb(,x). Ga-As-Sb system is known to have a significant solid phase miscibility gap from x = 0.2 to x = 0.8 at 600(DEGREES)C using a liquid phase epitaxy (LPE) growth technique. In this work, organometallic chemical vapor deposition (OM-CVD) has been shown to be a suitable growth technique for growing GaAs(,1-x)Sb(,x) alloys lying in the region of solid immiscibility. Conditions for growth of GaAs(,1-x)Sb(,x) layers with x as high as 0.7 on GaAs substrates are described for temperatures between 580 and 650(DEGREES)C. Effects of substrate orientation on growth characteristics are noted, and comparisons of growth on (511) and (100) GaAs faces are made. The experimental results indicate that growth is being controlled by surface reaction kinetics. A simple model based on kinetic control is presented. InSb is one of the most extensively examined semiconductors because of the small energy bandgap which is suitable for 3-5 (mu)m wavelength detection, and it also has highest mobility of any III-V compounds. OM-CVD has been used to epitaxially grow high quality InSb for the first time in this work. InSb with excellent morphology was achieved on both (100) and (111)B InSb substrates. The measured electron mobility at 300(DEGREES)K of undoped InSb grown on (100) GaAs semi-insulating substrates was 40,000 cm('2)/V -sec at a carrier concentration of N(,D)-N(,A) = 1.2 x 10('15)cm(' -3) has been measured at 77(DEGREES)K.Experimental data suggests that a dislocation scattering mechanism represents a significant mobility limiting process. InAs(,1-x)Sb(,x), with x (TURN) 0.6, has the lowest bandgap (=0.1 eV at 300(DEGREES)K) of any of the III-V ternary compounds. This bandgap is suitable for detectors in the 8-12 (mu)m wavelength region where an atmosphere window exists. So far, InAs(,1-x)Sb(,x) with 0.55 < x < 0.75 has not been achieved by LPE and molecular

  16. Model for the Vaporization of Mixed Organometallic Compounds in the Metalorganic Chemical Vapor Deposition of High Temperature Superconducting Films

    NASA Technical Reports Server (NTRS)

    Meng, Guangyao; Zhou, Gang; Schneider, Roger L.; Sarma, Bimal K.; Levy, Moises

    1993-01-01

    A model of the vaporization and mass transport of mixed organometallics from a single source for thin film metalorganic chemical vapor deposition is presented. A stoichiometric gas phase can be obtained from a mixture of the organometallics in the desired mole ratios, in spite of differences in the volatilities of the individual compounds. Proper film composition and growth rates are obtained by controlling the velocity of a carriage containing the organometallics through the heating zone of a vaporizer.

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

    ERIC Educational Resources Information Center

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

    ERIC Educational Resources Information Center

    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…

  19. Organometallic Compounds and Polymers with Second and Third Order Nonlinear Optical Properties

    DTIC Science & Technology

    1993-05-06

    Nonlinear Optical Properties of Inorganic Coordination Polymers . William Chiang, Mark E. Thompson, Donna Van Engen , "Organic Materials for Nonlinear...Organometallic Compounds and Polymers with Second and Third Order Nonlinear Optical Pro. -c.AUTHOR(S) 61102F 2303 All Mark E. Thompson, PI 7. PERFORMING...scale Sc -Cr $5 Fe > Co. Polar coordination polymers were prepared in which excellent polar order was found in the polyermic chains. however, the

  20. Mössbauer effect studies on organometallic237Np-compounds

    NASA Astrophysics Data System (ADS)

    Adrian, G.; Appel, H.; Bohlander, R.; Haffner, H.; Kanellakopulos, B.

    1988-02-01

    A series of organometallic compounds of tetravalent Neptunium was studied by Moessbauer methods. Three of them will be presented here. Their molecular structure is close to C3v symmetry. The data were parameterised on the basis of an anisotropic paramagnetic relaxation model and will be interpreted for each individual compound. In general it can be stated that distortions from axially symmetric hyperfine parameters were observed, no magnetic ordering occured at all temperatures above 1.5 K and anisotropic relaxation frequencies had to be introduced to fit the spectra.

  1. Organometallic ruthenium(II) arene compounds with antiangiogenic activity.

    PubMed

    Nowak-Sliwinska, Patrycja; van Beijnum, Judy R; Casini, Angela; Nazarov, Alexey A; Wagnieres, Georges; van den Bergh, Hubert; Dyson, Paul J; Griffioen, Arjan W

    2011-06-09

    The antimetastatic ruthenium(II) compounds [Ru(η(6)-p-cymene)Cl(2)(PTA)] (PTA = 1,3,5-triaza-7-phosphaadamantane) (RAPTA-C) and [Ru(η(6)-toluene)Cl(2)(PTA)] (RAPTA-T), as well as their analogues [Ru(η(6)-p-cymene)Cl(2)(DAPTA)] (DAPTA = (3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane)) (DAPTA-C) and [Ru(η(6)-toluene)Cl(2)(DAPTA)] (DAPTA-T), respectively, were tested in in vitro bioassays for endothelial cell function. All compounds showed low toxicity profiles and similar dose-dependent antiproliferative effects in endothelial cells at ≥100 μg/mL (∼200 μM). EC migration, measured 6 h after drug exposure, was also efficiently inhibited (ED(50) of ∼300 μg/mL, ∼500 μM, for all compounds). Since no cytostatic effect was noted, the inhibition of proliferation was considered mainly to consist of antiangiogenic activity. RAPTA-T and DAPTA-C were also tested in vivo in the chicken chorioallantoic membrane (CAM) assay and found to inhibit CAM development. Importantly, effective prevention of revascularization of the CAM after vaso-occlusive photodynamic therapy was observed. The reported ruthenium complexes show promising antimetastatic activity involving inhibition of angiogenesis and therefore are attractive agents for development of anticancer therapies based on combination of chemo- and angiostatic treatments.

  2. Absorption of organic compounds and organometallics on ceramic substrates for wear reduction

    SciTech Connect

    Kennedy, P.J.; Agarwala, V.S.

    1996-12-31

    The concept of employing thermally stable compounds (that is, metal oxides) as high temperature vapor phase ceramic lubricants was investigated. A major part of this study was devoted to the development of various calorimetric and tribological techniques that could be used to determine interfacial reactions between thermally stable compounds and ceramic substrates such as zirconia and alumina. This interaction is pivotal in understanding the mechanism of high temperature lubricity. The approach consisted of selecting low sublimation temperature materials and measuring their thermodynamic interactions as vapors with the ceramic substrates. The materials studied included two easily sublimable organic compounds (that is, naphthalene and salicylic acid) and several organometallics (for example, copper phthalocyanine). Thermodynamic data such as heat of adsorption, packing density, and reversibility of the adsorption were obtained on some of these compounds and were related to wear characteristics. All of these compounds provided effective lubrication at room temperature. Copper phthalocyanine was an effective lubricant at temperatures up to 400 C.

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

    DOEpatents

    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.

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

    PubMed

    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.

  5. The Deposition of Metal Thin Films in Vacuum from the Decomposition of Selected Organometallic Compounds.

    NASA Astrophysics Data System (ADS)

    Stauf, Gregory Thomas

    The deposition of thin metal films is of great importance in a variety of technological areas. A method which is gaining increasing attention is Organometallic Chemical Vapor Deposition (MOCVD or OMVPE). Despite widespread use of CVD, little systematic work has been done to evaluate new source complexes. Thermodynamic studies are particularly important, since these factors control whether the compound will decompose in such a way as to give a desired coating with low levels of contamination. In this work we have used (Mn(CO)_5 ) _2(mu -SiH_2) to deposit Mn_2 Si, Pd(eta-C_5 H_5)(eta -C_3H_5) to deposit Pd, Fe(eta-C_5 H_5)_2 to deposit Fe, and Ni(eta-C _5H_5)_2 to deposit Ni. We first studied the gas-phase decomposition thermodynamics of these compounds, as well as Pt(eta-C_3H _5)(eta-C _5H_5), by electron and photon impact mass spectroscopy, and photoabsorption. We then made coatings by pyrolysis and laser photolysis, and analyzed them by scanning electron microscopy and x-ray electron spectroscopy, as well as in some cases Auger electron spectroscopy, Rutherford backscattering spectroscopy, x -ray diffraction and transmission electron microscopy. Several conclusions can be drawn relating the thermodynamic results and the coating outcomes. The methods for thermodynamic studies discussed herein are seen to allow some prediction of contamination levels and coating feasibility with these compounds.

  6. Electromagnetic absorption and conductivity of organometallic TiOx-Py plasma compounds

    NASA Astrophysics Data System (ADS)

    González-Salgado, Francisco; Olayo, Maria Guadalupe; García-Rosales, Genoveva; Gómez, Lidia Maria; González-Torres, Maribel; Cruz, Guillermo J.

    2016-05-01

    Organometallic compounds made of titanium oxide (TiOx) and pyrrole (Py) were synthesized by plasma to combine the photoelectronic activity of TiO and Py in hybrid materials with potential use in photostimulated processes as photoelectronic devices in pollutant degradation or in solar photocollectors. The Ti precursors were based on titanium tetrapropoxide combined with Py in 1:1 mass ratio in a vacuum tubular glass reactor under resistive electrical glow discharges of water vapor plasmas. The TiOx-Py hybrid compounds with x in the 2.75-3.55 interval absorbed electromagnetic radiation in two regions with different intensities. The first and most intense one was from approximately 190 to 350 nm and the other from roughly 350 to 900 nm, which indicates that in the first interval, the TiO fraction dominates the absorption and that the activity of the second region belonged to Py segments. The electrical conductivity was in the (10-6-10-10) S/m interval with activation energy in the (0.015-2.42) eV range, depending on the reaction time and synthesis conditions.

  7. Analysis of the mechanism of action of potent antibacterial hetero-tri-organometallic compounds: a structurally new class of antibiotics.

    PubMed

    Wenzel, Michaela; Patra, Malay; Senges, Christoph Helmut Rudi; Ott, Ingo; Stepanek, Jennifer Janina; Pinto, Antonio; Prochnow, Pascal; Vuong, Cuong; Langklotz, Sina; Metzler-Nolte, Nils; Bandow, Julia Elisabeth

    2013-07-19

    Two hetero-tri-organometallic compounds with potent activity against Gram-positive bacteria including multi-resistant Staphylococcus aureus (MRSA) were identified. The compounds consist of a peptide nucleic acid backbone with an alkyne side chain, substituted with a cymantrene, a (dipicolyl)Re(CO)3 moiety, and either a ferrocene (FcPNA) or a ruthenocene (RcPNA). Comparative proteomic analysis indicates the bacterial membrane as antibiotic target structure. FcPNA accumulation in the membrane was confirmed by manganese tracing with atomic absorption spectroscopy. Both organometallics disturbed several essential cellular processes taking place at the membrane such as respiration and cell wall biosynthesis, suggesting that the compounds affect membrane architecture. Correlating with enhanced antibacterial activity, oxidative stress was induced only by the ferrocene-substituted compound. The organometallics described here target the cytoplasmic membrane, a clinically proven antibacterial target structure, feature a bactericidal but non-bacteriolytic mode of action and limited cytotoxicity within the limits of solubility. Thus, FcPNA represents a promising lead structure for the development of a new synthetic class of antibiotics.

  8. Theoretical Study of Indium Compounds of Interest for Organometallic Chemical Vapor Deposition

    NASA Technical Reports Server (NTRS)

    Cardelino, B. H.; Moore, C. E.; Cardelino, C. A.; Frazier, D. O.; Backmann, K. J.

    2000-01-01

    The structural. electronic and therinochemical properties of indium compounds which are of interest in halide transport and organometallic chemical vapor deposition processes have been studied by ab initio and statistical mechanics methods. The compounds reported include: indium halides and hydrides (InF, InCl, InCl3, InH, InH2, InH3); indium clusters (In2, In3); methylindium, dimethylindium, and their hydrogen derivatives [In(CH3), In(CH3)H, In(CH3)H2, In(CH3)2, In(CH3)2H]; dimethyl-indium dimer [In2(CH3)4], trimethyl-indium [In(CH3)3]; dehydrogenated methyl, dimethyl and trimethylindium [In(CH3)2CH2, In(CH3)CH2, In(CH2)], trimethylindium adducts with ammonia, trimethylamine and hydrazine [(CH3)3In:NH3, (CH3)3In:N(CH3)3, (CH3)3In:N(H2)N(H2)]; dimethylamino-indium and methylimino-indium [In(CH3)2(NH2), In(CH3)(NH)]; indium nitride and indium nitride dimer (InN, In2N2), indium phosphide, arsenide and antimonide ([InP, InAs, InSb). The predicted electronic properties are based on density functional theory calculations; the calculated thermodynamic properties are reported following the format of the JANAF (Joint Army, Navy, NASA, Air Force) Tables. Equilibrium compositions at two temperatures (298 and 1000 K) have been analyzed for groups of competing simultaneous reactions.

  9. Theoretical Study of Indium Compounds of Interest for Organometallic Chemical Vapor Deposition

    NASA Technical Reports Server (NTRS)

    Cardelino, B. H.; Moore, C. E.; Cardelino, C. A.; Frazier, D. O.; Backmann, K. J.

    2000-01-01

    The structural. electronic and therinochemical properties of indium compounds which are of interest in halide transport and organometallic chemical vapor deposition processes have been studied by ab initio and statistical mechanics methods. The compounds reported include: indium halides and hydrides (InF, InCl, InCl3, InH, InH2, InH3); indium clusters (In2, In3); methylindium, dimethylindium, and their hydrogen derivatives [In(CH3), In(CH3)H, In(CH3)H2, In(CH3)2, In(CH3)2H]; dimethyl-indium dimer [In2(CH3)4], trimethyl-indium [In(CH3)3]; dehydrogenated methyl, dimethyl and trimethylindium [In(CH3)2CH2, In(CH3)CH2, In(CH2)], trimethylindium adducts with ammonia, trimethylamine and hydrazine [(CH3)3In:NH3, (CH3)3In:N(CH3)3, (CH3)3In:N(H2)N(H2)]; dimethylamino-indium and methylimino-indium [In(CH3)2(NH2), In(CH3)(NH)]; indium nitride and indium nitride dimer (InN, In2N2), indium phosphide, arsenide and antimonide ([InP, InAs, InSb). The predicted electronic properties are based on density functional theory calculations; the calculated thermodynamic properties are reported following the format of the JANAF (Joint Army, Navy, NASA, Air Force) Tables. Equilibrium compositions at two temperatures (298 and 1000 K) have been analyzed for groups of competing simultaneous reactions.

  10. Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds. Sublimation, Vaporization and Fusion Enthalpies From 1880 to 2010

    NASA Astrophysics Data System (ADS)

    Acree, William; Chickos, James S.

    2010-12-01

    A compendium of phase change enthalpies published within the period 1880-2010 is reported. Phase change enthalpies including fusion, vaporization, and sublimation are included for organic, organometallic, and a few inorganic compounds. This compendium is a combination of three previous series focusing on phase change enthalpies updated to 2009. Sufficient data are presently available for some compounds to permit thermodynamic cycles to be constructed, an important manner of evaluating the reliability of the measurements. Temperature adjustments of phase change enthalpies from the temperature of measurement to the standard reference temperature, T=298.15 K, are briefly discussed and a protocol for doing so is illustrated.

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

    PubMed

    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

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

    PubMed

    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.

  13. Organometallic chemistry in non-classical environments.

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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).

  15. Protective Actions of 17β-Estradiol and Progesterone on Oxidative Neuronal Injury Induced by Organometallic Compounds

    PubMed Central

    Ishihara, Yasuhiro; Takemoto, Takuya; Yamazaki, Takeshi

    2015-01-01

    Steroid hormones synthesized in and secreted from peripheral endocrine glands pass through the blood-brain barrier and play a role in the central nervous system. In addition, the brain possesses an inherent endocrine system and synthesizes steroid hormones known as neurosteroids. Increasing evidence shows that neuroactive steroids protect the central nervous system from various harmful stimuli. Reports show that the neuroprotective actions of steroid hormones attenuate oxidative stress. In this review, we summarize the antioxidative effects of neuroactive steroids, especially 17β-estradiol and progesterone, on neuronal injury in the central nervous system under various pathological conditions, and then describe our recent findings concerning the neuroprotective actions of 17β-estradiol and progesterone on oxidative neuronal injury induced by organometallic compounds, tributyltin, and methylmercury. PMID:25815107

  16. Spectroscopic studies of organometallic compounds on single crystal metal surfaces: Surface acetylides of silver (110)

    NASA Astrophysics Data System (ADS)

    Madix, Robert J.

    The nature of compounds formed by the reaction of organic molecules with metal surfaces can be studied with a battery of analytical methods based on both physicals and chemical understanding. In this paper the application of UPS, XPS, LEED and EELS as well as temperature programmed reaction spectroscopy (TPRS) and chemical titration methods to the characterization of surface complexes is discussed. Particular emphasis is given to the reaction of acetylene with a single crystal surface of silver, Ag(110). Previous work has shown that this surface, when clean, is unreactive to hydrocarbons, alcohols and carboxylic acids under ultra high vacuum conditions. Preadsorption of oxygen, however, renders the surface reactive, and a wide variety of organometallic surface compounds can be formed. As expected then, no stable adsorption state and no reaction was observed with clean Ag(110) following room temperature exposure to acetylene. Following exposure at 150 K, however, a weekly bound chemisorption state was observed to desorb at 195 K, indicating a binding energy to the surface of approximately 12 kcal/gmole. Reaction with preadsorbed oxygen gave water formulation upon dosing and produced surface intermediates which yeilded two acetylene desorption states at 195 and 175 K. Heating above 300 K to completely desorb the higher temperature state produced new, well-defined LEED Features due to residual surface carbon which disappeared when the surface was heated above 550 K. Clearly, there were distinc changes in the nature of the absorbed layer at 195, 300 and 550 K. These changes were reflected in XPS. For the weakly chemisorbed acetylene a large C(ls) peak at 285.6 eV with a small, broad, indistinc shoulder at higher binding energy (288.2) was observed. The spectrum of the species following acetylene desorption at 275 K, however, showed the formulation of a large C(ls) peak at 283.6 eV in addition to peaks characteristics of the weakly chemisorbed state. This result

  17. Exploring metallodrug-protein interactions by mass spectrometry: comparisons between platinum coordination complexes and an organometallic ruthenium compound.

    PubMed

    Casini, Angela; Gabbiani, Chiara; Michelucci, Elena; Pieraccini, Giuseppe; Moneti, Gloriano; Dyson, Paul J; Messori, Luigi

    2009-06-01

    Electrospray ionisation mass spectrometry was used to analyse the reactions of metal compounds with mixtures of selected proteins. Three representative medicinally relevant compounds, cisplatin, transplatin and the organometallic ruthenium compound RAPTA-C, were reacted with a pool of three proteins, ubiquitin, cytochrome c and superoxide dismutase, and the reaction products were analysed using high-resolution mass spectrometry. Highly informative electrospray ionisation mass spectra were acquired following careful optimisation of the experimental conditions. The formation of metal-protein adducts was clearly observed for the three proteins. In addition, valuable information was obtained on the nature of the protein-bound metallofragments, on their distribution among the three different proteins and on the binding kinetics. The platinum compounds were less reactive and considerably less selective in protein binding than RAPTA-C, which showed a high affinity towards ubiquitin and cytochrome c, but not superoxide dismutase. In addition, competition studies between cisplatin and RAPTA-C showed that the two metallodrugs have affinities for the same amino acid residues on protein binding.

  18. Rationalization of the inhibition activity of structurally related organometallic compounds against the drug target cathepsin B by DFT.

    PubMed

    Casini, Angela; Edafe, Fabio; Erlandsson, Mikael; Gonsalvi, Luca; Ciancetta, Antonella; Re, Nazzareno; Ienco, Andrea; Messori, Luigi; Peruzzini, Maurizio; Dyson, Paul J

    2010-06-21

    A series of organometallic compounds of general formula [(arene)M(PTA)(n)X(m)]Y (arene = eta(6)-C(10)H(14), eta-C(5)Me(5)); M = Ru(ii), Os(ii), Rh(iii) and Ir(iii); X = Cl, mPTA; Y = OTf, PF(6)) have been screened for their cytotoxicity and ability to inhibit cathepsin B in vitro, in comparison to the antimetastatic compound NAMI-A. The Ru and Os analogues and NAMI-A showed similar enzyme inhibition properties (with IC(50) values in the low muM range), whereas the Rh(iii) and Ir(iii) compounds were inactive. In order to build up a rational for the observed differences, DFT calculations of the metal complexes adducts with N-acetyl-l-cysteine-N'-methylamide, a mimic for the Cys residue in the cathepsin B active site, were performed to provide insights into binding thermodynamics in solution. Initial structure-activity relationships have been defined with the calculated binding energies of the M-S bonds correlating well with the observed inhibition properties of the compounds.

  19. Effects of Reaction Conditions on the Properties of Spherical Silver Powders Synthesized by Reduction of an Organometallic Compound

    NASA Astrophysics Data System (ADS)

    Chiang, Ying-Jung; Wang, Sea-Fue; Lu, Chun-An; Lin, Hong-Ching

    2014-09-01

    Silver powders were synthesized by reducing a silver organometallic compound, silver 2-ethylhexanoate, with di- n-octylamine. The effects of preparation conditions on the characteristics of the powders were investigated. Silver powders prepared from silver 2-ethylhexanoate and di- n-octylamine in the ratio 2:1 (MA21) at 150°C for 3 h had the best characteristics (average particle size 277 nm, narrow particle-size distribution, high tap density of 4.0 g/cm3), and were also obtained in high yield (98%). Use of an excessive amount of di- n-octylamine resulted in intense thermolysis and a low yield of silver powders of irregular morphology with a wide particle-size distribution. As the proportion of silver 2-ethylhexanoate was increased, the silver powders obtained had a bimodal particle-size distribution and a relatively low tap density. Silver films seemed to have high resistivity when the temperature used for synthesis of the silver powders was too low or reaction time was insufficient. The electrical resistivities of silver films prepared from MA21 powders and sintered at 300°C and 500°C for 30 min were 3.8 × 10-6 Ω cm and 2.3 × 10-6 Ω cm, respectively, close to that of bulk silver.

  20. Assessment of background concentrations of organometallic compounds (methylmercury, ethyllead and butyl- and phenyltin) in French aquatic environments.

    PubMed

    Cavalheiro, Joana; Sola, Cristina; Baldanza, Julie; Tessier, Emmanuel; Lestremau, François; Botta, Fabrizio; Preud'homme, Hugues; Monperrus, Mathilde; Amouroux, David

    2016-05-01

    The aim of this work is to estimate background concentrations of organometallic compounds, such as tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPhT), diphenyltin (DPhT), monophenyltin (MPhT), methylmercury (MeHg), inorganic mercury (iHg) and diethyllead (Et2Pb) in the aquatic environment at the French national scale. Both water and sediment samples were collected all over the country, resulting in 152 water samples and 123 sediment samples collected at 181 sampling points. Three types of surface water bodies were investigated: rivers (140 sites), lakes (19 sites) and coastal water (42 sites), spread along the 11 French river basins. The choice of sites was made on the basis of previous investigation results and the following target criteria: reference, urban sites, agricultural and industrial areas. The analytical method was properly validated for both matrices prior to analysis, resulting in low limits of quantification (LOQ), good precision and linearity in agreement with the Water Framework Directive demands. The results were first evaluated as a function of their river basins, type of surrounding pressure and water bodies. Later, background concentrations at the French national scale were established for both water and sediment matrices, as well as their threshold, i.e., the concentration that distinguishes background from anomalies or contaminations. Background concentrations in water are ranging between <0.04-0.14 ng Hg. L(-1) for MeHg, <0.14-2.10 ng Hg. L(-1) for iHg, <1.0-8.43 ng Pb. L(-1) for Et2Pb and 0.49-151 ng Sn. L(-1), <0.08-3.04 ng Sn. L(-1) and <0.08-0.25 ng Sn. L(-1) for MBT, DBT and TBT, respectively. For sediments, background concentrations were set as <0.09-1.11 ng Hg. g(-1) for MeHg, <0.06-24.3 ng Pb. g(-1) for Et2Pb and <1.4-13.4 ng Sn. g(-1), <0.82-8.54 ng Sn. g(-1), <0.25-1.16 ng Sn. g(-1) and <0.08-0.61 ng Sn. g(-1) for MBT, DBT, TBT and DPhT, respectively. TBT occurs in higher concentrations than the available

  1. Studies of the hydrogenation of small unsaturated molecules using organometallic cluster compounds as catalysts

    SciTech Connect

    Not Available

    1981-01-01

    Progress under contract DE-AC02-78ER04900 and plans for continued investigations of the reactivity of transition metal hydride cluster compounds with small heteronuclear unsaturated molecules are described. Research will include further elucidation of the mechanisms of hydrogen transfer from metal atoms to unsaturated substrates and studies of the structure and bonding of partially hydrogenated substrates coordinated to polynuclear metal centers. Investigations of the reactivity of the bridging hydride ligand and the chemistry of alkyl groups in clusters are planned. The development of heteronuclear clusters as homogeneous CO hydrogenation catalysts will be attempted.

  2. An Organometallic Compound which Exhibits a DNA Topology-Dependent One-Stranded Intercalation Mode.

    PubMed

    Ma, Zhujun; Palermo, Giulia; Adhireksan, Zenita; Murray, Benjamin S; von Erlach, Thibaud; Dyson, Paul J; Rothlisberger, Ursula; Davey, Curt A

    2016-06-20

    Understanding how small molecules interact with DNA is essential since it underlies a multitude of pathological conditions and therapeutic interventions. Many different intercalator compounds have been studied because of their activity as mutagens or drugs, but little is known regarding their interaction with nucleosomes, the protein-packaged form of DNA in cells. Here, using crystallographic methods and molecular dynamics simulations, we discovered that adducts formed by [(η(6) -THA)Ru(ethylenediamine)Cl][PF6 ] (THA=5,8,9,10-tetrahydroanthracene; RAED-THA-Cl[PF6 ]) in the nucleosome comprise a novel one-stranded intercalation and DNA distortion mode. Conversely, the THA group in fact remains solvent exposed and does not disrupt base stacking in RAED-THA adducts on B-form DNA. This newly observed DNA binding mode and topology dependence may actually be prevalent and should be considered when studying covalently binding intercalating compounds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Binding of Organometallic Ruthenium(II) Anticancer Compounds to Nucleobases: A Computational Study

    NASA Astrophysics Data System (ADS)

    Gossens, Christian; Tavernelli, Ivano; Rothlisberger, Ursula

    2009-09-01

    The reaction of the anticancer compound [(η6-benzene)Ru(en)(OH2)]2+ (1) toward the nucleobases guanine, adenine, and cytosine is studied computationally using DFT/BP86 calculations. The aqua leaving group of such compounds is known to undergo ligand exchange reactions with nucleophilic centers in DNA and preferentially with the N7 atom of guanine, N7(G). Our results show that an H-bonded reactant adduct with nucleobases is formed via either the aqua ligand (cis adduct) or the en (ethylenediamine) ligand (trans adduct) of 1. All studied nucleobases favor an H-bonded cis adduct. Only guanine forms also a trans reactant adduct in the gas phase. The guanine N7 and O6 atoms in this trans adduct are situated in an ideal position to form each a strong H-bond to both amino groups of the en ligand of 1. A docking study shows that this unique recognition pattern is also plausible for the interaction with double stranded DNA. For the reaction of 1 with guanine, we identified three different reaction pathways: (i) A cis (G)N7-Ru-OH2 transition state (TS). (ii) A direct trans reaction pathway. (iii) A 2-step trans mechanism. The activation energies for the cis pathway are smaller than for the trans pathways. The ultimately formed Ru-N7(G) product is characterized by a thermally stable H-bond between the O6(G) and a diamine-NH2 hydrogen.

  4. Distribution of organic and organometallic compounds in sediments from the Louisianian Province

    SciTech Connect

    Maruya, K.; Ertel, J.; Loganathan, B.

    1996-12-31

    In 1994, over 200 sediment samples were collected in accordance with EPA`s EMAP probabilistic sampling protocol from coastal and estuarine areas in the Louisianian Province (Gulf of Mexico). These samples represent a homogenate of 3 to 5 grabs from which the top 2 cm of surficial sediments were extracted. These samples were frozen and shipped to the Skidaway Institute of Oceanography for analysis of metal and organic constituents. Frozen sediments were freeze dried and up to 40 g were soxhlet extracted with CH{sub 2}Cl{sub 2}. This extract was then divided into several sub-aliquots for analysis of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides, organophosphate pesticides and organotin (butyl- and phenyltins) compounds. Interferences were removed using packed column chromatography and split extracts were analyzed by GC with the appropriate detection technique.

  5. Structure--activity relationship and mode of action of N-(6-ferrocenyl-2-naphthoyl) dipeptide ethyl esters: novel organometallic anticancer compounds.

    PubMed

    Mooney, Aine; Tiedt, Rachel; Maghoub, Thamir; O'Donovan, Norma; Crown, John; White, Blánaid; Kenny, Peter T M

    2012-06-14

    In this article, we report the findings of a comprehensive structure-activity relationship study of N-(6-ferrocenyl-2-naphthoyl) dipeptide ethyl esters, in which novel analogues were designed, synthesized, and evaluated in vitro for antiproliferative effect. Two new compounds, 2 and 16, showed potent nanomolar activity in the H1299 NSCLC cell line, with exceptional IC(50) values of 0.13 and 0.14 μM, respectively. These compounds were also found to have significant activity in the Sk-Mel-28 malignant melanoma cell line (IC(50) values of 1.10 and 1.06 μM, respectively). Studies were also conducted to elucidate the mode of action of these novel organometallic anticancer compounds. Cell cycle analysis in the H1299 cell line suggests these compounds induce apoptosis, while guanine oxidation studies confirm that 2 is capable of generating oxidative damage via a ROS-mediated mechanism.

  6. Organometallic Radiopharmaceuticals

    NASA Astrophysics Data System (ADS)

    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.

  7. Organometallic complexes: new tools for chemotherapy.

    PubMed

    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.

  8. Organometallic Neptunium Chemistry.

    PubMed

    Arnold, Polly L; Dutkiewicz, Michał S; Walter, Olaf

    2017-09-13

    Fifty years have passed since the foundation of organometallic neptunium chemistry, and yet only a handful of complexes have been reported, and even fewer have been fully characterized. Yet, increasingly, combined synthetic/spectroscopic/computational studies are demonstrating how covalently bonding, soft, carbocyclic organometallic ligands provide an excellent platform for advancing the fundamental understanding of the differences in orbital contributions and covalency in f-block metal-ligand bonding. Understanding the subtleties is the key to the safe handling and separations of the highly radioactive nuclei. This review describes the complexes that have been synthesized to date and presents a critical assessment of the successes and difficulties in their analysis and the bonding information they have provided. Because of increasing recent efforts to start new Np-capable air-sensitive inorganic chemistry laboratories, the importance of radioactivity, the basics of Np decay and its ramifications (including the radiochemical synthesis of one organometallic compound), and the available anhydrous starting materials are also surveyed. The review also highlights a range of instances in which important differences in the chemical behavior between Np and its closest neighbors, uranium and plutonium, are found.

  9. 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

    NASA Astrophysics Data System (ADS)

    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.

  10. TRIFLUOROMETHYL COMPOUNDS OF GERMANIUM

    DTIC Science & Technology

    FLUORIDES, *GERMANIUM COMPOUNDS, *HALIDES, *ORGANOMETALLIC COMPOUNDS, ALKYL RADICALS, ARSENIC COMPOUNDS, CHEMICAL BONDS, CHEMICAL REACTIONS ...CHLORIDES, CHLORINE COMPOUNDS, HYDROLYSIS, IODIDES, METHYL RADICALS, POTASSIUM COMPOUNDS, PYROLYSIS, STABILITY, SYNTHESIS, TIN COMPOUNDS.

  11. Synthesis of a sugar-organometallic compound 1,1‧-difurfurylferrocene and its microwave preparation of carbon/iron oxide nanocomposite

    NASA Astrophysics Data System (ADS)

    Zhao, Shanyu; Cooper, Daniel C.; Xu, Haixun; Zhu, Pinghua; Suggs, J. William

    2013-01-01

    In order to synthesize a carbon-metal or metal oxide combination sphere, carbonaceous resource furfural 1 was introduced, which was nucleophilic treated with 1,1‧-dilithioferrocene 2 to form a sugar-organometallic compound: ferrocenyl monosaccharide derivative 1,1‧-difurfurylferrocene 3. 1,1‧-Difurfurylferrocene 3 can be hydrothermally treated in a microwave reactor to give 300-500 nm microspheres with the α-Fe2O3 or Fe3O4 nanocrystals formed on the surface, which may be favorable for new magnetic materials preparation or instead of iron with other metal ions, versatile carbon/metal composites will be possibly synthesized for catalysis, drug delivery and magnetic uses.

  12. 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}

    SciTech Connect

    Acree, William; Chickos, James S.

    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.

  13. Organometallic neptunium(III) complexes.

    PubMed

    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.

  14. Organometallic neptunium(III) complexes

    NASA Astrophysics Data System (ADS)

    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.

  15. Organometallic Titanocene–Gold Compounds as Potential Chemotherapeutics in Renal Cancer. Study of their Protein Kinase Inhibitory Properties

    PubMed Central

    2015-01-01

    Early–late transition metal TiAu2 compounds [(η-C5H5)2Ti{OC(O)CH2PPh2AuCl}2] (3) and new [(η-C5H5)2Ti{OC(O)-4-C6H4PPh2AuCl}2] (5) were evaluated as potential anticancer agents in vitro against renal and prostate cancer cell lines. The compounds were significantly more effective than monometallic titanocene dichloride and gold(I) [{HOC(O)RPPh2}AuCl] (R = −CH2– 6, −4-C6H4– 7) derivatives in renal cancer cell lines, indicating a synergistic effect of the resulting heterometallic species. The activity on renal cancer cell lines (for 5 in the nanomolar range) was considerably higher than that of cisplatin and highly active titanocene Y. Initial mechanistic studies in Caki-1 cells in vitro coupled with studies of their inhibitory properties on a panel of 35 kinases of oncological interest indicate that these compounds inhibit protein kinases of the AKT and MAPKAPK families with a higher selectivity toward MAPKAPK3 (IC503 = 91 nM, IC505 = 117 nM). The selectivity of the compounds in vitro against renal cancer cell lines when compared to a nontumorigenic human embryonic kidney cell line (HEK-293T) and the favorable preliminary toxicity profile on C57black6 mice indicate that these compounds (especially 5) are excellent candidates for further development as potential renal cancer chemotherapeutics. PMID:25435644

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  18. Group IV organometallic compounds based on dianionic "pincer" ligands: synthesis, characterization, and catalytic activity in intramolecular hydroamination reactions.

    PubMed

    Luconi, Lapo; Rossin, Andrea; Motta, Alessandro; Tuci, Giulia; Giambastiani, Giuliano

    2013-04-08

    Neutral Zr(IV) and Hf(IV) diamido complexes stabilized by unsymmetrical dianionic N,C,N' pincer ligands have been prepared through the simplest and convenient direct metal-induced Caryl-H bond activation. Simple ligand modification has contributed to highlight the non-innocent role played by the donor atom set in the control of the cyclometallation kinetics. The as-prepared bis-amido catalysts were found to be good candidates for the intramolecular hydroamination/cyclization of primary aminoalkenes. The ability of these compounds to promote such a catalytic transformation efficiently (by providing, in some cases, fast and complete substrate conversion at room temperature) constitutes a remarkable step forward toward catalytic systems that can operate at relatively low catalyst loading and under milder reaction conditions. Kinetic studies and substrate-scope investigations, in conjunction with preliminary DFT calculations on the real systems, were used to elucidate the effects of the substrate substitution on the catalyst performance and to support the most reliable mechanistic path operative in the hydroamination reaction.

  19. Organometallic Chemistry of Molybdenum.

    ERIC Educational Resources Information Center

    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)

  20. Organometallic Chemistry of Molybdenum.

    ERIC Educational Resources Information Center

    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)

  1. Chromo- and Fluorogenic Organometallic Sensors

    NASA Astrophysics Data System (ADS)

    Fletcher, Nicholas C.; Lagunas, M. Cristina

    Compounds that change their absorption and/or emission properties in the presence of a target ion or molecule have been studied for many years as the basis for optical sensing. Within this group of compounds, a variety of organometallic complexes have been proposed for the detection of a wide range of analytes such as cations (including H+), anions, gases (e.g. O2, SO2, organic vapours), small organic molecules, and large biomolecules (e.g. proteins, DNA). This chapter focuses on work reported within the last few years in the area of organometallic sensors. Some of the most extensively studied systems incorporate metal moieties with intense long-lived metal-to-ligand charge transfer (MLCT) excited states as the reporter or indicator unit, such as fac-tricarbonyl Re(I) complexes, cyclometallated Ir(III) species, and diimine Ru(II) or Os(II) derivatives. Other commonly used organometallic sensors are based on Pt-alkynyls and ferrocene fragments. To these reporters, an appropriate recognition or analyte-binding unit is usually attached so that a detectable modification on the colour and/or the emission of the complex occurs upon binding of the analyte. Examples of recognition sites include macrocycles for the binding of cations, H-bonding units selective to specific anions, and DNA intercalating fragments. A different approach is used for the detection of some gases or vapours, where the sensor's response is associated with changes in the crystal packing of the complex on absorption of the gas, or to direct coordination of the analyte to the metal centre.

  2. Chemistry related to semiconductor growth involving organometallics

    NASA Astrophysics Data System (ADS)

    Husk, G. R.; Jones, K. A.; Paur, R. J.; Prater, J. T.

    1990-05-01

    OMVPE (OrganoMetallic Vapor-Phase Epitaxy) technology requirements for III-V compounds and chemistry related to semiconductor growth involving organometallics are discussed. The following subject areas are covered: semiconductor device requirements; Army II-VI deposition program/MOMBE (Metal Organic Molecular Beam Epitaxy) for IR detector applications; epitaxial growth of III-V's and II-VI's using organometallics; electrical device requirements; environmental and safety issues in MOVPE; quantum chemistry of vapor phase; carbon doping and selective epitaxy (tailoring growth chemistry in MOVPE); TBA/TBP precursors in GaAs and InP MOCVD; single source precursors for III-V OMCVD (OrganoMetallic Chemical Vapor Deposition) growth; alternate sources for MOMBE of AlGaAs; mechanism of incorporation of impurities and analysis of carbon contamination; growth on nonplanar and patterned substrates; CBE growth mechanisms; TriMethylamine Alane (a new robust precursor for MOMBE growth of AlGaAs); real-time determinations of OMCVD growth kinetics on GaAs by reflectance-difference spectroscopy; photoreflectance measurements; growth and doping mechanisms for HgCdTe; photoassisted CBE (Chemical Beam Epitaxy) of CdTe and HgCdTe alloys; in-situ analysis of ZnSe growth by OMCVD using X-ray scattering; biodegradation of GaAs IC chips and wafers; detailed models of compound semiconductor growth by MOCVD; gas phase probes of GaAs cluster chemistry; photodecomposition of organometallic compounds at 193 nm; manufacturing issues in MOCVD compound semiconductor technology.

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

    ERIC Educational Resources Information Center

    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…

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

    ERIC Educational Resources Information Center

    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…

  5. Optimisation of a headspace-solid-phase micro-extraction method for simultaneous determination of organometallic compounds of mercury, lead and tin in water by gas chromatography-tandem mass spectrometry.

    PubMed

    Beceiro-González, E; Guimaraes, A; Alpendurada, M F

    2009-07-17

    In this work, a headspace-solid-phase micro-extraction (HS-SPME) combined with gas chromatography-mass spectrometry (GC-MS) method for multielemental speciation of organometallic compounds of mercury, lead and tin in water samples was upgraded by the introduction of tandem mass spectrometry (MS/MS) as detection technique. The analytical method is based on the ethylation with NaBEt(4) and simultaneous headspace-solid-phase micro-extraction of the derivative compounds followed by GC-MS/MS analysis. The main experimental parameters influencing the extraction efficiency such as derivatisation time, extraction time and extraction temperature were optimized. The overall optimum extraction conditions were the following: a 50 microm/30 microm divinyl-benzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) SPME fibre, 150 min derivatisation time, 15 min extraction time, sample agitation at 250 rpm and 40 degrees C extraction temperature. The analytical characteristics of the HS-SPME method combined with GC-MS and GC-MS/MS were evaluated. The combination of both techniques HS-SPME and GC-MS/MS allowed to attain lower limits of detection (4-33 ng l(-1)) than those obtained by HS-SPME-GC-MS (17-45 ng l(-1)). The proposed method presented good linear regression coefficients (r(2)>0.9970) and repeatability (4.8-21.0%) for all the compounds under study. The accuracy of the method measured as the average percentage recovery of the compounds in spiked river water and seawater samples was higher than 80% for all the compounds studied, except for monobutyltin in the river water sample. A study of the uncertainty associated with the analytical results was also carried out.

  6. Inorganic and Organometallic Polymers

    NASA Astrophysics Data System (ADS)

    Chandrasekhar, Vadapalli

    This textbook is intended to give an understanding of the basic principles that constitute the field of non-conventional polymers containing inorganic and organometalic units as the repeating units. Each chapter will be self-explanatory with a good background so that it can be easily understood at the senior undergraduate level. The principles involved in the preparation of these polymers, their characterisation and their applications will be discussed. Basic inorganic chemistry required for the understanding of each topic is presented so that the content of the chapter is readily understood.

  7. Luminescent Di and Polynuclear Organometallic Gold(I)-M (Au2, {Au2Ag}n and {Au2Cu}n) Compounds Containing Bidentate Phosphanes as Active Antimicrobial Agents

    PubMed Central

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

    2012-01-01

    The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au2(mes)2(μ-LL)] (LL = dppe: 1,2-Bis(di-phenylphosphano)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 [Au2M(μ-mes)2(μ-LL)]A (M = Ag, A = ClO4−, L-L = dppe 2a, dppy 2b; M = Ag, A = SO3CF3−, L-L = dppe 3a, dppy 3b; M = Cu, A = PF6−, L-L = dppe 4a, dppy 4b). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au2(mes)2(μ-dppy)] 1b and [Au2Ag(μ-mes)2(μ-dppe)]SO3CF3 3a were determined by a single-crystal X-ray diffraction study. 3a in solid state is not a cyclic trinuclear Au2Ag derivative but it gives an open polymeric structure instead, with the {Au2(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 (metallophillic) 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 [Au2M(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 metallophylic interactions, as that observed for 3a. In solid state the heterometallic Au2M 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 [Au2Ag(μ-mes)2(μ-dppy)]ClO4 2b resulted luminescent in diluted DMSO solution

  8. Organometallic Chemistry. Final Progress Report

    SciTech Connect

    2003-07-14

    The Gordon Research Conference (GRC) on Organometallic Chemistry was held at Salve Regina, Newport, Rhode Island, 7/21-26/02. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

  9. Preparation of activated carbons with mesopores by use of organometallics

    SciTech Connect

    Yamada, Yoshio; Yoshizawa, Noriko; Furuta, Takeshi

    1996-12-31

    Activated carbons are commercially produced by steam or CO{sub 2} activation of coal, coconut shell and so on. In general the carbons obtained give pores with a broad range of distribution. The objective of this study was to prepare activated carbons from coal by use of various organometallic compounds. The carbons were evaluated for pore size by nitrogen adsorption experiments.

  10. Evidence for the involvement of 5f orbitals in the bonding and reactivity of organometallic actinide compounds: thorium(IV) and uranium(IV) bis(hydrazonato) complexes.

    PubMed

    Cantat, Thibault; Graves, Christopher R; Jantunen, Kimberly C; Burns, Carol J; Scott, Brian L; Schelter, Eric J; Morris, David E; Hay, P Jeffrey; Kiplinger, Jaqueline L

    2008-12-24

    Migratory insertion of diphenyldiazomethane into both metal-carbon bonds of the bis(alkyl) and bis(aryl) complexes (C(5)Me(5))(2)AnR(2) yields the first f-element bis(hydrazonato) complexes (C(5)Me(5))(2)An[eta(2)-(N,N')-R-N-N=CPh(2)](2) [An = Th, R = CH(3) (18), PhCH(2) (15), Ph (16); An = U, R = CH(3) (17), PhCH(2) (14)], which have been characterized by a combination of spectroscopy, electrochemistry, and X-ray crystallography. The two hydrazonato ligands adopt an eta(2)-coordination mode leading to 20-electron (for Th) and 22-electron (for U) complexes that have no transition-metal analogues. In fact, reaction of (C(5)H(5))(2)Zr(CH(3))(2) or (C(5)Me(5))(2)Hf(CH(3))(2) with diphenyldiazomethane is limited to the formation of the corresponding mono(hydrazonato) complex (C(5)R(5))(2)M[eta(2)-(N,N')-CH(3)-N-N=CPh(2)](CH(3)) (M = Zr, R = H or M = Hf, R = CH(3)). The difference in the reactivities of the group 4 metal complexes and the actinides was used as a unique platform for investigating in depth the role of 5f orbitals on the reactivity and bonding in actinide organometallic complexes. The electronic structure of the (C(5)H(5))(2)M[eta(2)-(N,N')-CH(3)-N-N=CH(2)](2) (M = Zr, Th, U) model complexes was studied using density functional theory (DFT) calculations and compared to experimental structural, electrochemical, and spectroscopic results. Whereas transition-metal bis(cyclopentadienyl) complexes are known to stabilize three ligands in the metallocene girdle to form saturated (C(5)H(5))(2)ML(3) species, in a bis(hydrazonato) system, a fourth ligand is coordinated to the metal center to give (C(5)H(5))(2)ML(4). DFT calculations have shown that 5f orbitals in the actinide complexes play a crucial role in stabilizing this fourth ligand by stabilizing both the sigma and pi electrons of the two eta(2)-coordinated hydrazonato ligands. In contrast, the stabilization of the hydrazonato ligands was found to be significantly less effective for the putative bis

  11. Potent organometallic osmium compounds induce mitochondria-mediated apoptosis and S-phase cell cycle arrest in A549 non-small cell lung cancer cells.

    PubMed

    van Rijt, Sabine H; Romero-Canelón, Isolda; Fu, Ying; Shnyder, Steve D; Sadler, Peter J

    2014-05-01

    The problems of acquired resistance associated with platinum drugs may be addressed by chemotherapeutics based on other transition metals as they offer the possibility of novel mechanisms of action. In this study, the cellular uptake and induction of apoptosis in A549 human non-small cell lung cancer cells of three promising osmium(II) arene complexes containing azopyridine ligands, [Os(η(6)-arene)(p-R-phenylazopyridine)X]PF6, where arene is p-cymene or biphenyl, R is OH or NMe2, and X is Cl or I, were investigated. These complexes showed time-dependent (4–48 h) potent anticancer activity with highest potency after 24 h (IC50 values ranging from 0.1 to 3.6 μM). Cellular uptake of the three compounds as quantified by ICP-MS, was independent of their logP values (hydrophobicity). Furthermore, maximum cell uptake was observed after 24 h, with evident cell efflux of the osmium after 48 and 72 h of exposure, which correlated with the corresponding IC50 values. The most active compound 2, [Os(η(6)-p-cymene)(NMe2-phenylazopyridine)I]PF6, was taken up by lung cancer cells predominately in a temperature-dependent manner indicating that energy-dependent mechanisms are important in the uptake of 2. Cell fractionation studies showed that all three compounds accumulated mainly in cellular membranes. Furthermore, compound 2 induced apoptosis and caused accumulation in the S-phase of the cell cycle. In addition, 2 induced cytochrome c release and alterations in mitochondrial membrane potential even after short exposure times, indicating that mitochondrial apoptotic pathways are involved. This study represents the first steps towards understanding the mode of action of this promising class of new osmium-based chemotherapeutics.

  12. Polyyn-diyls capped by diruthenium termini: a new family of carbon-rich organometallic compounds and distance-dependent electronic coupling therein.

    PubMed

    Xu, Guo-Lin; Zou, Gang; Ni, Yu-Hua; DeRosa, Maria C; Crutchley, Robert J; Ren, Tong

    2003-08-20

    Polyyn-diyls capped by Ru(2)(ap)(4) termini (ap = 2-anilinopyridinate), that is, [Ru2(ap)4](mu-C,C'-C2m)[Ru2(ap)4] (compounds 1-5 with m = 1-4 and 6), were synthesized through either a metathesis reaction between Ru2(ap)4Cl and LiC(2m)Li or a Glaser homocoupling reaction of Ru2(ap)4(CmH) under Eglinton/Hay conditions. X-ray diffraction studies of compounds 2 and 4 revealed both the linear rigid rod topology of these compounds and the fine structural details about the Ru2 cores and polyyn-diyl chains. Cyclic and differential pulse voltammetric (CV and DPV) measurements and spectroelectrochemical studies show that reduced and oxidized forms of 1, 2, 4, and 5 are donor-acceptor systems in which the Ru2 termini are coupled to varying degrees depending upon the length of the polyyn-diyl bridge.

  13. Structure investigations of group 13 organometallic carboxylates.

    PubMed

    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. Perfluorinated Ligands in Organometallic Chemistry

    DTIC Science & Technology

    1989-12-12

    Decacarbonyldimanganese. Organometallics, 1986, 1,2391. W.P. Henry and R.P. Hughes, Organic Synthesis Using Carbon Monoxide. Regiospecific Cobalt Mediated...Pentamethylcyclopentadiene with Decacarbonyldi manganese. Organometalllcs, 1986, 1,2391. 4. W.P. Henry and R.P. Hughes, Organic Synthesis Using Carbon

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

    DOEpatents

    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. Organic topological insulators in organometallic lattices.

    PubMed

    Wang, Z F; Liu, Zheng; Liu, Feng

    2013-01-01

    Topological insulators are a recently discovered class of materials having insulating bulk electronic states but conducting boundary states distinguished by nontrivial topology. So far, several generations of topological insulators have been theoretically predicted and experimentally confirmed, all based on inorganic materials. Here, based on first-principles calculations, we predict a family of two-dimensional organic topological insulators made of organometallic lattices. Designed by assembling molecular building blocks of triphenyl-metal compounds with strong spin-orbit coupling into a hexagonal lattice, this new classes of organic topological insulators are shown to exhibit nontrivial topological edge states that are robust against significant lattice strain. We envision that organic topological insulators will greatly broaden the scientific and technological impact of topological insulators.

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

    EPA Science Inventory

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

    EPA Science Inventory

    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...

  19. Use of ionic liquids as coordination ligands for organometallic catalysts

    DOEpatents

    Li, Zaiwei; Tang, Yongchun; Cheng; Jihong

    2009-11-10

    Aspects of the present invention relate to compositions and methods for the use of ionic liquids with dissolved metal compounds as catalysts for a variety of chemical reactions. Ionic liquids are salts that generally are liquids at room temperature, and are capable of dissolving a many types of compounds that are relatively insoluble in aqueous or organic solvent systems. Specifically, ionic liquids may dissolve metal compounds to produce homogeneous and heterogeneous organometallic catalysts. One industrially-important chemical reaction that may be catalyzed by metal-containing ionic liquid catalysts is the conversion of methane to methanol.

  20. Organometallic Chemistry and Catalysis in Industry.

    ERIC Educational Resources Information Center

    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. Conjugated organometallic materials containing tungsten centers

    NASA Astrophysics Data System (ADS)

    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

  2. An organometallic guide to the chemistry of hydrocarbon moieties on transition metal surfaces

    SciTech Connect

    Zaera, F.

    1995-12-01

    In this review what is known about the chemistry of hydrocarbon molecules on transition metal surfaces will be surveyed. Here the authors discuss the results reported to date on the structure and reactivity of the different types of hydrocarbon moieties that form on transition metal surfaces. One of the goals of this review is to provide an organometallic guide for the possible interactions of hydrocarbons with transition metals with the idea of examining their relation to the corresponding surface chemistry. The authors however limit the review of the organometallic literature to the information relevant to the surface systems, and also narrow the field to cover only molecules with carbon and hydrogen atoms; compounds containing other atoms (O, S, N) will be excluded. The present review is organized in the following manner. First, a brief discussion of the experimental techniques used to characterize both organometallic and surface systems is presented. A discussion of the coordination and structure of the different types of organic moieties, first in organometallic compounds and then on metal surfaces, follows. Here the systems are classified according to the type of bonding between the molecules and the metals. Next, the different elementary steps that such systems can undergo are summarized: C-H and C-C bond-breaking and bond-forming reactions, isomerizations, and others. Again, the chemistry of organometallic compounds is discussed first, and the surface chemistry is presented subsequently. A brief description of a few key nonelementary reactions is also given, including some catalytic processes. Lastly, a brief discussion on the main similarities and differences found so far between surface and organometallic systems, and on possible future directions for this field, is offered.

  3. Sizable band gap in organometallic topological insulator

    NASA Astrophysics Data System (ADS)

    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.

  4. Anticancer Organometallic Osmium(II)-p-cymene Complexes.

    PubMed

    Păunescu, Emilia; Nowak-Sliwinska, Patrycja; Clavel, Catherine M; Scopelliti, Rosario; Griffioen, Arjan W; Dyson, Paul J

    2015-09-01

    Osmium compounds are attracting increasing attention as potential anticancer drugs. In this context, a series of bifunctional organometallic osmium(II)-p-cymene complexes functionalized with alkyl or perfluoroalkyl groups were prepared and screened for their antiproliferative activity. Three compounds from the series display selectivity toward cancer cells, with moderate cytotoxicity observed against human ovarian carcinoma (A2780) cells, whereas no cytotoxicity was observed on non-cancerous human embryonic kidney (HEK-293) cells and human endothelial (ECRF24) cells. Two of these three cancer-cell-selective compounds induce cell death largely via apoptosis and were also found to disrupt vascularization in the chicken embryo chorioallantoic membrane (CAM) model. Based on these promising properties, these compounds have potential clinical applications.

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

    PubMed

    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.

  6. Combinatorial sythesis of organometallic materials

    DOEpatents

    Schultz, Peter G.; Xiang, Xiaodong; Goldwasser, Isy

    2002-07-16

    Methods and apparatus for the preparation and use of a substrate having an array of diverse materials in predefined regions thereon. A substrate having an array of diverse materials thereon is generally prepared by delivering components of materials to predefined regions on a substrate, and simultaneously reacting the components to form at least two materials. Materials which can be prepared using the methods and apparatus of the present invention include, for example, covalent network solids, ionic solids and molecular solids. More particularly, materials which can be prepared using the methods and apparatus of the present invention include, for example, inorganic materials, intermetallic materials, metal alloys, ceramic materials, organic materials, organometallic materials, non-biological organic polymers, composite materials (e.g., inorganic composites, organic composites, or combinations thereof), etc. Once prepared, these materials can be screened for useful properties including, for example, electrical, thermal, mechanical, morphological, optical, magnetic, chemical, or other properties. Thus, the present invention provides methods for the parallel synthesis and analysis of novel materials having useful properties.

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

    ERIC Educational Resources Information Center

    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…

  8. Hydrotreatment of bio-oil over Ni-based catalyst.

    PubMed

    Zhang, Xinghua; Wang, Tiejun; Ma, Longlong; Zhang, Qi; Jiang, Ting

    2013-01-01

    Inexpensive non-sulfided Ni-based catalysts were evaluated for hydrotreatments using phenol as model compound. HZSM-5, a zeolite with different ratio of Si/Al and γ-Al(2)O(3) were impregnated with Ni(NO(3))(2) · 6H(2)O and calcined at 450 °C. Conversion rates and product distribution for treatment of phenol at 160-240 °C in the presence of catalysts with nickel loads of 6, 10, 14 and 17 wt.% were determined. Phenol conversion was highest (91.8%) at 240 °C in the presence of HZSM-5(Si/Al = 38) loaded with 10% Ni. When hydrotreatment was carried out with bio-oil obtained from pyrolysis of pine sawdust under the optimal conditions determined for phenol, the pH of bio-oil increased from 2.27 to 4.07, and the hydrogen content increased from 6.28 to 7.01 wt.%. The decrease in acidity is desirable for the use of upgraded bio-oil.

  9. Organometallic Antitumour Agents with Alternative Modes of Action

    NASA Astrophysics Data System (ADS)

    Casini, Angela; Hartinger, Christian G.; Nazarov, Alexey A.; Dyson, Paul J.

    The therapeutic index of drugs that target DNA, a ubiquitous target present in nearly all cells, is low. Nevertheless, DNA has remained the primary target for medicinal chemists developing metal-based anticancer drugs, although DNA has been essentially abandoned in favour of non-genomic targets by medicinal chemists developing organic drugs. A number of organometallic drugs that target proteins/enzymes have been developed and these compounds, based on ruthenium, osmium and gold, are described in this chapter. Targets include cathepsin B, thioredoxin reductases, multidrug resistance protein (Pgp), glutathione S-transferases and kinases. It is found that compounds that inhibit these various targets are active against metastatic tumours, or tumours that are resistant to classical DNA damaging agents such as cisplatin, and therefore offer considerable potential in clinical applications.

  10. Automated building of organometallic complexes from 3D fragments.

    PubMed

    Foscato, Marco; Venkatraman, Vishwesh; Occhipinti, Giovanni; Alsberg, Bjørn K; Jensen, Vidar R

    2014-07-28

    A method for the automated construction of three-dimensional (3D) molecular models of organometallic species in design studies is described. Molecular structure fragments derived from crystallographic structures and accurate molecular-level calculations are used as 3D building blocks in the construction of multiple molecular models of analogous compounds. The method allows for precise control of stereochemistry and geometrical features that may otherwise be very challenging, or even impossible, to achieve with commonly available generators of 3D chemical structures. The new method was tested in the construction of three sets of active or metastable organometallic species of catalytic reactions in the homogeneous phase. The performance of the method was compared with those of commonly available methods for automated generation of 3D models, demonstrating higher accuracy of the prepared 3D models in general, and, in particular, a much wider range with respect to the kind of chemical structures that can be built automatically, with capabilities far beyond standard organic and main-group chemistry.

  11. Automated design of realistic organometallic molecules from fragments.

    PubMed

    Foscato, Marco; Occhipinti, Giovanni; Venkatraman, Vishwesh; Alsberg, Bjørn K; Jensen, Vidar R

    2014-03-24

    A method for the automated generation of realistic, synthetically accessible transition metal and organometallic complexes is described. Computational tools were designed to generate molecular fragments, preferably harvested from libraries of existing, stable compounds, to be used as building blocks for the construction of new molecules. These fragments are enriched with information about the number and type of possible connections to other fragments and are stored in library files. When connecting fragments in the subsequent building process, compatibility matrices, which define the connection rules between fragments, are used to delineate organometallic fragment spaces from which molecules can be generated in an automated fashion. The approach is flexible and allows ample structural variation at the same time as the combination of known fragments is easily restrained to avoid generation of exotic and unrealistic substructures and molecules. The method was tested in the generation of ruthenium complexes, with a given coordination environment, which can serve as candidates in catalyst development. The results demonstrate that molecules generated with the described method do not contain exotic arrangements of atoms and are by far more realistic than those obtained by the application of valence rules alone.

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

    PubMed

    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.

  13. Pulsed Laser Deposition of the Ni-Base Superalloy Films

    NASA Astrophysics Data System (ADS)

    Shin, Joonghan; Mazumder, Jyotirmoy

    2016-03-01

    Ni-base superalloy films were deposited on single-crystal (SC) Ni-base superalloy substrates from a target with the same alloy composition by pulsed laser deposition (PLD) technique. Microstructure and growth behavior of the films deposited were investigated by X-ray diffraction and scanning electron microscopy, and atomic force microscope. The homoepitaxial growth of the SC Ni-base superalloy film occurred at the 1123 K (850 °C) substrate temperature and 2 J/cm2 pulse energy. Films generally exhibited a strong polycrystalline characteristic as the substrate temperature and pulse energy increased. The SC film had a smooth surface. The measured root mean square roughness of the SC film surface was ~6 nm. Based on the Taguchi analysis, the substrate temperature and pulse energy were the most significant process parameters influencing the structural characteristics of the films. Also, the influence of the pulse repletion rate and deposition time was not found to be significant.

  14. A ferroelectric olefin-copper(I) organometallic polymer with flexible organic ligand (R)-MbVBP

    NASA Astrophysics Data System (ADS)

    Wang, Guo-Xi; Xing, Zheng; Chen, Li-Zhuang; Han, Guang-Fan

    2015-07-01

    Hydrothermal treatment of (R)-2-methyl-1,4-bis(4-vinylbenzyl)piperazine [(R)-MbVBP] and CuCl afforded a novel olefin-copper(I) coordination compound. Introducing the flexible ligand (R)-MbVBP allowed the olefin-copper(I) organometallic compound to crystallize in a polar point group P21. The compound was ferroelectric, and its electric hysteresis loop showed a remnant polarization (Pr) of 0.13-0.32 μC cm-2 and a coercive field (Ec) of 3.5-11 kV cm-1.

  15. Recent developments in TiNi-based shape memory alloys

    NASA Astrophysics Data System (ADS)

    Miyazaki, Shuichi; Kohl, Manfred

    1998-07-01

    Recently, a variety of manufacturing methods have enabled us to produce fine or thin shapes or unique structure of TiNi-based shape memory alloys: e.g., (a) rolled thin plates with a thickness less than 100 μm, (b) drawn fine wires with a diameter less than 50 μm, (c) drawn microtubes with an outer diameter less than 350 μm, (d) sputter-deposited thin films with a thickness less than 1 μm, (e) rapidly solidified ribbons of several tens μm thickness and (f) sintered porous structured materials. The characteristics and applications of these TiNi-based alloys are reviewed.

  16. Mechanistic study of organometallic vapor phase epitaxy

    SciTech Connect

    Stringfellow, G.B.

    1990-12-31

    Only AsH{sub 3} and PH{sub 3} have been used as the group V source molecules for organometallic vapor phase epitaxy (OMVPE) of III/V semiconductors until recently, since they have been the only precursors yielding device quality materials. This paper reviews recent work on the pyrolysis of individual organometallic molecules, with emphasis on the group V sources, including: (1) the methylarsines, di- and tri-methylarsine, (2) the ethylarsines, mono-, di-, and tri-ethylarsine, and (3) the singly substituted tertiarybutyl arsine and phosphine molecules. The pyrolysis and growth reactions occurring when both group III and group V precursors are present simultaneously, i.e., the reactions occuring during OMVPE growth of several III/V semiconductors, are also briefly reviewed.

  17. Mechanistic study of organometallic vapor phase epitaxy

    SciTech Connect

    Stringfellow, G.B.

    1990-01-01

    Only AsH{sub 3} and PH{sub 3} have been used as the group V source molecules for organometallic vapor phase epitaxy (OMVPE) of III/V semiconductors until recently, since they have been the only precursors yielding device quality materials. This paper reviews recent work on the pyrolysis of individual organometallic molecules, with emphasis on the group V sources, including: (1) the methylarsines, di- and tri-methylarsine, (2) the ethylarsines, mono-, di-, and tri-ethylarsine, and (3) the singly substituted tertiarybutyl arsine and phosphine molecules. The pyrolysis and growth reactions occurring when both group III and group V precursors are present simultaneously, i.e., the reactions occuring during OMVPE growth of several III/V semiconductors, are also briefly reviewed.

  18. Gamma-channel stabilization mechanism in Ni-base superalloys

    NASA Astrophysics Data System (ADS)

    Goerler, Johannes V.; Brinckmann, Steffen; Shchyglo, Oleg; Steinbach, Ingo

    2015-11-01

    A mechanism is presented which opposes coalescence of ?-precipitates in Ni-base superalloys. The mechanism is based on the non-linear behaviour of the elastic energy in ?-channels, caused by the misfit strain between matrix and precipitate, as a function of the channel width. Variation of the channel width causes a disjoining pressure dependent on the density of misfit dislocations.

  19. 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.

    PubMed

    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.

  20. Organometallics in High Energy Chemistry.

    DTIC Science & Technology

    1983-10-31

    in monomeric form even in nonpolar solvents, unlike similar aluminum alkyls and alkoxides. Compounds 2 through 4 form 1:1 complexes with xanthone. The...alkoxy group oxygen, as shown in reaction (6). AL(Owo2) 3 + 3CH2N2 Al(CH2 0% 0 ) 3 + 3N2 (6) This insertion reaction was found to occur in the alkyl and...addition of an aluminum alkyl to a double bond, as shown in reactions (7) and (8). Our Al(iBu) 3 + CH2 =CHCH 2CH3 (iBu) 2Al(CH 2) 3CH 3 + (7) ’. 2 CH3

  1. Preparation of uranium compounds

    DOEpatents

    Kiplinger, Jaqueline L; Montreal, Marisa J; Thomson, Robert K; Cantat, Thibault; Travia, Nicholas E

    2013-02-19

    UI.sub.3(1,4-dioxane).sub.1.5 and UI.sub.4(1,4-dioxane).sub.2, were synthesized in high yield by reacting turnings of elemental uranium with iodine dissolved in 1,4-dioxane under mild conditions. These molecular compounds of uranium are thermally stable and excellent precursor materials for synthesizing other molecular compounds of uranium including alkoxide, amide, organometallic, and halide compounds.

  2. 2012 Gordon Research Conference, Organometallic Chemistry, 8-13 2012

    SciTech Connect

    Hillhouse, Gregory

    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.

  3. The water soluble ruthenium(II) organometallic compound [Ru(p-cymene)(bis(3,5 dimethylpyrazol-1-yl)methane)Cl]Cl suppresses triple negative breast cancer growth by inhibiting tumor infiltration of regulatory T cells.

    PubMed

    Montani, Maura; Pazmay, Gretta V Badillo; Hysi, Albana; Lupidi, Giulio; Pettinari, Riccardo; Gambini, Valentina; Tilio, Martina; Marchetti, Fabio; Pettinari, Claudio; Ferraro, Stefano; Iezzi, Manuela; Marchini, Cristina; Amici, Augusto

    2016-05-01

    Ruthenium compounds have become promising alternatives to platinum drugs by displaying specific activities against different cancers and favorable toxicity and clearance properties. Here, we show that the ruthenium(II) complex [Ru(p-cymene)(bis(3,5-dimethylpyrazol-1-yl)methane)Cl]Cl (UNICAM-1) exhibits potent in vivo antitumor effects. When administered as four-dose course, by repeating a single dose (52.4mgkg-1) every three days, UNICAM-1 significantly reduces the growth of A17 triple negative breast cancer cells transplanted into FVB syngeneic mice. Pharmacokinetic studies indicate that UNICAM-1 is rapidly eliminated from kidney, liver and bloodstream thanks to its high hydrosolubility, exerting excellent therapeutic activity with minimal side effects. Immunohistological analysis revealed that the efficacy of UNICAM-1, mainly relies on its capacity to reverse tumor-associated immune suppression by significantly reducing the number of tumor-infiltrating regulatory T cells. Therefore, UNICAM-1 appears very promising for the treatment of TNBC. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. In vitro antimalarial activity of a new organometallic analog, ferrocene-chloroquine.

    PubMed

    Domarle, O; Blampain, G; Agnaniet, H; Nzadiyabi, T; Lebibi, J; Brocard, J; Maciejewski, L; Biot, C; Georges, A J; Millet, P

    1998-03-01

    The in vitro activities of new organometallic chloroquine analogs, based on 4-amino-quinoleine compounds bound to a molecule of ferrocene, were evaluated against chloroquine-susceptible, chloroquine-intermediate, and chloroquine-resistant, culture-adapted Plasmodium falciparum lineages by a proliferation test. One of the ferrocene analogs totally restored the activity of chloroquine against chloroquine-resistant parasites. This compound, associated with tartaric acid for better solubility, was highly effective. The role of the ferrocene in reversing chloroquine resistance is discussed, as is its potential use for human therapy.

  5. In Vitro Antimalarial Activity of a New Organometallic Analog, Ferrocene-Chloroquine

    PubMed Central

    Domarle, O.; Blampain, G.; Agnaniet, H.; Nzadiyabi, T.; Lebibi, J.; Brocard, J.; Maciejewski, L.; Biot, C.; Georges, A. J.; Millet, P.

    1998-01-01

    The in vitro activities of new organometallic chloroquine analogs, based on 4-amino-quinoleine compounds bound to a molecule of ferrocene, were evaluated against chloroquine-susceptible, chloroquine-intermediate, and chloroquine-resistant, culture-adapted Plasmodium falciparum lineages by a proliferation test. One of the ferrocene analogs totally restored the activity of chloroquine against chloroquine-resistant parasites. This compound, associated with tartaric acid for better solubility, was highly effective. The role of the ferrocene in reversing chloroquine resistance is discussed, as is its potential use for human therapy. PMID:9517929

  6. Organotitanoxanes with unique structure among transition-element organometallic oxide derivatives.

    PubMed

    Buitrago, Olga; Mosquera, Marta E G; Jiménez, Gerardo; Cuenca, Tomás

    2008-05-19

    The synthesis of novel titanoxane compounds, [{(TiCl)(Ti)[mu-(eta(5)-C5Me4SiMe2O-kappaO)]2(mu-O)}2(mu-O)] (4) and [{Ti[mu-(eta(5)-C5Me4SiMe2O-kappaO)](mu-O)}6] (5), by controlled hydrolysis of a dinuclear titanium/oxo complex is described. Complexes 4 and 5 show unprecedented structural features for organometallic oxide derivatives of transition elements and represent unique fully characterized examples of tetra- and hexanuclear organo-transition-metal oxide compounds with an open-chain and a monocyclic structure, respectively.

  7. Occurrence and Fate of Organic and Organometallic Pollutants in Municipal Wastewater Treatment Plants and Their Impact on Receiving Waters (Adour Estuary, France).

    PubMed

    Cavalheiro, J; Zuloaga, O; Prieto, A; Preudhomme, H; Amouroux, D; Monperrus, M

    2017-06-19

    To achieve a "Good Environmental Status by 2015," as demanded by the water framework directive, monitoring programs are needed to furnish data on target compounds. In this study, a first evaluation of influents and main emissions of 3 local wastewater treatment plants (WWTP) in the Adour estuary (southwest of France) was performed for 23 pollutants (10 musk fragrances, 5 alkylphenols, and 8 organometallics), as well as receiving estuarine water from the same area. High frequency of occurrence of these compounds was found in influents samples (musks: 22-100%; alkylphenols 11-100%; organometallics 0-100%) and effluents (musks: 0-100%; alkylphenols 0-100%; organometallics 0-100%). The removal efficiencies were calculated and varied from negative values up to 98% with the lowest values for synthetic musk compounds. Temporal variability of the target compounds also was studied, and a few tendencies were observed. Estimation of the daily output of each WWTP into the estuary also showed that galaxolide, nonylphenol, monobuthyltin, and inorganic mercury were the compounds discharged into the environment at the highest concentrations. Finally, the occurrence of these compounds in estuarine waters was evaluated; most of them were present at concentrations below the limits of quantification (musks: 0.53-41.5 ng/L; alkylphenols 3.4-410 ng/L; organometallics 0.02-0.70 ng/L) suggesting a low impact in the resulting receiving waters.

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

    PubMed

    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

  9. Sample treatment in chromatography-based speciation of organometallic pollutants.

    PubMed

    Gómez-Riza, J L; Morales, E; Giráldez, I; Sánchez-Rodas, D; Velasco, A

    2001-12-14

    Speciation analysis is nowadays performed routinely in many laboratories to control the quality of the environment, food and health. Chemical speciation analyses generally include the study of different oxidation state of elements or individual organometallic compounds. The determination of the different chemical forms of elements is still an analytical challenge, since they are often unstable and concentrations in different matrices of interest are in the microg l(-1) or even in the ng l(-1) range (e.g., estuarine waters) or ng g(-1) in sediments and biological tissues. For this reason, sensitive and selective analytical atomic techniques are being used as available detectors for speciation, generally coupled with chromatography for the time-resolved introduction of analytes into the atomic spectrometer. The complexity of these instrumental couplings has a straightforward consequence on the duration of the analysis, but sample preparation to separate and transfer the chemical species present in the sample into a solution to be accepted readily by a chromatographic column is the more critical step of total analysis, and demands considerable operator skills and time cost. Traditionally, liquid-liquid extraction has been employed for sample treatment with serious disadvantages, such as consumption, disposal and long-term exposure to organic solvent. In addition, they are usually cumbersome and time-consuming. Therefore, the introduction of new reagents such as sodium tetraethylborate for the simultaneous derivatization of several elements has been proposed. Other possibilities are based in the implementation of techniques for efficient and accelerated isolation of species from the sample matrix. This is the case for microwave-assisted extraction, solid-phase extraction and microextraction, supercritical fluid extraction or pressurized liquid extraction, which offer new possibilities in species treatment, and the advantages of a drastic reduction of the extraction

  10. Fabrication and study of double sintered TiNi-based porous alloys

    NASA Astrophysics Data System (ADS)

    Sergey, Anikeev; Valentina, Hodorenko; Timofey, Chekalkin; Victor, Gunther; Ji-hoon, Kang; Ji-soon, Kim

    2017-05-01

    Double-sintered porous TiNi-based alloys were fabricated and their structural characteristics and physico-mechanical properties were investigated. A fabrication technology of powder mixtures is elaborated in this article. Sintering conditions were chosen experimentally to ensure good structure and properties. The porous alloys were synthesized by solid-state double diffusion sintering (DDS) of Ti-Ni powder and prepare to obtain dense, crack-free, and homogeneous samples. The Ti-Ni compound sintered at various temperatures was investigated by scanning electron microscopy. Phase composition of the sintered alloys was determined by x-ray diffraction. Analysis of the data confirmed the morphology and structural parameters. Mechanical and physical properties of the sintered alloys were evaluated. DDS at 1250 °C was found to be optimal to produce porous samples with a porosity of 56% and mean pore size of 90 μm. Pore size distribution was unimodal within the narrow range of values. The alloys present enhanced strength and ductility, owing to both the homogeneity of the macrostructure and relative elasticity of the bulk, which is hardened by the Ni-rich precipitates. These results suggest the possibility to manufacture porous TiNi-based alloys for application as a new class of dental implants.

  11. In Situ Observation of Active Oxygen Species in Fe-Containing Ni-Based Oxygen Evolution Catalysts: The Effect of pH on Electrochemical Activity.

    PubMed

    Trześniewski, Bartek J; Diaz-Morales, Oscar; Vermaas, David A; Longo, Alessandro; Bras, Wim; Koper, Marc T M; Smith, Wilson A

    2015-12-09

    Ni-based oxygen evolution catalysts (OECs) are cost-effective and very active materials that can be potentially used for efficient solar-to-fuel conversion process toward sustainable energy generation. We present a systematic spectroelectrochemical characterization of two Fe-containing Ni-based OECs, namely nickel borate (Ni(Fe)-B(i)) and nickel oxyhydroxide (Ni(Fe)OOH). Our Raman and X-ray absorption spectroscopy results show that both OECs are chemically similar, and that the borate anions do not play an apparent role in the catalytic process at pH 13. Furthermore, we show spectroscopic evidence for the generation of negatively charged sites in both OECs (NiOO(-)), which can be described as adsorbed "active oxygen". Our data conclusively links the OER activity of the Ni-based OECs with the generation of those sites on the surface of the OECs. The OER activity of both OECs is strongly pH dependent, which can be attributed to a deprotonation process of the Ni-based OECs, leading to the formation of the negatively charged surface sites that act as OER precursors. This work emphasizes the relevance of the electrolyte effect to obtain catalytically active phases in Ni-based OECs, in addition to the key role of the Fe impurities. This effect should be carefully considered in the development of Ni-based compounds meant to catalyze the OER at moderate pHs. Complementarily, UV-vis spectroscopy measurements show strong darkening of those catalysts in the catalytically active state. This coloration effect is directly related to the oxidation of nickel and can be an important factor limiting the efficiency of solar-driven devices utilizing Ni-based OECs.

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

    PubMed

    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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. [Mechanistic examination of organometallic electron transfer reactions: Annual report, 1989

    SciTech Connect

    Not Available

    1989-12-31

    Our mechanistic examination of electron transfer reactions between organometallic complexes has required data from our stopped-flow infrared spectrophotometer that was constructed in the first year. Our research on organometallic electron transfer reaction mechanisms was recognized by an invitation to the Symposium on Organometallic Reaction Mechanisms at the National ACS meeting in Miami. We have obtained a reasonable understanding of the electron transfer reactions between metal cations and anions and between metal carbonyl anions and metal carbonyl dimers. In addition we have begun to obtain data on the outer sphere electron transfer between metal carbonyl anions and coordination complexes and on reactions involving cluster anions.

  14. UV excimer laser photochemistry of hybrid organometallic compounds of gallium

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Cleaver, W. M.; Stuke, M.; Barron, A. R.

    1992-09-01

    The gas phase ultraviolet (UV) excimer laser induced photolysis of the gallium-alkyls Ga( t-C4H9) n - (CH3)3- n ( n=0, 1, 2, 3) was studied, using photolysis wavelengths of 308, 248, and 193 nm. The photofragments Ga, GaH, and GaCH3 were detected by laser ionization time-of-flight mass spectroscopy, while the hydrocarbon products CH4, C2H6, HC(CH3)3 and H2C=C(CH3)2 were identified using Fourier transform infrared (FTIR) spectroscopy. The formation of the GaH photofragment, and a high olefin-to-alkane product ratio, for Ga( t-C4H9)2(CH3) and Ga( t-C4H9)3 are interpreted to indicate a β-hydrogen elimination process. However, β-hydrogen elimination only occurs after fission of the weakest Ga-C bond, thus no β-hydride elimination is observed for Ga( t-C4H9)(CH3)2. Detection of C2H6 for Ga(CH3)3 and Ga( t-C4H9)(CH3)2, but not for Ga( t-C4H9)2(CH3), shows that under our experimental conditions the formation of ethane is as a result of the reductive elimination of the methyl groups, and is not due to the recombination of two free methyl radicals.

  15. Organometallic perovskites for optoelectronic applications (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    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.

  16. Advanced polymer chemistry of organometallic anions

    SciTech Connect

    Chamberlin, R.M.; Abney, K.D.; Balaich, G.J.; Fino, S.A.

    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.

  17. Non-metallocene organometallic complexes and related methods and systems

    DOEpatents

    Agapie, Theodor; Golisz, Suzanne Rose; Tofan, Daniel; Bercaw, John E.

    2010-12-07

    A non-metallocene organometallic complex comprising a tridentate ligand and a metal bonded to a tridentate ligand, wherein two substituted aryl groups in the tridentate ligand are connected to a cyclic group at the ortho position via semi-rigid ring-ring linkages, and selected so to provide the resulting non-metallocene organometallic complex with a C.sub.S geometry, a C.sub.1 geometry, a C.sub.2 geometry or a C.sub.2v geometry. Method for performing olefin polymerization with a non-metallocene organometallic complex as a catalyst, related catalytic systems, tridentate ligand and method for providing a non-metallocene organometallic complex.

  18. High-sensitivity molecular organometallic resist for EUV (MORE)

    NASA Astrophysics Data System (ADS)

    Passarelli, James; Murphy, Michael; Del Re, Ryan; Sortland, Miriam; Dousharm, Levi; Vockenhuber, Michaela; Ekinci, Yasin; Neisser, Mark; Freedman, Daniel A.; Brainard, Robert L.

    2015-03-01

    We have developed organometallic carboxylate compounds [RnM(O2CR')2] capable of acting as negativetone EUV resists. Overall, the best and fastest resists contain antimony, are pentavalent and the carboxylate group contains a polymerizable olefin (e.g. acrylate, methacrylate or styrenecarboxylate). Evidence suggests that high sensitivity is achieved through the polymerization of olefins in the exposed region. We have performed a systematic sensitivity study of molecules of the type RnM(O2CR')2 where we have studied seven R groups, four main group metals (M), and three polymerizable carboxylate groups (O2CR'). We found that the greatest predictor of sensitivity of the RnSb(O2CR')2 resists is their level of polymerizable olefins. We mathematically define the polymerizable olefin loading (POL) as the ratio of the number of olefins vs. the number of non-hydrogen atoms. Linear and log plots of Emax vs. POL for a variety of molecules of the type R3Sb(O2CR')2 lend insight into the behaviour of these resists.

  19. Organometallic carboxylate resists for extreme ultraviolet with high sensitivity

    NASA Astrophysics Data System (ADS)

    Passarelli, James; Murphy, Michael; Re, Ryan Del; Sortland, Miriam; Hotalen, Jodi; Dousharm, Levi; Fallica, Roberto; Ekinci, Yasin; Neisser, Mark; Freedman, Daniel A.; Brainard, Robert L.

    2015-10-01

    We have developed organometallic carboxylate compounds [RnM)] capable of acting as negative-tone extreme ultraviolet (EUV) resists. The most sensitive of these resists contain antimony, three R-groups and two carboxylate groups, and carboxylate groups with polymerizable olefins (e.g., acrylate, methacrylate, or styrenecarboxylate). Evidence suggests that high sensitivity is achieved through the polymerization of olefins in the exposed region. We have performed a systematic sensitivity study of the molecules of the type RnM) where we have studied seven R groups, four main group metals (M), and three polymerizable carboxylate groups (O2CR‧). The sensitivity of these resists was evaluated using Emax or dose to maximum resist thickness after exposure and development. We found that the greatest predictor of sensitivity of the RnSb) resists is their level of polymerizable olefins. We mathematically define the polymerizable olefin loading (POL) as the ratio of the number of olefins versus the number of nonhydrogen atoms. Linear and log plots of Emax versus POL for a variety of molecules of the type R3Sb) lend insight into the behavior of these resists.

  20. Strain induced directional coarsening in Ni based superalloys

    SciTech Connect

    Veron, M.; Brechet, Y.; Louchet, F.

    1996-06-15

    Directional coarsening (or rafting) in Ni-based single crystal superalloys occurs after short times under stress at high temperature. This phenomenon results in a strongly anisotropic evolution of the microstructure that needs to be understood since it can occur in superalloy turbine blades during service. As the strain induced during creep seems to be responsible for the rafting phenomenon, it is worth studying the effect of a strain gradient on coarsened structures. A simple way to do this is to investigate the coarsening morphologies developed around an indentation.

  1. Stabilized metal nanoparticles from organometallic precursors for low temperature fuel cells.

    PubMed

    Ramirez-Meneses, E; Dominguez-Crespo, M A; Torres-Huerta, A M

    2013-01-01

    In this work, a review of articles and patents related to the utilization of colloidal metal nanoparticles produced by the decomposition of organometallic precursors as supported electrocatalysts in different electrochemical reactions including hydrogen evolution reaction (HER), oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) is discussed. In the case of stabilized metal nanoparticles, the kind of functional group contained in the stabilizer as well as the metal/stabilizer ratio, to evaluate the effect of particle size on the electrochemical performance, were also debated. Potential applications and perspectives of these electrocatalysts in proton exchange membrane fuel cells (PEMFC) are contended with reference to the role played by the coordination compounds and costs.

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

    ERIC Educational Resources Information Center

    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…

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

    ERIC Educational Resources Information Center

    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…

  4. Grain Boundary Curvature in a Model Ni-Based Superalloy (Preprint)

    DTIC Science & Technology

    2006-07-01

    AFRL-ML-WP-TP-2006-482 GRAIN BOUNDARY CURVATURE IN A MODEL Ni-BASED SUPERALLOY (PREPRINT) Kai Song and Mark Aindow JULY 2006... MODEL Ni-BASED SUPERALLOY (PREPRINT) 5c. PROGRAM ELEMENT NUMBER 62712E 5d. PROJECT NUMBER K720 5e. TASK NUMBER 01 6. AUTHOR(S) Kai Song...AFRL/WS 06-1882, 09 Aug 2006. 14. ABSTRACT The local grain boundary curvature in a model Ni-based superalloy was measured experimentally using

  5. Half-metallicity in 2D organometallic honeycomb frameworks

    NASA Astrophysics Data System (ADS)

    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.

  6. Half-metallicity in 2D organometallic honeycomb frameworks.

    PubMed

    Sun, Hao; Li, Bin; Zhao, Jin

    2016-10-26

    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.

  7. Compound

    NASA Astrophysics Data System (ADS)

    Suzumura, Akitoshi; Watanabe, Masaki; Nagasako, Naoyuki; Asahi, Ryoji

    2014-06-01

    Recently, Cu-based chalcogenides such as Cu3SbSe4, Cu2Se, and Cu2SnSe3 have attracted much attention because of their high thermoelectric performance and their common feature of very low thermal conductivity. However, for practical use, materials without toxic elements such as selenium are preferable. In this paper, we report Se-free Cu3SbS4 thermoelectric material and improvement of its figure of merit ( ZT) by chemical substitutions. Substitutions of 3 at.% Ag for Cu and 2 at.% Ge for Sb lead to significant reductions in the thermal conductivity by 37% and 22%, respectively. These substitutions do not sacrifice the power factor, thus resulting in enhancement of the ZT value. The sensitivity of the thermal conductivity to chemical substitutions in these compounds is discussed in terms of the calculated phonon dispersion and previously proposed models for Cu-based chalcogenides. To improve the power factor, we optimize the hole carrier concentration by substitution of Ge for Sb, achieving a power factor of 16 μW/cm K2 at 573 K, which is better than the best reported for Se-based Cu3SbSe4 compounds.

  8. Strength of nanoporous Ni-based superalloy membranes

    NASA Astrophysics Data System (ADS)

    Rösler, J.; Näth, O.

    2010-07-01

    Nanoporous Ni-based superalloy membranes are a new material class. They are fabricated from the two phase γ/γ' base material by thermomechanical processing, followed by selective phase extraction. Compared to other metallic membrane materials, they stand out due to an extremely regular and fine channel-like porosity on the nanoscale. This allows for particularly interesting applications in areas such as particle filtration, catalysis of chemical reactions or heat exchange. However, fundamental understanding of the mechanical behaviour is a prerequisite in all these cases. Thus, the microstructure property correlation of these novel materials is analyzed here, examining a γ'-membrane (where the γ-phase is leached out) by tensile testing. It will be demonstrated that nanoporous superalloy membranes are remarkably strong materials, provided the processing parameters are properly selected.

  9. Local structure of Iridium organometallic catalysts covalently bonded to carbon nanotubes.

    NASA Astrophysics Data System (ADS)

    Blasco, J.; Cuartero, V.; Subías, G.; Jiménez, M. V.; Pérez-Torrente, J. J.; Oro, L. A.; Blanco, M.; Álvarez, P.; Blanco, C.; Menéndez, R.

    2016-05-01

    Hybrid catalysts based on Iridium N-heterocyclic carbenes anchored to carbon nanotubes (CNT) have been studied by XAFS spectroscopy. Oxidation of CNT yields a large amount of functional groups, mainly hydroxyl groups at the walls and carboxylic groups at the tips, defects and edges. Different kinds of esterification reactions were performed to functionalize oxidized CNT with imidazolium salts. Then, the resulting products were reacted with an Ir organometallic compound to form hybrid catalysts efficient in hydrogen transfer processes. XANES spectroscopy agree with the presence of Ir(I) in these catalysts and the EXAFS spectra detected differences in the local structure of Ir atoms between the initial Ir organometallic compound and the Ir complexes anchored to the CNT. Our results confirm that the halide atom, present in the Ir precursor, was replaced by oxygen from -OH groups at the CNT wall in the first coordination shell of Ir. The lability of this group accounts for the good recyclability and the good efficiency shown by these hybrid catalysts.

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

    PubMed

    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.

  11. Isothermal Oxidation Comparison of Three Ni-Based Superalloys

    NASA Astrophysics Data System (ADS)

    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.

  12. Organic or organometallic template mediated clay synthesis

    SciTech Connect

    Gregar, K.C.; Winans, R.E.; Botto, R.E.

    1992-12-31

    A method is given for incorporating diverse varieties of intercalants or templates directly during hydrothermal synthesis of clays such as hectorite or montmorillonite-type layer-silicate clays. For a hectorite layer-silicate clay, refluxing a gel of silica sol, magnesium hydroxide sol and LiF for 2 days with an organic or organometallic intercalant or template results in crystalline products containing either (a) organic dye molecules such as ethyl violet and methyl green, (b) dye molecules such as alcian blue based on a Cu(II)-phthalocyannine complex, or (c) transition metal complexes such as Ru(II)phenanthroline and Co(III)sepulchrate or (d) water-soluble porphyrins and metalloporphyrins. Montmorillonite-type clays are made by the method taught by US patent No. 3,887,454 issued to Hickson, June 13, 1975; however, a variety of intercalants or templates may be introduced. The intercalants or templates should have water-solubility, positive charge, and thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays.

  13. Combinatorial screening of inorganic and organometallic materials

    DOEpatents

    Schultz, Peter G.; Xiang, Xiaodong; Goldwasser, Isy

    2002-01-01

    Methods and apparatus for the preparation and use of a substrate having an array of diverse materials in predefined regions thereon. A substrate having an array of diverse materials thereon is generally prepared by delivering components of materials to predefined regions on a substrate, and simultaneously reacting the components to form at least two materials. Materials which can be prepared using the methods and apparatus of the present invention include, for example, covalent network solids, ionic solids and molecular solids. More particularly, materials which can be prepared using the methods and apparatus of the present invention include, for example, inorganic materials, intermetallic materials, metal alloys, ceramic materials, organic materials, organometallic materials, non-biological organic polymers, composite materials (e.g., inorganic composites, organic composites, or combinations thereof), etc. Once prepared, these materials can be screened for useful properties including, for example, electrical, thermal, mechanical, morphological, optical, magnetic, chemical, or other properties. Thus, the present invention provides methods for the parallel synthesis and analysis of novel materials having useful properties.

  14. Organic or organometallic template mediated clay synthesis

    DOEpatents

    Gregar, Kathleen C.; Winans, Randall E.; Botto, Robert E.

    1994-01-01

    A method for incorporating diverse Varieties of intercalants or templates directly during hydrothermal synthesis of clays such as hectorite or montmorillonite-type layer-silicate clays. For a hectorite layer-silicate clay, refluxing a gel of silica sol, magnesium hydroxide sol and lithium fluoride for two days in the presence of an organic or organometallic intercalant or template results in crystalline products containing either (a) organic dye molecules such as ethyl violet and methyl green, (b) dye molecules such as alcian blue that are based on a Cu(II)-phthalocyannine complex, or (c) transition metal complexes such as Ru(II)phenanthroline and Co(III)sepulchrate or (d) water-soluble porphyrins and metalloporphyrins. Montmorillonite-type clays are made by the method taught by U.S. Pat. No. 3,887,454 issued to Hickson, Jun. 13, 1975; however, a variety of intercalants or templates may be introduced. The intercalants or templates should have (i) water-solubility, (ii) positive charge, and (iii) thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays.

  15. Organic or organometallic template mediated clay synthesis

    DOEpatents

    Gregar, K.C.; Winans, R.E.; Botto, R.E.

    1994-05-03

    A method is described for incorporating diverse varieties of intercalates or templates directly during hydrothermal synthesis of clays such as hectorite or montmorillonite-type layer-silicate clays. For a hectorite layer-silicate clay, refluxing a gel of silica sol, magnesium hydroxide sol and lithium fluoride for two days in the presence of an organic or organometallic intercalate or template results in crystalline products containing either (a) organic dye molecules such as ethyl violet and methyl green, (b) dye molecules such as alcian blue that are based on a Cu(II)-phthalocyannine complex, or (c) transition metal complexes such as Ru(II)phenanthroline and Co(III)sepulchrate or (d) water-soluble porphyrins and metalloporphyrins. Montmorillonite-type clays are made by the method taught by U.S. Pat. No. 3,887,454 issued to Hickson, Jun. 13, 1975; however, a variety of intercalates or templates may be introduced. The intercalates or templates should have (i) water-solubility, (ii) positive charge, and (iii) thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays. 22 figures.

  16. Tuning exchange interactions in organometallic semiconductors

    NASA Astrophysics Data System (ADS)

    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 < 25T) MCD and magneto-photoluminescence show evidence of spin-polarized band-edge excitons in the same materials.

  17. Sulfur-bonded thiophenes in organometallic rhenium complexes and adsorption of isocyanides on gold

    SciTech Connect

    Robertson, Mitchell Joe

    1993-08-01

    This dissertation contains results of research conducted in two different areas: (1) organometallic synthesis and reactivity, and (2) organometallic surface chemistry. In the synthesis and reactivity studies, sulfur coordination of thiophene and benzo[b]thiophene to the metal center in organometallic rhenium complexes is examined. In the surface chemistry studies, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) is used to analyze the adsorption of several isocyanides on the surface of gold powder. Results are compared and contrasted to known organometallic chemistry.

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

    SciTech Connect

    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.

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

    ERIC Educational Resources Information Center

    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…

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

    ERIC Educational Resources Information Center

    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…

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

    NASA Astrophysics Data System (ADS)

    Duncan, Andrew P.; Johnson, Adam R.

    2007-03-01

    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 responsible for researching and presenting selected papers to their classmates for analysis and discussion. Beyond mastery of basic organometallic principles, course goals for the students include improved proficiency in using the primary chemical literature and increased experience and confidence in researching, preparing, and delivering an informative oral presentation in individual and collaborative settings. Student performance is assessed based on performance on open-ended, take-home exams, quality of presentations, and contribution to in-class discussions. Student end-of-term survey responses indicate that this class model is successful as an introduction to organometallic chemistry.

  2. Toxicology of organic-inorganic hybrid molecules: bio-organometallics and its toxicology.

    PubMed

    Fujie, Tomoya; Hara, Takato; Kaji, Toshiyuki

    2016-01-01

    Bio-organometallics is a research strategy of biology that uses organic-inorganic hybrid molecules. The molecules are expected to exhibit useful bioactivities based on the unique structure formed by interaction between the organic structure and intramolecular metal(s). However, studies on both biology and toxicology of organic-inorganic hybrid molecules have been incompletely performed. There can be two types of toxicological studies of bio-organometallics; one is evaluation of organic-inorganic hybrid molecules and the other is analysis of biological systems from the viewpoint of toxicology using organic-inorganic hybrid molecules. Our recent studies indicate that cytotoxicity of hybrid molecules containing a metal that is nontoxic in inorganic forms can be more toxic than that of hybrid molecules containing a metal that is toxic in inorganic forms when the structure of the ligand is the same. Additionally, it was revealed that organic-inorganic hybrid molecules are useful for analysis of biological systems important for understanding the toxicity of chemical compounds including heavy metals.

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

    NASA Astrophysics Data System (ADS)

    Ma, Jia; Sahai, Yogeshwar; Buchheit, Rudolph G.

    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 -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 -2 for NaBH 4/O 2 fuel cell at 60 °C, 665 mW cm -2 for NaBH 4/H 2O 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.

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

    NASA Astrophysics Data System (ADS)

    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.

  5. Slip Analysis in a Ni-base Superalloy

    NASA Technical Reports Server (NTRS)

    Westbrooke, Eboni F.; Forero, Luis E.; Ebrahimi, Fereshteh

    2004-01-01

    A Ni-base superalloy single crystal with Gamma/Gamma' structure was tested at room temperature along the , <110> and <111> directions. Consistent with previously reported investigations, this alloy did not obey the Schmid law and the CRSS (critical resolved shear stress) was noticeably lower for the <111>-oriented samples. Furthermore, the strain hardening rate decreased and the degree of deformation localization increased in the order of <111>, and <110> orientations. The appearance and orientation of deformation traces were found to depend on the loading orientation as well as the amount of strain. In general, when Gamma'-particles were sheared, the traces followed the expected octahedral shear planes. It is demonstrated that the wavy deformation traces that do not follow the {111} planes are associated with changes in the gamma-channels width and the falling off of the gamma-particles. In this paper the evolution of deformation bands are discussed in terms of plastic localization at microscopic, mesoscopic and macroscopic levels.

  6. Ni-based nanoalloys: Towards thermally stable highly magnetic materials

    SciTech Connect

    Palagin, Dennis Doye, Jonathan P. K.

    2014-12-07

    Molecular dynamics simulations and density functional theory calculations have been used to demonstrate the possibility of preserving high spin states of the magnetic cores within Ni-based core-shell bimetallic nanoalloys over a wide range of temperatures. We show that, unlike the case of Ni–Al clusters, Ni–Ag clusters preserve high spin states (up to 8 μ{sub B} in case of Ni{sub 13}Ag{sub 32} cluster) due to small hybridization between the electronic levels of two species. Intriguingly, such clusters are also able to maintain geometrical and electronic integrity of their cores at temperatures up to 1000 K (e.g., for Ni{sub 7}Ag{sub 27} cluster). Furthermore, we also show the possibility of creating ordered arrays of such magnetic clusters on a suitable support by soft-landing pre-formed clusters on the surface, without introducing much disturbance in geometrical and electronic structure of the cluster. We illustrate this approach with the example of Ni{sub 13}Ag{sub 38} clusters adsorbed on the Si(111)–(7×7) surface, which, having two distinctive halves to the unit cell, acts as a selective template for cluster deposition.

  7. Catalytic arene hydrogenation using early transition metal hydride compounds

    SciTech Connect

    Rothwell, I.P.

    1993-03-15

    Progress was achieved in four areas: development of surface supported Group 5 metal organometallic compounds for catalytic arene hydrogenation, isolation and reactivity of possible intermediates in catalytic arene hydrogenation, synthesis and characterization of new d[sup 0]-metal hydride compounds, and stoichiometric reactivity of d[sup 0] metal hydrido, aryloxide compounds. (DLC)

  8. ROMP Synthesis of Iron-Containing Organometallic Polymers.

    PubMed

    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.

  9. Ligand Rearrangements of Organometallic Complexes inSolution

    SciTech Connect

    Shanoski, Jennifer E.

    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.

  10. In –Situ Spectroscopic Investigation of Immobilized Organometallic Catalysts

    SciTech Connect

    Davis, Robert, J.

    2007-11-14

    Immobilized organometallic catalysts, in principle, can give high rates and selectivities like homogeneous catalysts with the ease of separation enjoyed by heterogeneous catalysts. However, the science of immobilized organometallics has not been developed because the field lies at the interface between the homogeneous and heterogeneous catalysis communities. By assembling an interdisciplinary research team that can probe all aspects of immobilized organometallic catalyst design, the entire reacting system can be considered, where the transition metal complex, the complex-support interface and the properties of the support can all be considered simultaneously from both experimental and theoretical points of view. Researchers at Georgia Tech and the University of Virginia are studying the fundamental principles that can be used to understand and design future classes of immobilized organometallic catalysts. In the framework of the overall collaborative project with Georgia Tech, our work focused on (a) the X-ray absorption spectroscopy of an immobilized Pd-SCS-O complex (b) the mode of metal leaching from supported Pd catalysts during Heck catalysis and (c) the mode of deactivation of Jacobsen’s Co-salen catalysts during the hydrolytic kinetic resolution of terminal epoxides. Catalysts containing supported Pd pincer complexes, functionalized supports containing mercapto and amine groups, and oligomeric Co-salen catalysts were synthesized at Georgia Tech and sent to the University of Virginia. Incorporation of Pd onto several different kinds of supports (silica, mercapto-functionalized silica, zeolite Y) was performed at the University of Virginia.

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

    PubMed

    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.

  12. Organometalic carbosilane polymers containing vanadium and their preparation

    NASA Technical Reports Server (NTRS)

    Yajima, S.; Okamura, K.; Shishido, T.; Fukuda, K.

    1983-01-01

    The present invention concerns a new organometallic polymer material containing in part a vanadium-siloxane linkage (V-0-Si), which has excellent resistance to heat and oxidation and a high residue ratio after high temperature treatment in a non-oxidizing atmosphere, for example, nitrogen, argon, helium, ammonia, or hydrogen.

  13. Rational design of an organometallic glutathione transferase inhibitor

    SciTech Connect

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

    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.

  14. Strategies to prepare and use functionalized organometallic reagents.

    PubMed

    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.

  15. In situ electrochemical activation of Ni-based colloids from an NiCl2 electrode and their advanced energy storage performance.

    PubMed

    Chen, Kunfeng; Xue, Dongfeng

    2016-10-06

    The formation of electrochemical activated cations in electrode materials to induce multiple-electron transfer reactions is a challenge for high-energy storage systems. Herein, highly electroactive Ni-based colloidal electrode materials have been synthesized by in situ electrochemical activation of a NiCl2 electrode. The highest specific capacitance of the activated Ni-based electrodes was 10 286 F g(-1) at a current density of 3 A g(-1), indicating that a three-electron Faradaic redox reaction (Ni(3+) ↔ Ni) occurred. Upon potential cycling and constant potential activation, a decrease in the charge transfer resistance can be found. Activation and utilization of multiple-electron reactions is an efficient route to increase the energy density of supercapacitors. This newly designed colloidal pseudocapacitor is compatible with inorganic pseudocapacitor chemistry, which enables us to use metal cations directly via their commercial salts rather than their oxide/hydroxide compounds.

  16. Femtosecond Time-Resolved Infrared Spectra of Organometallic Complexes Bound to a Dinuclear Metal Center

    NASA Astrophysics Data System (ADS)

    Brown-Xu, Samantha E.; Durr, Christopher B.

    2012-06-01

    Compounds of the form M2L2L'2, where M2 is a quadruply bonded metal center (M = Mo or W) and L and L' are conjugated organic ligands, are known to show interesting photophysical properties and exhibit intense metal-to-ligand charge transfer (MLCT) transitions throughout the visible spectrum. Recently, we have modified one of the ligands to incorporate a transition metal carbonyl complex bound to an organic moiety. Following excitation into the MLCT band, the vibrational modes of the organometallic ligand can be observed by fs time-resolved infrared (TRIR) spectroscopy. This allows for a visualization of where the electron density resides in the excited states, which provides useful information for designing new materials that could later be incorporated into solar devices.

  17. Use of methylselenol for organometallic vapor-phase epitaxy of ZnSe

    NASA Astrophysics Data System (ADS)

    Fujita, Shizuo; Sakamoto, Takao; Isemura, Masashi; Fujita, Shigeo

    1988-03-01

    Heteroepitaxial films of ZnSe on GaAs substrates have been grown by atmospheric-pressure organometallic vapor-phase epitaxy using a new selenium source, methylselenol, CH 3SeH (MSeH). Gas-phase prereaction with a group-II source material was suppressed compared with hydride sources, e.g., H 2Se. The practical growth temperature was 300-400°C, which was sufficiently lower than 500°C used in the growth with dialkyl compounds. The epilayers exhibited a fairly smooth surface morphology and good crystallographic properties. Higher quality epilayers can be expected with source repurification or synthesis via purer chemical processes.

  18. Organometallic Chemical Vapor Deposition of ZrF4-Based Fluoride Glasses

    NASA Astrophysics Data System (ADS)

    Fujiura, Kazuo; Ohishi, Yasutake; Takahashi, Shiro

    1989-01-01

    By organometallic chemical vapor deposition (OMCVD), fluoride glasses in a ZrF4-BaF2 binary system are successfully synthesized. β-Diketone chelates of Zr and Ba as starting materials can be volatilized and completely fluorinated with HF gas into ZrF4-BaF2 compounds. 65 mol%ZrF4-35 mol%BaF2 powder synthesized by OMCVD is identified as homogeneous glass by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). By this method, ZrF4 is also obtained in an amorphous state. The OMCVD is available for preparation of fluoride glass, which is promising for optical fiber.

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

    PubMed

    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.

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

    PubMed

    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. Copyright © 2011 John Wiley & Sons, Ltd.

  1. Microstructural characterisation of friction stir welding joints of mild steel to Ni-based alloy 625

    SciTech Connect

    Rodriguez, J.; Ramirez, A.J.

    2015-12-15

    In this study, 6-mm-thick mild steel and Ni-based alloy 625 plates were friction stir welded using a tool rotational speed of 300 rpm and a travel speed of 100 mm·min{sup −1}. A microstructural characterisation of the dissimilar butt joint was performed using optical microscopy, scanning and transmission electron microscopy, and energy dispersive X-ray spectroscopy (XEDS). Six different weld zones were found. In the steel, the heat-affected zone (HAZ) was divided into three zones and was composed of ferrite, pearlite colonies with different morphologies, degenerated regions of pearlite and allotriomorphic and Widmanstätten ferrite. The stir zone (SZ) of the steel showed a coarse microstructure consisting of allotriomorphic and Widmanstätten ferrite, degenerate pearlite and MA constituents. In the Ni-based alloy 625, the thermo-mechanically affected zone (TMAZ) showed deformed grains and redistribution of precipitates. In the SZ, the high deformation and temperature produced a recrystallised microstructure, as well as fracture and redistribution of MC precipitates. The M{sub 23}C{sub 6} precipitates, present in the base material, were also redistributed in the stir zone of the Ni-based alloy. TMAZ in the steel and HAZ in the Ni-based alloy could not be identified. The main restorative mechanisms were discontinuous dynamic recrystallisation in the steel, and discontinuous and continuous dynamic recrystallisation in the Ni-based alloy. The interface region between the steel and the Ni-based alloy showed a fcc microstructure with NbC carbides and an average length of 2.0 μm. - Highlights: • Comprehensive microstructural characterisation of dissimilar joints of mild steel to Ni-based alloy • Friction stir welding of joints of mild steel to Ni-based alloy 625 produces sound welds. • The interface region showed deformed and recrystallised fcc grains with NbC carbides and a length of 2.0 μm.

  2. Estimate of conjugate gamma and gamma prime compositions in Ni-base superalloys

    NASA Technical Reports Server (NTRS)

    Dreshfield, R. L.

    1977-01-01

    Approaches for estimating the composition of the matrix phase of alloys from the melt composition are reviewed. The first method is based on assigning essentially fixed stoichiometry to precipitating phases and is typified by PHACOMP. The second method uses analytical geometry to interpret phase diagrams and is applicable to a two-phase region of a six-component Ni-base system. The geometric method is also applicable to commercial Ni-base superalloys.

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

    NASA Technical Reports Server (NTRS)

    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.

  4. Inorganic and Organometallic Molecular Wires for Single-Molecule Devices.

    PubMed

    Tanaka, Yuya; Kiguchi, Manabu; Akita, Munetaka

    2017-04-06

    Recent developments of single-molecule conductance measurements allow us to understand fundamental conducting properties of molecular wires. While a wide variety of organic molecular wires have been studied so far, inorganic and organometallic molecular wires have received much less attention. However, molecular wires with transition-metal atoms show interesting features and functions distinct from those of organic wires. These properties originate mainly from metal-ligand dπ-pπ interactions and metal-metal d-d interactions. Thanks to the rich combination of metal atoms and supporting ligands, frontier orbital energies of the molecular wires can be finely tuned to lead to highly conducting molecular wires. Moreover, the unique electronic structures of metal complexes are susceptible to subtle environmental changes, leading to potential functional molecular devices. This article reviews recent advances in the single-molecule conductance study of inorganic and organometallic molecular wires. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. An Organometallic Future in Green and Energy Chemistry?

    SciTech Connect

    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.

  6. Organo-metallic thin film for erasable optical recording medium

    NASA Astrophysics Data System (ADS)

    Shu, Juping; Zhou, Jian P.; Xu, Shi Z.

    1991-11-01

    An erasable optical recording medium was made by vacuum deposition of copper tetra cyanoquino dimethane organometallic materials writable and erasable with an He-Ne laser. With He-Ne laser output power of 13 mW at 632 nm, the threshold pulse width was 0.2 - 2 microsecond(s) . The readout signal contrast was 29%. The write-erase cycles were observed under optimum condition.

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

    PubMed

    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.

  8. Sunlight induced cycloaddition and host-guest property of self-assembled organometallic macrocycles based on a versatile building block.

    PubMed

    Wu, Tong; Weng, Lin-Hong; Jin, Guo-Xin

    2012-05-11

    Organometallic rectangle 1 which undergoes [2+2] cycloaddition upon irradiation with sunlight and organometallic prism 3 which displayed interesting host-guest property were self-assembled based on a versatile building block.

  9. Lipid nanocapsules loaded with an organometallic tamoxifen derivative as a novel drug-carrier system for experimental malignant gliomas.

    PubMed

    Allard, Emilie; Passirani, Catherine; Garcion, Emmanuel; Pigeon, Pascal; Vessières, Anne; Jaouen, Gérard; Benoit, Jean-Pierre

    2008-09-10

    Ferrocenyl diphenol tamoxifen derivative (Fc-diOH) is one of the most active molecules of a new class of organometallic drugs, showing in vitro antiproliferative effects on both hormone-dependent and independent breast cancer cells. For the first time, Fc-diOH was tested on a 9L glioma model according to two encapsulation strategies: lipid nanocapsules (LNC) and swollen micelles. LNC showed a higher drug loading capacity because of a larger oily core in their structure and were able to be up taken by glioma cells. The large amount of PEG present at the micellar interface prevented interaction with cytoplasm membrane which led to a low level of micelle cell uptake and no biological activity. On the contrary, Fc-diOH cytostatic activity was conserved after its encapsulation in LNC and was very effective on 9L-glioma cells as the IC(50) was about 0.6 microM. Interestingly, Fc-diOH-loaded LNC showed low toxicity levels when in contact with healthy cells, conferring a functional specificity of this compound on tumour cells. Finally, Fc-diOH LNC treatment was able to lower significantly both tumour mass and volume evolution after 9L-cell implantation into rats which evidenced for the first time the in vivo efficacy of this new kind of organometallic compound.

  10. Electronic structures of organometallic complexes of f elements. Part 45. Comparison of phenomenological and calculated crystal field parameters of lanthanide organyls estimated on the basis of simple models

    NASA Astrophysics Data System (ADS)

    Jank, S.; Reddmann, H.; Amberger, H.-D.

    1998-09-01

    The crystal field (CF) parameters of Nd[N(SiMe 3) 2] 3, (THF) 3Li( μ-Cl)Nd[N(SiMe 3) 2] 3 and Nd[N(SiMe 3) 2] 3(CNC 6H 11) 2 (which are considered as model compounds for the corresponding σ-bonded organometallic complexes with [CH(SiMe 3) 2] - ligands), as well as those of organometallic π complexes of the types (Me 3SiC 5H 4) 3Pr and (C 8H 8)Pr[HB(3,5-Me 2pz) 3], were estimated on the basis of simple model calculations (point charge electrostatic model, simple overlap model, angular overlap model) and were compared with the results of CF calculations adopting the phenomenological model. The comparison suggests that these straightforward model calculations may provide satisfactory CF parameters for σ complexes but give poor results for π complexes of the lanthanides.

  11. Field-induced conductance switching by charge-state alternation in organometallic single-molecule junctions

    NASA Astrophysics Data System (ADS)

    Schwarz, Florian; Kastlunger, Georg; Lissel, Franziska; Egler-Lucas, Carolina; Semenov, Sergey N.; Venkatesan, Koushik; Berke, Heinz; Stadler, Robert; Lörtscher, Emanuel

    2016-02-01

    Charge transport through single molecules can be influenced by the charge and spin states of redox-active metal centres placed in the transport pathway. These intrinsic properties are usually manipulated by varying the molecule's electrochemical and magnetic environment, a procedure that requires complex setups with multiple terminals. Here we show that oxidation and reduction of organometallic compounds containing either Fe, Ru or Mo centres can solely be triggered by the electric field applied to a two-terminal molecular junction. Whereas all compounds exhibit bias-dependent hysteresis, the Mo-containing compound additionally shows an abrupt voltage-induced conductance switching, yielding high-to-low current ratios exceeding 1,000 at bias voltages of less than 1.0 V. Density functional theory calculations identify a localized, redox-active molecular orbital that is weakly coupled to the electrodes and closely aligned with the Fermi energy of the leads because of the spin-polarized ground state unique to the Mo centre. This situation provides an additional slow and incoherent hopping channel for transport, triggering a transient charging effect in the entire molecule with a strong hysteresis and large high-to-low current ratios.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Preparation and characterization of Ni-based perovskite catalyst for steam CO2 reforming of methane.

    PubMed

    Yang, Eun-Hyeok; Kim, Sang Woo; Ahn, Byong Song; Moon, Dong Ju

    2013-06-01

    Steam CO2 reforming of methane was investigated over Ni-based perovskite catalyst to produce desired H2/CO ratio by adjusting the feed ratio of CH4, CO2 and H2O for floating GTL process application. La modified perovskites were prepared by the Pechini method and calcined in air and the Ni-based catalysts were prepared by dispersing Ni on the La modified perovskite by an incipient wetness impregnation. The catalysts before and after the reaction were characterized by N2 physisoprtion, CO chemisoprtion, XRD, TPR and SEM techniques. To control desired H2/CO ratio, simulation for SCR was carried out by Aspen plus, and product distribution for SCR was investigated in a fixed bed reactor system using feed ratio estimated by simulation. The Ni-based perovskite catalysts were found to give CH4 and CO2 conversions of up to 82% and 60% respectively to yield a H2/CO product ratio close to 2.

  15. Microstructure-Sensitive Extreme Value Probabilities for High Cycle Fatigue of Ni-Base Superalloy IN100 (Preprint)

    DTIC Science & Technology

    2009-03-01

    AFRL-RX-WP-TP-2009-4123 MICROSTRUCTURE-SENSITIVE EXTREME VALUE PROBABILITIES FOR HIGH CYCLE FATIGUE OF Ni- BASE SUPERALLOY IN100 (PREPRINT...PROBABILITIES FOR HIGH CYCLE FATIGUE OF Ni-BASE SUPERALLOY IN100 (PREPRINT) 5a. CONTRACT NUMBER In-house 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER...statistical framework to investigate the microstructure-sensitive fatigue response of the PM Ni-base superalloy IN100. To accomplish this task, we

  16. Small Fatigue Crack Growth and Failure Mode Transitions in a Ni-Base Superalloy at Elevated Temperature (Preprint)

    DTIC Science & Technology

    2010-02-01

    AFRL-RX-WP-TP-2010-4070 SMALL FATIGUE CRACK GROWTH AND FAILURE MODE TRANSITIONS IN A Ni-BASE SUPERALLOY AT ELEVATED TEMPERATURE (Preprint...CRACK GROWTH AND FAILURE MODE TRANSITIONS IN A Ni-BASE SUPERALLOY AT ELEVATED TEMPERATURE (Preprint) 5a. CONTRACT NUMBER IN HOUSE 5b. GRANT...by ANSI Std. Z39-18 Page 1 of 28 Small Fatigue Crack Growth and Failure Mode Transitions in a Ni-Base Superalloy at Elevated Temperature M. J

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

    PubMed

    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.

  18. [Progress of organometallic complexes and their application to organic electroluminescent materials].

    PubMed

    Zhou, Rui; An, Zhong-Wei; Chai, Sheng-Yong

    2004-08-01

    Organic electroluminescent (EL) material is one of most prospective display materials in flat panel display. Organometallic complexes, which have five or six member ring structures, with high stability, high melting point and high fluorescence quantum efficiency, are widely applied in organic EL devices. The recent progress in organometallic complexes is summarized in terms of the electroluminescence of ligands and metal atoms.

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

    NASA Astrophysics Data System (ADS)

    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.

  20. A study on coke deposition in Ni-based catalysts for CO2 reforming of methane

    NASA Astrophysics Data System (ADS)

    Yahya, Erny Azwin; Zabidi, Noor Asmawati Mohd; Kait, Chong Fai

    2016-11-01

    Cobalt (Co) and niobium (Nb) promoted Ni-based catalysts have been prepared by a wet impregnation method. The influence of these promoters on properties and performance of Ni-based catalyst supported on γ-Al2O3 for CO2 reforming of methane reaction has been studied. CO2 reforming of methane reaction has been conducted at atmospheric pressure for 5 h at 850 °C. Results show that Nb promoted catalysts show higher conversion of CH4 and CO2 (44.5%) compared to that of unpromoted catalyst. Meanwhile, the amount of coke formed was lower on the promoted catalysts compared to that of unpromoted catalyst.

  1. Effect of Surface Roughness on the Oxidation Behavior of the Ni-Base Superalloy ME3

    NASA Astrophysics Data System (ADS)

    Evans, Jeffrey L.

    2010-10-01

    Ni-base superalloys are used in applications, such as jet aircraft engines and power production facilities that require excellent elevated temperature oxidation resistance. This present work evaluated the effect of surface roughness on the oxidation behavior of the Ni-base superalloy ME3. Isothermal oxidation tests were performed in air at different times to investigate the oxide growth kinetics. The surface oxides were also characterized using scanning electron microscopy and x-ray diffraction. The surface roughness was measured using a linear scanning profilometer. The surface roughness measurements were correlated to the oxidation rates and an empirical model is proposed to describe the effect of surface roughness on the oxidation behavior.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Catalytic arene hydrogenation using early transition metal hydride compounds. Progress report

    SciTech Connect

    Rothwell, I.P.

    1993-03-15

    Progress was achieved in four areas: development of surface supported Group 5 metal organometallic compounds for catalytic arene hydrogenation, isolation and reactivity of possible intermediates in catalytic arene hydrogenation, synthesis and characterization of new d{sup 0}-metal hydride compounds, and stoichiometric reactivity of d{sup 0} metal hydrido, aryloxide compounds. (DLC)

  4. Supported organometallic complexes, surface chemistry, spectroscopy, and catalysis

    SciTech Connect

    Marks, T.J.

    1993-04-01

    Goal 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. Nature of adsorbed species is probed by a battery of chemical and physicochemical techniques, to understand the nature of the molecule-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.

  5. Fundamental organometallic reactions: Applications on the CYBER 205

    NASA Technical Reports Server (NTRS)

    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.

  6. Growth and characterization of GaAs, AlGaAs and their heterostructures by organometallic vapor phase epitaxy

    SciTech Connect

    Shealy, J.R.

    1983-01-01

    Organometallic Vapor Phase Epitaxy (OMVPE) is a cold wall vapor desposition technique using organometallic and/or hydride sources for the fabrication of a variety of epitaxial compound semiconductor alloys on suitable substrates. The use of the OMVPE process to produce high quality GaAs, AlGaAs, and their heterostructures on GaAs substrates using trimethygalium (TMG), trimethylalumium (TMA), and arsine is described. For GaAs epitaxial films, the unintentional residual donor sand acceptors have been identified using far-infrared photo-ionization data, and low temperature photoluminescence, respectively, and their concentrations have been evaluated using Hall data. For the growth of AlGaAs films, it was observed that poor quality films were obtained due to oxygen contamination of the layer during growth. A series of graded bandgap heterostructures and abrupt quantum well heterostructures were grown over a variety of growth conditions. Composition gradings were controlled over a full range of alloy compositions on distances as small as 500 - 1000 A, and a 40 A quantum well heterostructure was obtained at low growth temperatures (550/sup 0/C). Finally, results are presented on a few devices which incorporate metallurgical junctions and heterojunctions with the GaAs/AlGaAs system. These devices include a microwave vertical FET structure, graded bandgap solar cells, and light emitting diodes.

  7. Two-Photon Absorption in Organometallic Bromide Perovskites.

    PubMed

    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.

  8. Magnetic Exchange Interactions in Long Range Ordered Diluted Organometallic Semiconductors

    NASA Astrophysics Data System (ADS)

    Rawat, Naveen; Manning, Lane; Furis, Madalina

    2015-03-01

    Exchange Interactions in diluted organometallic crystalline thin films of Phthalocyanines made of a mixture of organo-soluble derivatives of metal-free (H2Pc) molecule and MnPc is investigated. The tuning of optical and magnetic properties in organometallics is driven by their emergence in optoelectronic applications involving flexible electronics. Thin films with metal to metal-free Pc ratios ranging from 1: 1 to 1:10 were fabricated using solution processing that produces macroscopic grains. In the case of Mn-Pc, our previos measurements showed enhanced hybridization of ligand π-electronic states with the Mn d-orbitals as well as indirect exchange interaction similar to that of RKKY type exchange. The evolution of Zeeman splitting of specific MCD-active states resulted in enhanced effective π-electrons g-factors, analogous to diluted magnetic semiconductors (DMS) systems. Recent Variable temperature Magnetic Circular Dichroism (VTVH-MCD) measurements has now revealed that the exchange interaction is Antiferromagnetic. Recent MCD data for mixed derivatives will be presented along with their temperature dependance that further probes this exchange interaction. NSF award 1056589

  9. CNET of France uses organo-metallic epitaxy for laser

    NASA Astrophysics Data System (ADS)

    1985-11-01

    CNET's Bagneux laboratory has just determine the characteristics of the first 1.3 microns GaInAsP laser chips produced by means of organo-metallic epitaxy on InP at atmospheric pressure. The results of the first complete after test (pulsed threshold current density of 1,200 A/sq cm at room temperature for laser 100 microns wide and 500 microns long; low feature dispersion, high quantity yield) are encouraging. They seem to indicate that with appropriate structures (for example, embedded ribbon lasers), it may be possible to construct direct current lasers that function at room temperature with threshold currents of 30 to 100 mA. The results are among the best in the world (CNET's threshold current is only 40% greater than the Thomson record achieved with a reduced-pressure organo-metallic epitaxial method) and are comparable to those recently publilshed by Bell Labs (3,600 A/sq cm at 1.36 microns, the first to have determined the characteristics of lasers made using the same method.

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

    PubMed

    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.

  11. Reactive codoping of GaAlInP compound semiconductors

    DOEpatents

    Hanna, Mark Cooper [Boulder, CO; Reedy, Robert [Golden, CO

    2008-02-12

    A GaAlInP compound semiconductor and a method of producing a GaAlInP compound semiconductor are provided. The apparatus and method comprises a GaAs crystal substrate in a metal organic vapor deposition reactor. Al, Ga, In vapors are prepared by thermally decomposing organometallic compounds. P vapors are prepared by thermally decomposing phospine gas, group II vapors are prepared by thermally decomposing an organometallic group IIA or IIB compound. Group VIB vapors are prepared by thermally decomposing a gaseous compound of group VIB. The Al, Ga, In, P, group II, and group VIB vapors grow a GaAlInP crystal doped with group IIA or IIB and group VIB elements on the substrate wherein the group IIA or IIB and a group VIB vapors produced a codoped GaAlInP compound semiconductor with a group IIA or IIB element serving as a p-type dopant having low group II atomic diffusion.

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

    PubMed

    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

  13. [An antiserum directed against phenobarbital with an organometallic tracer: production and characterization].

    PubMed

    Mariet, F; Brossier, P

    1991-01-01

    In order to develop a new immunoassay procedure based on the use of organometallic labels, antisera are raising against sedative-hypnotic drug: phenobarbital. Immunization was performed in rabbits with parasuccinylamidophenobarbital coupled to bovine-serum-albumin. The evaluation of the specificity and the affinity constants of antisera are studied against different hypnotic or antiepileptic drugs and the metallotracer (phenobarbital labelled with an organometallic fragment derived from cymantrene). The most important result of this study indicates that the organometallic moiety of the metallotracer did not disturb neither the inhibition (% inhibition = 110) nor the affinity constant (Ka = 2.10(8) L/M) of the phenobarbital.

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

    PubMed

    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).

  15. Naturally Efficient Emitters: Luminescent Organometallic Complexes Derived from Natural Products

    NASA Astrophysics Data System (ADS)

    Zhang, Wen-Hua; Young, David J.

    2013-08-01

    Naturally occurring molecules offer intricate structures and functionality that are the basis of modern medicinal chemistry, but are under-represented in materials science. Herein, we review recent literature describing the use of abundant and relatively inexpensive, natural products for the synthesis of ligands for luminescent organometallic complexes used for organic light emitting diodes (OLEDs) and related technologies. These ligands are prepared from the renewable starting materials caffeine, camphor, pinene and cinchonine and, with the exception of caffeine, impart performance improvements to the emissive metal complexes and resulting OLED devices, with emission wavelengths that span the visible spectrum from blue to red. The advantages of these biologically-derived molecules include improved solution processibility and phase homogeneity, brighter luminescence, higher quantum efficiencies and lower turn-on voltages. While nature has evolved these carbon-skeletons for specific purposes, they also offer some intriguing benefits in materials science and technology.

  16. Superparamagnetic nickel nanoparticles obtained by an organometallic approach

    NASA Astrophysics Data System (ADS)

    Ramírez-Meneses, E.; Betancourt, I.; Morales, F.; Montiel-Palma, V.; Villanueva-Alvarado, C. C.; Hernández-Rojas, M. E.

    2011-01-01

    Nickel nanoparticles were prepared by decomposition of the organometallic precursor Ni(COD)2 (COD=cycloocta-1,5-diene) dissolved in organic media in the presence of anthranilic acid as stabilizer. Transmission electron microscopy revealed nickel nanoparticles with a mean size of 4.2 ± 1.1 nm and selected area electron diffraction showed the formation of fcc nickel. FTIR spectroscopy confirmed the presence of modified anthranilic acid on the surface of the Ni nanoparticles suggesting that it is able to interact with the metal particles. The magnetic response of the nanoparticles was established as being of superparmagnetic character, for which a detailed quantitative analysis resulted in a mean magnetic moment of 2652 μB per particle together with a blocking temperature of 32 K.

  17. Electronic configurations and magnetic anisotropy in organometallic metallocenes

    SciTech Connect

    Nawa, Kenji Kitaoka, Yukie; Nakamura, Kohji; Akiyama, Toru; Ito, Tomonori

    2015-05-07

    Electronic configurations and magnetic anisotropy of organometallic metallocenes (MCp{sub 2}s) were investigated by means of first principles calculations based on the constraint density functional theory. The results predict that the ground states for M = Cr, Mn, Fe, Co, and Ni are the {sup 3}E{sub 2g}, {sup 2}E{sub 2g}, {sup 1}A{sub 1g}, {sup 2}E{sub 1g}, and {sup 3}A{sub 2g} states, respectively. The magnetizations of the CoCp{sub 2} and NiCp{sub 2} energetically favor highly orienting along the perpendicular and parallel directions to the cyclopentadienyl (Cp) plane, respectively, and the others show almost no preference for the magnetic easy axis.

  18. Investigation of Chemical Bonding in In Situ Cryocrystallized Organometallic Liquids.

    PubMed

    Sirohiwal, Abhishek; Hathwar, Venkatesha R; Dey, Dhananjay; Chopra, Deepak

    2017-08-02

    This Communication presents the crystal structure of the organometallic complexes (η(4) -1,3-cyclohexadiene) iron tricarbonyl (I) and (methyl cyclopentadienyl) manganese tricarbonyl (II) which are both liquid at room temperature. The crystal structures were determined using a state-of-the-art in situ cryocrystallization technique. The bonding features were elucidated using topological analysis of charge density in the framework of quantum theory of atoms in molecules (QTAIM) and theoretical charge density analysis (multipolar refinement), to decipher the metal-carbonyl, metal-olefin and metal-carbocyclic ligand interactions in these complexes. Complex I displayed a simultaneous interplay of a "synergic effect" (σ-donation and π-back-bonding in the metal and an end-on coordinated carbonyl interaction) as well as consistency with the Dewar-Chatt-Duncanson (DCD) model (metal and side-on coordinated π-ligand interactions). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Organometallic Rhenium Complexes Divert Doxorubicin to the Mitochondria.

    PubMed

    Imstepf, Sebastian; Pierroz, Vanessa; Rubbiani, Riccardo; Felber, Michael; Fox, Thomas; Gasser, Gilles; Alberto, Roger

    2016-02-18

    Doxorubicin, a well-established chemotherapeutic agent, is known to accumulate in the cell nucleus. By using ICP-MS, we show that the conjugation of two small organometallic rhenium complexes to this structural motif results in a significant redirection of the conjugates from the nucleus to the mitochondria. Despite this relocation, the two bioconjugates display excellent toxicity toward HeLa cells. In addition, we carried out a preliminarily investigation of aspects of cytotoxicity and present evidence that the conjugates disrupt the mitochondrial membrane potential, are strong inhibitors of human Topoisomerase II, and induce apoptosis. Such derivatives may enhance the therapeutic index of the aggressive parent drug and overcome drug resistance by influencing nuclear and mitochondrial homeostasis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Flat Chern Band in a Two-Dimensional Organometallic Framework

    NASA Astrophysics Data System (ADS)

    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, namely the flat chern band (FCB), has recently been proposed, in which carriers experience strong Coulomb interaction as well as topological frustration that in together spawn unprecedented topological strongly-correlated electronic states, such as high-temperature fractional quantum hall state. Despite the proposal of several theoretical lattice models, however, it remains a doubt whether such a ``romance of flatland'' could exist in a real material. Here, we present a first-principles design to realize a nearly FCB right around the Fermi level in a two-dimensional (2D) Indium-Phenylene Organometallic Framework (IPOF). Our design in addition provides a general strategy to synthesize topologically nontrivial materials in virtue of organic chemistry and nanotechnology. Supported by DOE-BES and ARL

  1. Flat Chern Band in a Two-Dimensional Organometallic Framework

    NASA Astrophysics Data System (ADS)

    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.

  2. Half metal in two-dimensional hexagonal organometallic framework.

    PubMed

    Hu, Hao; Wang, Zhengfei; Liu, Feng

    2014-12-01

    Two-dimensional (2D) hexagonal organometallic framework (HOMF) made of triphenyl-metal molecules bridged by metal atoms has been recently shown to exhibit exotic electronic properties, such as half-metallic and topological insulating states. Here, using first-principles calculations, we investigate systematically the structural, electronic, and magnetic properties of such HOMFs containing 3d transition metal (TM) series (Sc to Cu). Two types of structures are found for these HOMFs: a buckled structure for those made of TMs with less half-filled 3d band and a twisted structure otherwise. The HOMFs show both ferromagnetic and antiferromagnetic properties, as well as nonmagnetic properties, due to the electronic configuration of the TM atoms. The V, Mn, and Fe lattices are ferromagnetic half metals with a large band gap of more than 1.5 eV in the insulating spin channel, making them potential 2D materials for spintronics application.

  3. Chromocene in porous polystyrene: an example of organometallic chemistry in confined spaces.

    PubMed

    Estephane, Jane; Groppo, Elena; Vitillo, Jenny G; Damin, Alessandro; Lamberti, Carlo; Bordiga, Silvia; Zecchina, Adriano

    2009-04-07

    In this work, we present an innovative approach to investigate the structure and the reactivity of a molecularly dispersed organometallic compound. The poly(4-ethylstyrene-co-divinylbenzene) microporous system (PS) is used as "solid solvent" able to molecularly disperse CrCp2, allowing: (i) its full characterization by means of spectroscopic techniques; (ii) the pressure and temperature dependent study of its interaction towards simple molecules like CO freely diffusing through the pores; (iii) the accurate determination of the reaction enthalpies by both direct microcalorimetric measurements and by an indirect spectroscopic approach. The experimental results are compared with quantum-mechanical calculations adopting the DFT approximation with two different functionals (namely BP86 and B3-LYP), showing the limitations and the potentialities of DFT methods in predicting the properties of open shell systems. It is concluded that modern DFT methods are able to give a coherent view of the vibrational properties of the CrCp2 molecule (and of the complex formed upon CO adsorption) that well match the experimental results, while the energetic predictions should be taken with care as they are significantly dependent on the functionals used.

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

    PubMed

    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.

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

    SciTech Connect

    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.

  6. Organometallic Routes into the Nanorealms of Binary Fe-Si Phases

    PubMed Central

    Kolel-Veetil, Manoj K.; Keller, Teddy M.

    2010-01-01

    The Fe-Si binary system provides several iron silicides that have varied and exceptional material properties with applications in the electronic industry. The well known Fe-Si binary silicides are Fe3Si, Fe5Si3, FeSi, α-FeSi2 and β-FeSi2. While the iron-rich silicides Fe3Si and Fe5Si3 are known to be room temperature ferromagnets, the stoichiometric FeSi is the only known transition metal Kondo insulator. Furthermore, Fe5Si3 has also been demonstrated to exhibit giant magnetoresistance (GMR). The silicon-rich β-FeSi2 is a direct band gap material usable in light emitting diode (LED) applications. Typically, these silicides are synthesized by traditional solid-state reactions or by ion beam-induced mixing (IBM) of alternating metal and silicon layers. Alternatively, the utilization of organometallic compounds with reactive transition metal (Fe)-carbon bonds has opened various routes for the preparation of these silicides and the silicon-stabilized bcc- and fcc-Fe phases contained in the Fe-Si binary phase diagram. The unique interfacial interactions of carbon with the Fe and Si components have resulted in the preferential formation of nanoscale versions of these materials. This review will discuss such reactions.

  7. The state and catalytic properties of (Ni + Pd)/SiO{sub 2} systems obtained by grafting organometallic complexes on the surface of SiO{sub 2}

    SciTech Connect

    Koval`chuk, V.I.; Chesnokov, N.V.; Naimushina, L.V.

    1995-05-01

    The adsorption and catalytic properties of Pd/SiO{sub 2}, Ni/SiO{sub 2}, and (Pd + Ni)/SiO{sub 2} samples obtained by grafting organometallic Pd and Ni compounds on the support surface are studied. Bimetallic Pd-Ni catalysts are shown to have an additive catalytic action in the hydrogenation of benzene. Synergistic effects are detected in the reactions of ethane hydrogenolysis, CO hydrogenation, and propylene hydroformylation. The obtained data show that the surface of bimetallic cluster particles becomes enriched with palladium atoms.

  8. Organometallic catalysts for primary phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    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.

  9. Organometallic catalysts for primary phosphoric acid fuel cells

    NASA Astrophysics Data System (ADS)

    Walsh, Fraser

    1987-03-01

    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.

  10. A synchrotron study of microstructure gradient in laser additively formed epitaxial Ni-based superalloy

    PubMed Central

    Xue, Jiawei; Zhang, Anfeng; Li, Yao; Qian, Dan; Wan, Jingchun; Qi, Baolu; Tamura, Nobumichi; Song, Zhongxiao; Chen, Kai

    2015-01-01

    Laser additive forming is considered to be one of the promising techniques to repair single crystal Ni-based superalloy parts to extend their life and reduce the cost. Preservation of the single crystalline nature and prevention of thermal mechanical failure are two of the most essential issues for the application of this technique. Here we employ synchrotron X-ray microdiffraction to evaluate the quality in terms of crystal orientation and defect distribution of a Ni-based superalloy DZ125L directly formed by a laser additive process rooted from a single crystalline substrate of the same material. We show that a disorientation gradient caused by a high density of geometrically necessary dislocations and resultant subgrains exists in the interfacial region between the epitaxial and stray grains. This creates a potential relationship of stray grain formation and defect accumulation. The observation offers new directions on the study of performance control and reliability of the laser additive manufactured superalloys. PMID:26446425

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

    NASA Astrophysics Data System (ADS)

    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.

  12. A synchrotron study of microstructure gradient in laser additively formed epitaxial Ni-based superalloy

    SciTech Connect

    Xue, Jiawei; Zhang, Anfeng; Li, Yao; Qian, Dan; Wan, Jingchun; Qi, Baolu; Tamura, Nobumichi; Song, Zhongxiao; Chen, Kai

    2015-10-08

    Laser additive forming is considered to be one of the promising techniques to repair single crystal Ni-based superalloy parts to extend their life and reduce the cost. Preservation of the single crystalline nature and prevention of thermal mechanical failure are two of the most essential issues for the application of this technique. Here we employ synchrotron X-ray microdiffraction to evaluate the quality in terms of crystal orientation and defect distribution of a Ni-based superalloy DZ125L directly formed by a laser additive process rooted from a single crystalline substrate of the same material. We show that a disorientation gradient caused by a high density of geometrically necessary dislocations and resultant subgrains exists in the interfacial region between the epitaxial and stray grains. This creates a potential relationship of stray grain formation and defect accumulation. In conclusion, the observation offers new directions on the study of performance control and reliability of the laser additive manufactured superalloys.

  13. Simulation of γ' Precipitation Kinetics in a Commercial Ni-Base Superalloy

    NASA Astrophysics Data System (ADS)

    Fahrmann, M. G.; Metzler, D. A.

    2016-11-01

    The ability to accurately simulate the precipitation kinetics of γ' and other strengthening phases in Ni-base superalloys is of great interest to industry. Several commercial simulation tools such as TC-PRISMA (Thermo-Calc, Sweden) and PanPrecipitation (Computherm, USA) have been made available in recent years. This paper reports the outcome of a validation study on wrought Ni-base superalloy HAYNES® 282® alloy for two scenarios of commercial interest: (1) the precipitation of γ' during continuous cooling, and (2) the precipitation of γ' during two-step aging. The simulation results are validated against experimental data. Any discrepancies are discussed in the context of the uncertainty in key material properties (such as interfacial energies), model assumptions, and experimental errors.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

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

    SciTech Connect

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

    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.

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

    NASA Technical Reports Server (NTRS)

    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.

  18. Organometallic Iridium(III) Anticancer Complexes with New Mechanisms of Action: NCI-60 Screening, Mitochondrial Targeting, and Apoptosis

    PubMed Central

    2013-01-01

    Platinum complexes related to cisplatin, cis-[PtCl2(NH3)2], are successful anticancer drugs; however, other transition metal complexes offer potential for combating cisplatin resistance, decreasing side effects, and widening the spectrum of activity. Organometallic half-sandwich iridium (IrIII) complexes [Ir(Cpx)(XY)Cl]+/0 (Cpx = biphenyltetramethylcyclopentadienyl and XY = phenanthroline (1), bipyridine (2), or phenylpyridine (3)) all hydrolyze rapidly, forming monofunctional G adducts on DNA with additional intercalation of the phenyl substituents on the Cpx ring. In comparison, highly potent complex 4 (Cpx = phenyltetramethylcyclopentadienyl and XY = N,N-dimethylphenylazopyridine) does not hydrolyze. All show higher potency toward A2780 human ovarian cancer cells compared to cisplatin, with 1, 3, and 4 also demonstrating higher potency in the National Cancer Institute (NCI) NCI-60 cell-line screen. Use of the NCI COMPARE algorithm (which predicts mechanisms of action (MoAs) for emerging anticancer compounds by correlating NCI-60 patterns of sensitivity) shows that the MoA of these IrIII complexes has no correlation to cisplatin (or oxaliplatin), with 3 and 4 emerging as particularly novel compounds. Those findings by COMPARE were experimentally probed by transmission electron microscopy (TEM) of A2780 cells exposed to 1, showing mitochondrial swelling and activation of apoptosis after 24 h. Significant changes in mitochondrial membrane polarization were detected by flow cytometry, and the potency of the complexes was enhanced ca. 5× by co-administration with a low concentration (5 μM) of the γ-glutamyl cysteine synthetase inhibitor L-buthionine sulfoximine (L-BSO). These studies reveal potential polypharmacology of organometallic IrIII complexes, with MoA and cell selectivity governed by structural changes in the chelating ligands. PMID:23618382

  19. Organometallic Iridium(III) anticancer complexes with new mechanisms of action: NCI-60 screening, mitochondrial targeting, and apoptosis.

    PubMed

    Hearn, Jessica M; Romero-Canelón, Isolda; Qamar, Bushra; Liu, Zhe; Hands-Portman, Ian; Sadler, Peter J

    2013-01-01

    Platinum complexes related to cisplatin, cis-[PtCl2(NH3)2], are successful anticancer drugs; however, other transition metal complexes offer potential for combating cisplatin resistance, decreasing side effects, and widening the spectrum of activity. Organometallic half-sandwich iridium (Ir(III)) complexes [Ir(Cp(x))(XY)Cl](+/0) (Cp(x) = biphenyltetramethylcyclopentadienyl and XY = phenanthroline (1), bipyridine (2), or phenylpyridine (3)) all hydrolyze rapidly, forming monofunctional G adducts on DNA with additional intercalation of the phenyl substituents on the Cp(x) ring. In comparison, highly potent complex 4 (Cp(x) = phenyltetramethylcyclopentadienyl and XY = N,N-dimethylphenylazopyridine) does not hydrolyze. All show higher potency toward A2780 human ovarian cancer cells compared to cisplatin, with 1, 3, and 4 also demonstrating higher potency in the National Cancer Institute (NCI) NCI-60 cell-line screen. Use of the NCI COMPARE algorithm (which predicts mechanisms of action (MoAs) for emerging anticancer compounds by correlating NCI-60 patterns of sensitivity) shows that the MoA of these Ir(III) complexes has no correlation to cisplatin (or oxaliplatin), with 3 and 4 emerging as particularly novel compounds. Those findings by COMPARE were experimentally probed by transmission electron microscopy (TEM) of A2780 cells exposed to 1, showing mitochondrial swelling and activation of apoptosis after 24 h. Significant changes in mitochondrial membrane polarization were detected by flow cytometry, and the potency of the complexes was enhanced ca. 5× by co-administration with a low concentration (5 μM) of the γ-glutamyl cysteine synthetase inhibitor L-buthionine sulfoximine (L-BSO). These studies reveal potential polypharmacology of organometallic Ir(III) complexes, with MoA and cell selectivity governed by structural changes in the chelating ligands.

  20. Organometallic acetylides of Pt(II), Au(I) and Hg(II) as new generation optical power limiting materials.

    PubMed

    Zhou, Gui-Jiang; Wong, Wai-Yeung

    2011-05-01

    Within the scope of nonlinear optics, optical power limiting (OPL) materials are commonly regarded as an important class of compounds which can protect the delicate optical sensors or human eyes from sudden exposure to damaging intense laser beams. Recent efforts have been devoted to developing organometallic acetylide complexes, dendrimers and polymers as high performance OPL materials of the next generation which can favorably optimize the optical limiting/transparency trade-off issue. These metallated materials offer a new avenue towards a new family of highly transparent homo- and heterometallic optical limiters with good solution processability which outperform those of current state-of-the-art visible-light-absorbing competitors such as fullerenes, metalloporphyrins and metallophthalocyanines. This critical review aims to provide a detailed account on the recent advances of these novel OPL chromophores. Their OPL activity was shown to depend strongly on the electronic characters of the aryleneethynylene ligand and transition metal moieties as well as the conjugation chain length of the compounds. Strategies including copolymerization with other transition metals, change of structural geometry, use of a dendritic platform and variation of the type and content of transition metal ions would strongly govern their photophysical behavior and improve the resulting OPL responses. Special emphasis is placed on the structure-OPL response relationships of these organometallic acetylide materials. The research endeavors for realizing practical OPL devices based on these materials have also been presented. This article concludes with perspectives on the current status of the field, as well as opportunities that lie just beyond its frontier (106 references).

  1. Novel concept of functional oxide coatings providing enhanced oxidation resistance to Ni-based superalloys

    SciTech Connect

    Pedraza, F. Balmain, J. Bonnet, G. Bouchaud, B.

    2014-01-01

    Graphical abstract: - Highlights: • New concept for providing extended oxidation resistance to Ni-based superalloys. • Oxygen-defective nanostructured oxide coatings reduce the oxygen partial pressure at the substrate interface. • Pre-oxidation of the substrate during annealing with the formation of alpha-alumina. • Growth of CeAlO{sub 3} perovskite enhancing the adherence of the ceria top coat. • Microstructural stability of the coating system with no SRZ formation upon exposure. - Abstract: Aluminide-coated Ni-based superalloys are prone to microstructural instabilities during long-term exposure at high temperature with the growth of a secondary reaction zone (SRZ) detrimental from a mechanical viewpoint. This has been since overcome by the use of thermodynamically stable coatings (γ-Ni/γ′-Ni{sub 3}Al). However, additions of Pt and Hf are required to provide the formation of an exclusive α-Al{sub 2}O{sub 3} scale and improved oxidation resistance in cyclic and isothermal regimes. The present work proposes a new coating system that relies on the use of a superficial nanostructured functional oxide providing the establishment of a stable alumina while avoiding SRZ formation. Tailored oxygen-defective and multi-cracked coatings were designed for 2nd generation Ni-based superalloys and generated by electrosynthesis using a water-based solution. Cyclic oxidation tests were carried out at 1100 °C in air and the oxidation properties and the microstructural stability of the coating system were demonstrated.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Vacuum Brazing Diamond Grits with Cu-based or Ni-based Filler Metal

    NASA Astrophysics Data System (ADS)

    Qi, Wenchun; Lu, Jinbin; Li, Yang; Xu, Shuai; Zhong, Sujuan; Wang, Bangfu; Qiu, Xinkai

    2017-08-01

    Diamond grits were brazed using Cu-Sn-Cr and Ni-Cr-B-Si filler metals, and the brazed grits were examined for microstructure (SEM, EDS, XRD), microhardness, and compression strength. Results showed that the microstructure of the Cu-based filler metal was uniform and consisted of α-Cu + (α-Cu + δ). Its wettability to the diamond was better than Ni-based filler due to the formation of a thin carbide reaction layer that improved the bond strength between the diamond and steel. The Cu-based filler led to reduced thermal damage to the diamond. The Cr in the filler metal diffused to the steel substrate to form a reaction layer at the filler/steel substrate interface. The microhardness of the Ni filler metal (810-830 HV0.3) was significantly higher than that of Cu filler metal (170-230 HV0.3). The compressive load values of the diamond grits brazed with Cu-based or Ni-based filler metal were 93.7 and 49.2% of the original diamond, and the TI values were 83.7 and 59.8% of the original diamond. Grinding experiments for failure mode in monolayer tools revealed that the tools brazed with Cu-based filler metal had a lower macro-fracture ratio than those brazed using the Ni-based filler.

  4. Vacuum Brazing Diamond Grits with Cu-based or Ni-based Filler Metal

    NASA Astrophysics Data System (ADS)

    Qi, Wenchun; Lu, Jinbin; Li, Yang; Xu, Shuai; Zhong, Sujuan; Wang, Bangfu; Qiu, Xinkai

    2017-06-01

    Diamond grits were brazed using Cu-Sn-Cr and Ni-Cr-B-Si filler metals, and the brazed grits were examined for microstructure (SEM, EDS, XRD), microhardness, and compression strength. Results showed that the microstructure of the Cu-based filler metal was uniform and consisted of α-Cu + (α-Cu + δ). Its wettability to the diamond was better than Ni-based filler due to the formation of a thin carbide reaction layer that improved the bond strength between the diamond and steel. The Cu-based filler led to reduced thermal damage to the diamond. The Cr in the filler metal diffused to the steel substrate to form a reaction layer at the filler/steel substrate interface. The microhardness of the Ni filler metal (810-830 HV0.3) was significantly higher than that of Cu filler metal (170-230 HV0.3). The compressive load values of the diamond grits brazed with Cu-based or Ni-based filler metal were 93.7 and 49.2% of the original diamond, and the TI values were 83.7 and 59.8% of the original diamond. Grinding experiments for failure mode in monolayer tools revealed that the tools brazed with Cu-based filler metal had a lower macro-fracture ratio than those brazed using the Ni-based filler.

  5. Hydroconversion of heavy crude oils using soluble metallic compounds in the presence of hydrogen or methane

    SciTech Connect

    Morales, A.; Salazar, A.; Ovalles, C.; Filgueiras, E.

    1996-12-31

    The hydroconversion of heavy crude oil was studied under thermal and catalytic conditions using soluble organo-metallic compounds of Mo, Fe, Cr, V, Ni, and Co as a catalyst precursors. All catalysts are effective for the hydroconversion, however, molybdenum and nickel compounds are preferred.

  6. Tribromobenzene on Cu(111): Temperature-dependent formation of halogen-bonded, organometallic, and covalent nanostructures

    SciTech Connect

    Fan, Qitang; Wang, Tao; Zhu, Junfa; Liu, Liming; Zhao, Jin; Gottfried, J. Michael

    2015-03-14

    The temperature-controlled surface-assisted synthesis of halogen bonded, organometallic, and covalent nanostructures based on 1,3,5-tribromo-benzene (TriBB) was studied with scanning tunneling microscopy and X-ray photoemission spectroscopy in ultrahigh vacuum. Vapor deposition of TriBB onto a Cu(111) surface held at 90 K leads to the formation of large domains of a honeycomb-like organic monolayer structure stabilized by triangular nodes with Br⋯Br intermolecular bonds. Upon annealing the organic monolayer to ∼140 K, a new hexagonal close-packed structure with intact TriBB molecules connected by Cu adatoms is formed. Further warming up the sample to 300 K gives rise to the scission of C–Br bonds and formation of C–Cu–C bonds between phenyl fragments such that stable dendritic organometallic networks are formed. Larger islands of organometallic networks are obtained by maintaining the temperature of Cu(111) at 420 K during deposition of TriBB. Simultaneously, large islands of Br atoms are formed around the organometallic networks. Annealing the more extended organometallic network (prepared at 420 K) to 520 K leads to the formation of a branched covalent organic framework (COF) which comprises structural elements of porous graphene and is surrounded by Br islands. These organometallic networks and COFs appear as small dendritic and branched domains, most likely due to the steric influence exerted by the Br islands.

  7. Tribromobenzene on Cu(111): Temperature-dependent formation of halogen-bonded, organometallic, and covalent nanostructures

    NASA Astrophysics Data System (ADS)

    Fan, Qitang; Wang, Tao; Liu, Liming; Zhao, Jin; Zhu, Junfa; Gottfried, J. Michael

    2015-03-01

    The temperature-controlled surface-assisted synthesis of halogen bonded, organometallic, and covalent nanostructures based on 1,3,5-tribromo-benzene (TriBB) was studied with scanning tunneling microscopy and X-ray photoemission spectroscopy in ultrahigh vacuum. Vapor deposition of TriBB onto a Cu(111) surface held at 90 K leads to the formation of large domains of a honeycomb-like organic monolayer structure stabilized by triangular nodes with Br⋯Br intermolecular bonds. Upon annealing the organic monolayer to ˜140 K, a new hexagonal close-packed structure with intact TriBB molecules connected by Cu adatoms is formed. Further warming up the sample to 300 K gives rise to the scission of C-Br bonds and formation of C-Cu-C bonds between phenyl fragments such that stable dendritic organometallic networks are formed. Larger islands of organometallic networks are obtained by maintaining the temperature of Cu(111) at 420 K during deposition of TriBB. Simultaneously, large islands of Br atoms are formed around the organometallic networks. Annealing the more extended organometallic network (prepared at 420 K) to 520 K leads to the formation of a branched covalent organic framework (COF) which comprises structural elements of porous graphene and is surrounded by Br islands. These organometallic networks and COFs appear as small dendritic and branched domains, most likely due to the steric influence exerted by the Br islands.

  8. Effect of fuel gas composition in chemical-looping combustion with Ni-based oxygen carriers. 1. Fate of sulfur

    SciTech Connect

    Garcia-Labiano, F.; de Diego, L.F.; Gayan, P.; Adanez, J.; Abad, A.; Dueso, C.

    2009-03-15

    Chemical-looping combustion (CLC) has been suggested among the best alternatives to reduce the economic cost of CO{sub 2} capture using fuel gas because CO{sub 2} is inherently separated in the process. For gaseous fuels, natural gas, refinery gas, or syngas from coal gasification can be used. These fuels may contain different amounts of sulfur compounds, such as H{sub 2}S and COS. An experimental investigation of the fate of sulfur during CH{sub 4} combustion in a 500 W{sub th} CLC prototype using a Ni-based oxygen carrier has been carried out. The effect on the oxygen carrier behavior and combustion efficiency of several operating conditions such as temperature and H{sub 2}S concentration has been analyzed. Nickel sulfide, Ni3S{sub 2}, was formed at all operating conditions in the fuel reactor, which produced an oxygen carrier deactivation and lower combustion efficiencies. However, the oxygen carrier recovered their initial reactivity after certain time without sulfur addition. The sulfides were transported to the air reactor where SO{sub 2} was produced as final gas product. Agglomeration problems derived from the sulfides formation were never detected during continuous operation. Considering both operational and environmental aspects, fuels with sulfur contents below 100 vppm H{sub 2}S seem to be adequate to be used in an industrial CLC plant.

  9. In vitro antifilarial activity of organometallic complexes against infective larvae of Molinema dessetae and adult females of Brugia pahangi.

    PubMed

    Loiseau, P M; Jaffe, J J; Craciunescu, D G

    1998-08-01

    New organometallic complexes having protozoocidal properties were evaluated for their in vitro antifilarial activity using two models: infective larvae of Molinema dessetae and adult females of Brugia pahangi. The compound most active on the M. dessetae model was Ir(I)-COD-pentamidine tetraphenylborate with an EC50 = 6 +/- 1 microM after 7-day-incubation. In the 2-aminobenzothiazole series, Ruthenium was more potent than Iridium for antifilarial activity. A dithiocarbamate function significantly enhanced the antifilarial activity. The compounds derived from benzimidazole were inactive whatever the metal (Iridium or Rhodium). The other compounds exhibited EC50 ranging from 10 to 31 microM. On adult female Brugia pahangi in vitro, Pt-DDH-N-acetylleucine, Pt-diminazene and Pd-Cl4-piperazine at 20 microM began to kill both microfilariae and the developing embryos within the mothers on day 2. The compounds, except for Pd-Cl4-piperazine, killed the adults after 5 days. Rh-Cl-2-chloropyridine caused obvious slowing of the adults from day 3 onward but did not affect the viability of adults, microfilariae or developing embryos. In vivo antifilarial investigations are necessary to appreciate the real advantage of heavy metal complexes in the experimental treatment of filariasis.

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

    PubMed

    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.

  11. Organometallic Nonlinear Optical (NLO) Polymers. 2. Synthesis of Main-Chain Organometallic Polymers and a Structural Study of Ferrocene NLO-Phores

    DTIC Science & Technology

    1992-05-10

    Organometallics 1990, 9, 853. Wright, M. E.; Toplikar, E. G. in "Advances in New Materials , Contemporary Topics in Polymer Sicence ,", Salamone, J. C., Riffle...formation of an intractable polymeric material of unknown structure. The homopolymerization of 6 by the Knoevenagel technique afforded the desired...polycondensation. The transesterification polymerization resulted in formation of an intractable polymeric material of unknown structure. The

  12. Investigation on corrosion and wear behaviors of nanoparticles reinforced Ni-based composite alloying layer

    NASA Astrophysics Data System (ADS)

    Xu, Jiang; Tao, Jie; Jiang, Shuyun; Xu, Zhong

    2008-04-01

    In order to investigate the role of amorphous SiO 2 particles in corrosion and wear resistance of Ni-based metal matrix composite alloying layer, the amorphous nano-SiO 2 particles reinforced Ni-based composite alloying layer has been prepared by double glow plasma alloying on AISI 316L stainless steel surface, where Ni/amorphous nano-SiO 2 was firstly predeposited by brush plating. The composition and microstructure of the nano-SiO 2 particles reinforced Ni-based composite alloying layer were analyzed by using SEM, TEM and XRD. The results indicated that the composite alloying layer consisted of γ-phase and amorphous nano-SiO 2 particles, and under alloying temperature (1000 °C) condition, the nano-SiO 2 particles were uniformly distributed in the alloying layer and still kept the amorphous structure. The corrosion resistance of composite alloying layer was investigated by an electrochemical method in 3.5%NaCl solution. Compared with single alloying layer, the amorphous nano-SiO 2 particles slightly decreased the corrosion resistance of the Ni-Cr-Mo-Cu alloying layer. X-ray photoelectron spectroscopy (XPS) revealed that the passive films formed on the composite alloying consisted of Cr 2O 3, MoO 3, SiO 2 and metallic Ni and Mo. The dry wear test results showed that the composite alloying layer had excellent friction-reduced property, and the wear weight loss of composite alloying layer was less than 60% of that of Ni-Cr-Mo-Cu alloying layer.

  13. Potential and limitations of microanalysis SEM techniques to characterize borides in brazed Ni-based superalloys

    SciTech Connect

    Ruiz-Vargas, J.; Siredey-Schwaller, N.; Noyrez, P.; Mathieu, S.; Bocher, P.; and others

    2014-08-15

    Brazed Ni-based superalloys containing complex phases of different Boron contents remain difficult to characterize at the micrometer scale. Indeed Boron is a light element difficult to measure precisely. The state-of-the-art microanalysis systems have been tested on a single crystal MC2 based metal brazed with BNi-2 alloy to identify boride precipitates. Effort has been made to evaluate the accuracy in Boron quantitation. Energy-dispersive and wavelength-dispersive X-ray spectroscopy attached to a Scanning Electron Microscope have first been used to determine the elemental composition of Boron-free phases, and then applied to various types of borides. Results have been compared to the ones obtained using a dedicated electron probe microanalysis, considered here as the reference technique. The most accurate method to quantify Boron using EDS is definitely by composition difference. A precision of 5 at.% could be achieved with optimized data acquisition and post-processing schemes. Attempts that aimed at directly quantifying Boron with various standards using EDS or coupled EDS/WDS gave less accurate results. Ultimately, Electron Backscatter Diffraction combined with localized EDS analysis has proved invaluable in conclusively identifying micrometer sized boride precipitates; thus further improving the characterization of brazed Ni-based superalloys. - Highlights: • We attempt to accurately identify Boron-rich phases in Ni-based superalloys. • EDS, WDS, EBSD systems are tested for accurate identification of these borides. • Results are compared with those obtained by electron probe microanalysis. • Boron was measured with EDS by composition difference with a precision of 5 at. %. • Additional EBSD in phase identification mode conclusively identifies the borides.

  14. Mesoscale modeling and simulation of microstructure evolution during dynamic recrystallization of a Ni-based superalloy

    NASA Astrophysics Data System (ADS)

    Chen, Fei; Cui, Zhenshan; Ou, Hengan; Long, Hui

    2016-10-01

    Microstructural evolution and plastic flow characteristics of a Ni-based superalloy were investigated using a simulative model that couples the basic metallurgical principle of dynamic recrystallization (DRX) with the two-dimensional (2D) cellular automaton (CA). Variation of dislocation density with local strain of deformation is considered for accurate determination of the microstructural evolution during DRX. The grain topography, the grain size and the recrystallized fraction can be well predicted by using the developed CA model, which enables to the establishment of the relationship between the flow stress, dislocation density, recrystallized fraction volume, recrystallized grain size and the thermomechanical parameters.

  15. Oxidation Resistance of Low-Temperature Pack Aluminizing Coatings on Ni-Base Superalloy

    NASA Astrophysics Data System (ADS)

    Yuan, Bifei; Yu, Longwen; Lu, Guiwu

    A nickel-base superalloy has been used to deposit the aluminide coating by low-temperature pack cementation process. The high temperature oxidation tests on aluminized alloys and the uncoated specimens are carried out at 1000°C for 10h. It is observed that a dense and protective Al2O3 surface layer is produced on the aluminized alloy, and the aluminizing process has greatly enhanced the high temperature oxidation resistance of the Ni-base superalloy at 1000°C. As a contrast, the uncoated specimen begins to be failure when treated only for 6h at the same temperature.

  16. Measuring Depth-dependent Dislocation Densities and Elastic Strains in an Indented Ni-based Superalloy

    SciTech Connect

    Barabash, O.M.; Santella, M.; Barabash, R.I.; Ice, G.E.; Tischler, J.

    2011-12-14

    The indentation-induced elastic-plastic zone in an IN 740 Ni-based superalloy was studied by three-dimensional (3-D) x-ray microdiffraction and electron back scattering diffraction (EBSD). Large lattice reorientations and the formation of geometrically necessary dislocations are observed in the area with a radius of {approx}75 {mu}m. A residual compression zone is found close to the indent edge. An elastic-plastic transition is observed at {approx}20 {mu}m from the indent edge. Depth dependent dislocation densities are determined at different distances from the indent edge.

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

    NASA Astrophysics Data System (ADS)

    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.

  18. Metal Temperature Evaluation Method Based on Microstructure Change of Ni Based Superalloy

    NASA Astrophysics Data System (ADS)

    Okada, Ikuo; Taneike, Masaki; Oguma, Hidetaka

    It is known that among numerous factors, industrial turbine Inlet gas Temperature (TIT, hereafter) has greatest influence on thermal efficiency of industrial gas turbine. In order to achieve higher thermal efficiency, TIT has already reached as high as 1500°C, which has been realized owing to improvement and development of cooling configuration and materials for hot parts. On the other hand, to operate gas turbines soundly, it is necessary to evaluate metal temperature of hot parts precisely. So, metal temperature evaluation methods of Ni base superalloy were investigated and developed based on coarsening phenomenon of γ' phase and carbide particles.

  19. Switching on elusive organometallic mechanisms with photoredox catalysis.

    PubMed

    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.

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

    PubMed

    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.

  1. Switching on Elusive Organometallic Mechanisms with Photoredox Catalysis

    PubMed Central

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

    2015-01-01

    Transition metal-catalyzed cross-coupling reactions have become one of the most utilized carbon–carbon and carbon–heteroatom bond-forming reactions in chemical synthesis. More 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 couplings1,2. 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. In this manuscript, 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 significantly, 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 (SET) catalysts. PMID:26266976

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

    SciTech Connect

    Vecchi, Paul Anthony

    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.

  3. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

    SciTech Connect

    Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher; Geohegan, David B.; Xiao, Kai

    2016-03-01

    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-performance and cost-effective optoelectronic devices.

  4. Switching on elusive organometallic mechanisms with photoredox catalysis

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    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.

  5. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

    DOE PAGES

    Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou; ...

    2016-03-01

    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- ionsmore » 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-performance and cost-effective optoelectronic devices.« less

  6. Magnetism of phthalocyanine-based organometallic single porous sheet.

    PubMed

    Zhou, Jian; Sun, Qiang

    2011-09-28

    A two-dimensional (2D) periodic Fe phthalocyanine (FePc) single-layer sheet has very recently been synthesized experimentally (Abel, M.; et al. J. Am. Chem. Soc.2011, 133, 1203), providing a novel pathway for achieving 2D atomic sheets with regularly and separately distributed transition-metal atoms for unprecedented applications. Here we present first-principles calculations based on density functional theory to investigate systematically the electronic and magnetic properties of such novel organometallics (labeled as TMPc, TM = Cr-Zn) as free-standing sheets. Among them, we found that only the 2D MnPc framework is ferromagnetic, while 2D CrPc, FePc, CoPc, and CuPc are antiferromagnetic and 2D NiPc and ZnPc are nonmagnetic. The difference in magnetic couplings for the studied systems is related to the different orbital interactions. Only MnPc displays metallic d(xz) and d(yz) orbitals that can hybridize with p electrons of Pc, which mediates the long-range ferromagnetic coupling. Monte Carlo simulations based on the Ising model suggest that the Curie temperature (T(C)) of the 2D MnPc framework is ∼150 K, which is comparable to the highest T(C) achieved experimentally, that of Mn-doped GaAs. The present study provides theoretical insight leading to a better understanding of novel phthalocyanine-based 2D structures beyond graphene and BN sheets.

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

    PubMed

    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.

  8. Synthesis, Characterization, and C-H Activation Reactions of Novel Organometallic O-donor Ligated Rh(III) Complexes

    SciTech Connect

    Tenn, William J.; Conley, Brian L.; Bischof, Steven M.; Periana, Roy A.

    2010-09-17

    The synthesis and characterization of the O-donor ligated, air and water stable organometallic complexes trans- (2), and cis-(hfac-O,O) 2Rh(CH3)(py) (3), trans-(hfac-O,O)2Rh(C6H5)(py) (4), cis-(hfac-O,O)2Rh(C6H5)(py) (5), and cis-(hfac-O,O)2Rh(Mes)(py) (6) (where hfac-O,O = κ 2-O,O-1,1,1,5,5,5-hexafluoroacetylacetonato) are reported. These compounds are analogues to the O-donor iridium complexes that are active catalysts for the hydroarylation and C–H activation reactions as well as the bis-acetylacetonato rhodium complexes, which we recently reported. The trans-complex 2 undergoes a quantitative trans to cis isomerization in cyclohexane to form 3, which activates C–H bonds in both benzene and mesitylene to form compounds 5 and 6, respectively. All of these compounds are air and water stable and do not lead to decomposition products. Complex 5 promotes hydroarylation of styrene by benzene to generate dihydrostilbene.

  9. Understanding the electron-stimulated surface reactions of organometallic complexes to enable design of precursors for electron beam-induced deposition

    NASA Astrophysics Data System (ADS)

    Spencer, Julie A.; Rosenberg, Samantha G.; Barclay, Michael; Wu, Yung-Chien; McElwee-White, Lisa; Howard Fairbrother, D.

    2014-12-01

    Standard practice in electron beam-induced deposition (EBID) is to use precursors designed for thermal processes, such as chemical vapor deposition (CVD). However, organometallic precursors that yield pure metal deposits in CVD often create EBID deposits with high levels of organic contamination. This contamination negatively impacts the deposit's properties (e.g., by increasing resistivity or decreasing catalytic activity) and severely limits the range of potential applications for metal-containing EBID nanostructures. To provide the information needed for the rational design of precursors specifically for EBID, we have employed an ultra-high vacuum (UHV) surface science approach to identify the elementary reactions of organometallic precursors during EBID. These UHV studies have demonstrated that the initial electron-induced deposition of the surface-bound organometallic precursors proceeds through desorption of one or more of the ligands present in the parent compound. In specific cases, this deposition step has been shown to proceed via dissociative electron attachment, involving low-energy secondary electrons generated by the interaction of the primary beam with the substrate. Electron beam processing of the surface-bound species produced in the initial deposition event usually causes decomposition of the residual ligands, creating nonvolatile fragments. This process is believed to be responsible for a significant fraction of the organic contaminants typically observed in EBID nanostructures. A few ligands (e.g., halogens) can, however, desorb during electron beam processing while other ligands (e.g., PF3, CO) can thermally desorb if elevated substrate temperatures are used during deposition. Using these general guidelines for reactivity, we propose some design strategies for EBID precursors. The ultimate goal is to minimize organic contamination and thus overcome the key bottleneck for fabrication of relatively pure EBID nanostructures.

  10. Effect of exposure in steam or argon on the creep properties of Ni-based alloys: Creep properties of Ni-based alloys

    SciTech Connect

    Dryepondt, S.; Unocic, K. A.; Pint, B. A.

    2012-09-17

    Although expensive, Ni-based superalloys are of interest for the ultrasupercritical steam program because of their good creep and oxidation resistance at temperature above 700 C. However, the effect of steam oxidation on the alloy mechanical properties is unknown, and creep specimens of alloy CCA617, 740 and 230 were pre-oxidized for 2000 and 4000h in steam at 800 C before testing in air at the same temperature. Exposure in steam decreased the creep properties of alloy CCA617 compared with as fabricated material, had less of an effect on alloy 740, and did not affect alloy 230. Testing of a specimen repolished after steam exposure as well as microstructure observation indicate that the oxidation affected zone at the specimen surface is not responsible for the properties degradation. Surprisingly, a similar time anneal in an inert environment resulted in a drastic decrease of creep rupture life and an increase in the creep rate and elongation at rupture. TEM analysis revealed that the mechanical properties decrease for alloy CCA617 is related to the absence of precipitates in the grain.

  11. Thermosensitive Ni-based magnetic particles for self-controlled hyperthermia applications

    NASA Astrophysics Data System (ADS)

    Pandey, Sudip; Quetz, Abdiel; Aryal, Anil; Dubenko, Igor; Mazumdar, Dipanjan; Stadler, Shane; Ali, Naushad

    2017-04-01

    A number of ferromagnetic alloys in the bulk-form "thermoseeds" have been investigated for localized self-controlled hyperthermia treatment of cancer by substituting V, Mo, Cu, and Ga for Ni. The samples were prepared by arc-melting technique and annealed at 1223 K (950 °C) for 12 h in sealed quartz tubes. The structural, magnetic, and magnetocaloric properties of the samples were studied, using room temperature X-ray diffraction and a Superconducting Quantum Interference Device (SQUID) magnetometer. The magnetocaloric parameters (magnetic entropy changes, refrigeration capacity (RC), and hysteretic effects) have been calculated. It has been shown that recrystallization, i.e., annealing time and temperature, is crucial for controlling the heating characteristics of the seeds. A linear decrease in Curie temperature (TC) from 380 K (107 °C) to 200 K (-73 °C) was observed with increasing substitution of Ni by V, Mo, Cu, and Ga, while the magnetization value remained nearly constant for all substitutions. The optimal composition of these Ni-based alloys has been determined in order to allow self-controlling hyperthermia, implying a Curie temperature near the therapeutic level, 315-318 K (41-45 °C). The results showed that an extraordinary self-regulating heating effect has been achieved in Ni-based magnetic materials, which may create new vistas for hyperthermia cancer treatment.

  12. Castability of Traditionally Wrought Ni-Based Superalloys for USC Steam Turbines

    SciTech Connect

    Jablonski, P D; Cowen, C J; Hawk, J A; Evens, N; Maziasz, P

    2011-02-27

    The high temperature components within conventional coal fired power plants are manufactured from ferritic/martensitic steels. In order to reduce greenhouse gas emissions the efficiency of pulverized coal steam power plants must be increased. The proposed steam temperature in the Advanced Ultra Supercritical (A-USC) power plant is high enough (760°C) that ferritic/martensitic steels will not work due to temperature limitations of this class of materials; thus Ni-based superalloys are being considered. The full size castings are quite substantial: ~4in thick, several feet in diameter and weigh 5-10,000lb each half. Experimental castings were quite a bit smaller, but section size was retained and cooling rate controlled in order to produce relevant microstructures. A multi-step homogenization heat treatment was developed in order to better deploy the alloy constituents. The castability of two traditionally wrought Ni-based superalloys to which minor alloy adjustments have been made in order to improve foundry performance is further explored.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Creep Crack Initiation and Growth Behavior for Ni-Base Superalloys

    NASA Astrophysics Data System (ADS)

    Nagumo, Yoshiko; Yokobori, A. Toshimitsu, Jr.; Sugiura, Ryuji; Ozeki, Go; Matsuzaki, Takashi

    The structural components which are used in high temperature gas turbines have various shapes which may cause the notch effect. Moreover, the site of stress concentration might have the heterogeneous microstructural distribution. Therefore, it is necessary to clarify the creep fracture mechanism for these materials in order to predict the life of creep fracture with high degree of accuracy. In this study, the creep crack growth tests were performed using in-situ observational testing machine with microscope to observe the creep damage formation and creep crack growth behavior. The materials used are polycrystalline Ni-base superalloy IN100 and directionally solidified Ni-base superalloy CM247LC which were developed for jet engine turbine blades and gas turbine blades in electric power plants, respectively. The microstructural observation of the test specimens was also conducted using FE-SEM/EBSD. Additionally, the analyses of two-dimensional elastic-plastic creep finite element using designed methods were conducted to understand the effect of microstructural distribution on creep damage formation. The experimental and analytical results showed that it is important to determine the creep crack initiation and early crack growth to predict the life of creep fracture and it is indicated that the highly accurate prediction of creep fracture life could be realized by measuring notch opening displacement proposed as the RNOD characteristic.

  15. Hot corrosion testing of Ni-based alloys and coatings in a modified Dean rig

    NASA Astrophysics Data System (ADS)

    Steward, Jason Reid

    Gas turbine blades are designed to withstand a variety of harsh operating conditions. Although material and coating improvements are constantly administered to increase the mean time before turbine refurbishment or replacement, hot corrosion is still considered as the major life-limiting factor in many industrial and marine gas turbines. A modified Dean rig was designed and manufactured at Tennessee Technological University to simulate the accelerated hot corrosion conditions and to conduct screening tests on the new coatings on Ni-based superalloys. Uncoated Ni-based superalloys, Rene 142 and Rene 80, were tested in the modified Dean rig to establish a testing procedure for Type I hot corrosion. The influence of surface treatments on the hot corrosion resistance was then investigated. It was found that grit-blasted specimens showed inferior hot corrosion resistance than that of the polished counterpart. The Dean rig was also used to test model MCrAlY alloys, pack cementation NiAl coatings, and electro-codeposited MCrAlY coatings. Furthermore, the hot corrosion attack on the coated-specimens were also assessed using a statistical analysis approach.

  16. Steam Oxidation Behavior of Advanced Steels and Ni-Based Alloys at 800 °C

    NASA Astrophysics Data System (ADS)

    Dudziak, T.; Boroń, L.; Deodeshmukh, V.; Sobczak, J.; Sobczak, N.; Witkowska, M.; Ratuszek, W.; Chruściel, K.

    2017-02-01

    This publication studies the steam oxidation behavior of advanced steels (309S, 310S and HR3C) and Ni-based alloys (Haynes® 230®, alloy 263, alloy 617 and Haynes® 282®) exposed at 800 °C for 2000 h under 1 bar pressure, in a pure water steam system. The results revealed that all exposed materials showed relatively low weight gain, with no spallation of the oxide scale within the 2000 h of exposure. XRD analysis showed that Ni-based alloys developed an oxide scale consisting of four main phases: Cr2O3 (alloy 617, Haynes® 282®, alloy 263 and Haynes® 230®), MnCr2O4 (alloy 617, Haynes® 282® and Haynes® 230®), NiCr2O4 (alloy 617) and TiO2 (alloy 263, Haynes® 282®). In contrast, advanced steels showed the development of Cr2O3, MnCr2O4, Mn7SiO12, FeMn(SiO4) and SiO2 phases. The steel with the highest Cr content showed the formation of Fe3O4 and the thickest oxide scale.

  17. Sparing surgery with the use of TiNi-based endografts in larynx cancer patients.

    PubMed

    Muhamedov, Marat; Kulbakin, Denis; Gunther, Victor; Choynzonov, Evgeniy; Chekalkin, Timofey; Hodorenko, Valentina

    2015-02-01

    Purpose of this study was to improve a technique of sparing surgery in patients with laryngeal cancer by using TiNi-based endografts and to achieve well functional and oncological results after laryngectomy. Totally 120 patients with laryngeal cancer were observed (T2-3 N0-1 M0 ). We have developed a method of laryngeal reconstruction using TiNi-based endografts. All endografts show the superelastic behavior recovering the shape. All patients have undergone different types of sparing surgeries with simultaneous replacement with endografts. Voice function was completely saved in 112 cases and partially in 8 ones. Respiratory function was fully restored in 106 patients. The protective function of the larynx was achieved in 116 patients. The technique allowed to achieve well oncological (the 5-year and overall recurrence-free survival rates of all 120 patients were 83% and 76%, respectively) and functional (larynx function was saved in 93% of cases) outcomes after extensive and subtotal resections in patients with locally distributed larynx cancer. © 2014 Wiley Periodicals, Inc.

  18. A synchrotron study of microstructure gradient in laser additively formed epitaxial Ni-based superalloy

    DOE PAGES

    Xue, Jiawei; Zhang, Anfeng; Li, Yao; ...

    2015-10-08

    Laser additive forming is considered to be one of the promising techniques to repair single crystal Ni-based superalloy parts to extend their life and reduce the cost. Preservation of the single crystalline nature and prevention of thermal mechanical failure are two of the most essential issues for the application of this technique. Here we employ synchrotron X-ray microdiffraction to evaluate the quality in terms of crystal orientation and defect distribution of a Ni-based superalloy DZ125L directly formed by a laser additive process rooted from a single crystalline substrate of the same material. We show that a disorientation gradient caused bymore » a high density of geometrically necessary dislocations and resultant subgrains exists in the interfacial region between the epitaxial and stray grains. This creates a potential relationship of stray grain formation and defect accumulation. In conclusion, the observation offers new directions on the study of performance control and reliability of the laser additive manufactured superalloys.« less

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

    NASA Technical Reports Server (NTRS)

    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.

  20. Steam Oxidation Behavior of Advanced Steels and Ni-Based Alloys at 800 °C

    NASA Astrophysics Data System (ADS)

    Dudziak, T.; Boroń, L.; Deodeshmukh, V.; Sobczak, J.; Sobczak, N.; Witkowska, M.; Ratuszek, W.; Chruściel, K.

    2017-03-01

    This publication studies the steam oxidation behavior of advanced steels (309S, 310S and HR3C) and Ni-based alloys (Haynes® 230®, alloy 263, alloy 617 and Haynes® 282®) exposed at 800 °C for 2000 h under 1 bar pressure, in a pure water steam system. The results revealed that all exposed materials showed relatively low weight gain, with no spallation of the oxide scale within the 2000 h of exposure. XRD analysis showed that Ni-based alloys developed an oxide scale consisting of four main phases: Cr2O3 (alloy 617, Haynes® 282®, alloy 263 and Haynes® 230®), MnCr2O4 (alloy 617, Haynes® 282® and Haynes® 230®), NiCr2O4 (alloy 617) and TiO2 (alloy 263, Haynes® 282®). In contrast, advanced steels showed the development of Cr2O3, MnCr2O4, Mn7SiO12, FeMn(SiO4) and SiO2 phases. The steel with the highest Cr content showed the formation of Fe3O4 and the thickest oxide scale.

  1. Organometallic Palladium Complexes with a Water-Soluble Iminophosphorane Ligand as Potential Anticancer Agents

    PubMed Central

    Carreira, Monica; Calvo-Sanjuán, Rubén; Sanaú, Mercedes; Marzo, Isabel; Contel, María

    2012-01-01

    The synthesis and characterization of a new water-soluble iminophosphorane ligand TPA=N-C(O)-2BrC6H4 (C,N-IM; TPA = 1,3,5-triaza-7-phosphaadamantane) 1 is reported. Oxidative addition of 1 to Pd2(dba)3 affords the orthopalladated dimer [Pd(μ-Br){C6H4(C(O)N=TPA-kC,N)-2}]2 (2) as a mixture of cis and trans isomers (1:1 molar ratio) where the iminophosphorane moeity behaves as a C,N-pincer ligand. By addition of different neutral or monoanionic ligands to 2, the bridging bromide can be cleaved and a variety of hydrophilic or water-soluble mononuclear organometallic palladium(II) complexes of the type [Pd{C6H4(C(O)N=TPA-kC,N)-2}(L-L)] (L-L = acac (3); S2CNMe2 (4); 4,7-Diphenyl-1,10-phenanthrolinedisulfonic acid disodium salt C12H6N2(C6H4SO3Na)2 (5)); [Pd{C6H4(C(O)N=TPA-kC,N)-2}(L)Br] (L = P(mC6H4SO3Na)3 (6); P(3-Pyridyl)3 (7)) and, [Pd(C6H4(C(O)N=TPA)-2}(TPA)2Br] (8) are obtained as single isomers. All new complexes were tested as potential anticancer agents and their cytotoxicity properties were evaluated in vitro against human Jurkat-T acute lymphoblastic leukemia cells, normal T-lymphocytes (PBMC) and DU-145 human prostate cancer cells. Compounds [Pd(μ-Br){C6H4(C(O)N=TPA-kC,N)-2}]2 (2) and [Pd{C6H4(C(O)N=TPA-kC,N)-2}(acac)] 3 (which has been crystallographically characterized) display the higher cytotoxicity against the above mentioned cancer cell lines while being less toxic to normal T-lymphocytes (peripheral blood mononuclear cells: PBMC). In addition, 3 is very toxic to cisplatin resistant Jurkat shBak indicating a cell death pathway that may be different to that of cisplatin. The interaction of 2 and 3 with plasmid (pBR322) DNA is much weaker than that of cisplatin pointing to an alternative biomolecular target for these cytotoxic compounds. All the compounds show an interaction with human serum albumin (HSA) faster than that of cisplatin. PMID:23066172

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

    PubMed

    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

  3. Combining Organometallic Reagents, the Sulfur Dioxide Surrogate DABSO, and Amines: A One-Pot Preparation of Sulfonamides, Amenable to Array Synthesis**

    PubMed Central

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

    2015-01-01

    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. PMID:25431118

  4. The direct synthesis of organic and organometallic-containing MICA-type aluminosilicates

    SciTech Connect

    Carrado, K.A.; Awaluddin, A.

    1993-08-01

    Layer-silicate clay structures can provide supramolecular organization for catalysis, chiral reactions, colloid science, and electron transfer. The authors have successfully modified the experimental preparations of several different layer silicates in order to incorporate a wide variety of organic and organometallic molecules in the clay galleries. Synthesis and physical characterization of these materials are described and compared to ion-exchanged natural clay analogs. In addition, the photophysical properties of organometallic Ru(II) complexes incorporated by direct hydrothermal crystallization into synthetic clays were measured. 3 tabs, 21 refs.

  5. Performance of Alumina-Forming Austenitic Steels, Fe-base and Ni-base alloys exposed to metal dusting environments

    SciTech Connect

    Vande Put Ep Rouaix, Aurelie; Unocic, Kinga A; Pint, Bruce A; Brady, Michael P

    2011-01-01

    A series of conventional Fe- and Ni- base, chromia- and alumina- forming alloys, and a newly developed creep-resistant, alumina-forming austenitic steel were developed and its performance relative to conventional Fe- and Ni-based chromia-forming alloys was evaluated in metal dusting environments with a range of water vapor contents. Five 500h experiments have been performed at 650 C with different water vapor contents and total pressures. Without water vapor, the Ni-base alloys showed greater resistance to metal dusting than the Fe-base alloys, including AFA. However, with 10-28% water vapor, more protective behavior was observed with the higher-alloyed materials and only small mass changes were observed. Longer exposure times are in progress to further differentiate performance.

  6. DISTRIBUTION OF ORGANIC AND ORGANOMETALLIC COMPOUNDS IN SEDIMENTS FROM THE GULF OF MEXICO

    EPA Science Inventory

    In 1994, over 200 sediment samples were collected in accordance with EPA's Environmental Monitoring and Assessment (EMAP) probabilistic sampling protocol from coastal and estuarine locations in the Louisianian Province (Gulf of Mexico). Organic extracts of homogenized aliquots we...

  7. DISTRIBUTION OF ORGANIC AND ORGANOMETALLIC COMPOUNDS IN SEDIMENTS FROM THE GULF OF MEXICO

    EPA Science Inventory

    In 1994, over 200 sediment samples were collected in accordance with EPA's Environmental Monitoring and Assessment (EMAP) probabilistic sampling protocol from coastal and estuarine locations in the Louisianian Province (Gulf of Mexico). Organic extracts of homogenized aliquots we...

  8. Photodissociation dynamics of organometallic compounds: Study of the dihydride complex H2Fe(CO)4

    SciTech Connect

    Heitz, M. C.; Daniel, C.

    1996-04-01

    The photodissociation of the dihydride complex H2Fe(CO)4 has been investigated by a theoretical approach, involving time-dependent wave packet propagations on potential energy surfaces (PES) obtained from CASSCF-MRCI calculations. A two dimensions simulation is proposed, allowing the study of two concurrents processes, namely photoinduced elimination of molecular hydrogen vs loss of a carbonyl ligand. Three singlet excited states {sup 1}bA1(x{sup 2}-y{sup 2}{yields}{sigma}g*), {sup 1}aB2(x{sup 2}-y{sup 2}{yields}{sigma}u*), {sup 1}aB1(yz{yields}{sigma}g*) has been identified in the range of energy corresponding to the experimental absorption spectrum. Wave packets propagations performed separately on the three PES describe the elementary processes contributing to the photochemical behavior of the molecule. The absorption spectrum reflecting these different processes, has been calculated, using the time dependent formalism.

  9. Two-step solid-state synthesis of PEPPSI-type compounds.

    PubMed

    Adams, Christopher J; Lusi, Matteo; Mutambi, Emily M; Guy Orpen, A

    2015-06-14

    The two-step mechanochemical preparation of carbene-pyridine complexes of palladium and platinum is reported. The organometallic products, which represent a class of commercially available catalysts, are rapidly formed in excellent yield proving solvent-free synthesis to be a viable synthetic alternative even in the case of NHC-containing compounds.

  10. Ni-base superalloy powder-processed porous layer for gas cooling in extreme environments

    DOE PAGES

    White, Emma M. H.; Heidloff, Andrew J.; Byrd, David J.; ...

    2016-05-26

    Extreme high temperature conditions demand novel solutions for hot gas filters and coolant access architectures, i.e., porous layers on exposed components. These high temperatures, for example in current turbine engines, are at or exceeding current material limits for high temperature oxidation/corrosion, creep resistance, and, even, melting temperature. Thus novel blade designs allowing greater heat removal are required to maintain airfoil temperatures below melting and/ or rapid creep deformation limits. Gas atomized Ni-base superalloy powders were partially sintered into porous layers to allow full-surface, transpirational cooling of the surface of airfoils. Furthermore, these powder-processed porous layers were fully characterized for surface,more » morphology, cross-sectional microstructure, and mechanical strength characteristics. A sintering model based on pure Ni surface diffusion correlated well with the experimental results and allowed reasonable control over the partial sintering process to obtain a specified level of porosity within the porous layer.« less

  11. Ni-base superalloy powder-processed porous layer for gas cooling in extreme environments

    SciTech Connect

    White, Emma M. H.; Heidloff, Andrew J.; Byrd, David J.; Anderson, Ross D.; Anderson, Iver E.

    2016-05-26

    Extreme high temperature conditions demand novel solutions for hot gas filters and coolant access architectures, i.e., porous layers on exposed components. These high temperatures, for example in current turbine engines, are at or exceeding current material limits for high temperature oxidation/corrosion, creep resistance, and, even, melting temperature. Thus novel blade designs allowing greater heat removal are required to maintain airfoil temperatures below melting and/ or rapid creep deformation limits. Gas atomized Ni-base superalloy powders were partially sintered into porous layers to allow full-surface, transpirational cooling of the surface of airfoils. Furthermore, these powder-processed porous layers were fully characterized for surface, morphology, cross-sectional microstructure, and mechanical strength characteristics. A sintering model based on pure Ni surface diffusion correlated well with the experimental results and allowed reasonable control over the partial sintering process to obtain a specified level of porosity within the porous layer.

  12. Interdiffusion Behavior of Pt-Diffused gamma+gamma' Coatings on Ni-Based Superalloys

    SciTech Connect

    Zhang, Ying; Stacy, J P; Pint, Bruce A; Haynes, James A; Hazel, Brian T; Nagaraj, Ben

    2008-01-01

    Platinum-diffused {gamma} + {gamma}{prime} coatings ({approx} 20 at.% Al, {approx} 22 at.% Pt) were synthesized on Rene 142 and Rene N5 Ni-based superalloys by electroplating the substrates with {approx} 7 {micro}m of Pt, followed by an annealing treatment in vacuum at 1175 C. In order to study the compositional and microstructural evolution of these coatings at elevated temperatures, interdiffusion experiments were carried out on coated specimens in the temperature range of 900-1050 C for various durations. Composition profiles of the alloying elements in the {gamma} + {gamma}{prime} coatings before and after diffusion experiments were determined by electron probe microanalysis. Although the change of the Al content in the coatings was minimal under these interdiffusion conditions, the decrease of the Pt content and increase of the diffusion depth of Pt into the substrate alloys were significant. A preliminary diffusion model was used to estimate the Pt penetration depth after diffusion.

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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

    The microstructure of the Ni-based superalloy MAR-M246 (Hf) which is used in manufacturing the components of the Space Shuttle Main Engine was investigated. In the first year, the superalloy will be studied using optical photomicrographs and the differential thermal analysis. During this period, the existing experimental equipment like cutting, grinding/polishing machines, metallurgical microscope will be used to but/polish and take the photomicrographs. At present, only a 35 mm camera attachment with the olympus inverted metallurgical microscope is being used. Due to this, there was considerable delay in processing photographs. A Perkin-Elmer Differential Thermal Analyzer (DTA-1700) was ordered and finally installed on April 28, 1987. Preliminary test runs were made on silver as well as MAR-M246 (Hf).

  15. Ni-base superalloy powder-processed porous layer for gas cooling in extreme environments

    SciTech Connect

    White, Emma M. H.; Heidloff, Andrew J.; Byrd, David J.; Anderson, Ross D.; Anderson, Iver E.

    2016-05-26

    Extreme high temperature conditions demand novel solutions for hot gas filters and coolant access architectures, i.e., porous layers on exposed components. These high temperatures, for example in current turbine engines, are at or exceeding current material limits for high temperature oxidation/corrosion, creep resistance, and, even, melting temperature. Thus novel blade designs allowing greater heat removal are required to maintain airfoil temperatures below melting and/ or rapid creep deformation limits. Gas atomized Ni-base superalloy powders were partially sintered into porous layers to allow full-surface, transpirational cooling of the surface of airfoils. Furthermore, these powder-processed porous layers were fully characterized for surface, morphology, cross-sectional microstructure, and mechanical strength characteristics. A sintering model based on pure Ni surface diffusion correlated well with the experimental results and allowed reasonable control over the partial sintering process to obtain a specified level of porosity within the porous layer.

  16. Reduction of chromium in Ni-base superalloys through element substitution and rapid solidification processing

    NASA Technical Reports Server (NTRS)

    Fraser, H. D.; Muddl, B. C.

    1982-01-01

    The reduction in the use of Cr in Ni base superalloys by the combined approaches of both elemental substitution and rapid solidification processing is studied. The elements Si, Zr, Y and Hf were chosen as potential partial substitutes for Cr in Waspaloy and IN 713LC sine their separate addition to other alloys has previously resulted in enhanced oxidation resistance. The roles of Cr and these replacement elements in determining the microstructure and properties are evaluated. The elements Si, Zr, and Y and Hf are used as partial replacements for Cr in the base superalloys and these resultant alloys are processed using rapid solidification techniques. The mechanical properties and oxidation resistance of the processed materials are evaluated. The microstructure is characterized using state of the art techniques (e.g. analytical transmission electron microscopy), and the mechanism by which these structures are produced is determined.

  17. Enhanced carbon tolerance on Ni-based reforming catalyst with Ir alloying: A DFT study

    NASA Astrophysics Data System (ADS)

    Ahn, Kiyong; Choi, Sungjun; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Jedo; Kim, Hyoungchul

    2017-10-01

    Carbon deposition is a major cause of performance degradation for the Ni-based catalyst used in steam reforming of hydrocarbons. In this work, we perform first principle calculations to show that carbon tolerance behavior can be significantly enhanced by alloying Ni with Ir. The most stable atomic structure predicted by the surface phased diagram shows that Ir atoms prefer to stay on the surface of the alloy ensuring their exposure to the incoming gas. We find that the presence of Ir atoms suppress the surface migration of carbon atoms and weaken the stability of the adsorbed carbon agglomerates. Finally, we elucidate that the local reactivity change caused by the shift in the d-band structure is responsible for such good carbon tolerance behavior.

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

    NASA Technical Reports Server (NTRS)

    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.

  19. Corrosion behavior aspects of Ni-base self-fluxing coatings

    NASA Astrophysics Data System (ADS)

    Paulin, C.; Chicet, D. L.; Istrate, B.; Panţuru, M.; Munteanu, C.

    2016-08-01

    Due to the development of thermal spray deposition technologies, thus obtained layers have more applications and fields of use. One of the coatings with increased application is the one produced from Ni-based self-fluxing alloys, which besides the good wear resistance, shows a satisfactory corrosion resistance. In this study it was observed the behavior of three types of coatings produced by Flame Spray method, both at wear and especially corrosion in the environment simulating acid rain. As a result of the experiments it was found that these layers became compact enough after applying the self-fluxing heat treatment, so in their structure are not present defects such as pores and micro-cracks, unmelted particles etc., which could be points of corrosion initiation.

  20. Microstructure and creep resistance of a diffusionally aluminized Ni-base superalloy

    NASA Astrophysics Data System (ADS)

    Sah, Injin; Kim, Sung Hwan; Jang, Changheui

    2016-11-01

    An aluminide layer was formed on a wrought Ni-base superalloy by the diffusional aluminizing method, which involves a physical vapor deposition of Al followed by two-step heat treatment in vacuum. Microstructural analysis revealed the presence of an aluminide layer, inter-diffusion zone (IDZ), and affected substrate, all of which developed due to the inter-diffusion of deposited Al and elements in the matrix. In addition, a wide carbide free zone, in which grain boundaries were mostly denuded of carbides, was found below the IDZ. Depth profiling analysis using a glow discharge spectrometer confirmed the reduced carbon content in the carbide free zone. At 900 °C, the diffusionally aluminized specimens showed a decrease in creep-rupture life caused by the presence of the carbide free zone. Fracture surface and cross-section microstructure observation confirmed the detrimental effect of the carbide free zone on the creep resistance of the diffusionally aluminized Alloy 617.

  1. Development of Ni-based Sulfur Resistant Catalyst for Diesel Reforming

    SciTech Connect

    Gunther Dieckmann

    2006-06-30

    In order for diesel fuel to be used in a solid oxide fuel cell auxiliary power unit, the diesel fuel must be reformed into hydrogen, carbon monoxide and carbon dioxide. One of the major problems facing catalytic reforming is that the level of sulfur found in low sulfur diesel can poison most catalysts. This report shows that a proprietary low cost Ni-based reforming catalyst can be used to reform a 7 and 50 ppm sulfur containing diesel fuel for over 500 hours of operation. Coking, which appears to be route of catalyst deactivation due to metal stripping, can be controlled by catalyst modifications, introduction of turbulence, and/or by application of an electromagnetic field with a frequency from {approx}50 kHz to 13.56 MHz with field strength greater than about 100 V/cm and more preferably greater about 500 V/cm.

  2. FeNi-based magnetoimpedance multilayers: Tailoring of the softness by magnetic spacers

    NASA Astrophysics Data System (ADS)

    Svalov, A. V.; Fernandez, E.; Garcia-Arribas, A.; Alonso, J.; Fdez-Gubieda, M. L.; Kurlyandskaya, G. V.

    2012-04-01

    The microstructure and magnetic properties of sputtered permalloy films and FeNi(170 nm)/X/FeNi(170 nm) (X = Co, Fe, Gd, Gd-Co) sandwiches were studied. Laminating of the thick FeNi film with various spacers was done in order to control the magnetic softness of FeNi-based multilayers. In contrast to the Co and Fe spacers, Gd and Gd-Co magnetic spacers improved the softness of the FeNi/X/FeNi sandwiches. The magnetoimpedance responses were measured for [FeNi/Ti(6 nm)]2/FeNi and [FeNi/Gd(2 nm)]2/FeNi multilayers in a frequency range of 1-500 MHz: for all frequencies under consideration the highest magnetoimpedance variation was observed for [FeNi/Gd(2 nm)]2/FeNi multilayers.

  3. Reduction of chromium in Ni-base superalloys through element substitution and rapid solidification processing

    NASA Technical Reports Server (NTRS)

    Fraser, H. D.; Muddl, B. C.

    1982-01-01

    The reduction in the use of Cr in Ni base superalloys by the combined approaches of both elemental substitution and rapid solidification processing is studied. The elements Si, Zr, Y and Hf were chosen as potential partial substitutes for Cr in Waspaloy and IN 713LC sine their separate addition to other alloys has previously resulted in enhanced oxidation resistance. The roles of Cr and these replacement elements in determining the microstructure and properties are evaluated. The elements Si, Zr, and Y and Hf are used as partial replacements for Cr in the base superalloys and these resultant alloys are processed using rapid solidification techniques. The mechanical properties and oxidation resistance of the processed materials are evaluated. The microstructure is characterized using state of the art techniques (e.g. analytical transmission electron microscopy), and the mechanism by which these structures are produced is determined.

  4. An anisotropic micromechanics model for predicting the rafting direction in Ni-based single crystal superalloys

    NASA Astrophysics Data System (ADS)

    Li, Shuang-Yu; Wu, Wen-Ping; Chen, Ming-Xiang

    2016-02-01

    An anisotropic micromechanics model based on the equivalent inclusion method is developed to investigate the rafting direction of Ni-based single crystal superalloys. The micromechanical model considers actual cubic structure and orthogonal anisotropy properties. The von Mises stress, elastic strain energy density, and hydrostatic pressure in different inclusions of micromechanical model are calculated when applying a tensile or compressive loading along the [001] direction. The calculated results can successfully predict the rafting direction for alloys exhibiting a positive or a negative mismatch, which are in agreement with pervious experimental and theoretical studies. Moreover, the elastic constant differences and mismatch degree of the matrix and precipitate phases and their influences on the rafting direction are carefully discussed.

  5. Analysis of WC/Ni-Based Coatings Deposited by Controlled Short-Circuit MIG Welding

    NASA Astrophysics Data System (ADS)

    Vespa, P.; Pinard, P. T.; Gauvin, R.; Brochu, M.

    2012-06-01

    This study investigates the recently developed controlled short-circuit metal inert gas (CSC-MIG) welding system for depositing WC/Ni-based claddings on carbon steel substrates. WC/Ni-based coatings deposited by CSC-MIG were analyzed by optical light microscopy and scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy (EDS) and electron backscatter diffraction (EBSD) capabilities. X-ray diffraction (XRD) and hardness measurements of depositions are also reported. The CSC-MIG welding system provides a significant amount of user control over the current waveform during welding and has lower heat input when compared with traditional MIG welding. Heat input for the analyzed coatings ranged from 10.1 to 108.7 J/mm. Metallurgically bonded coatings free from spatter and with 0.75% average porosity were produced. It was found that the detrimental decarburization of the WC particles seen in thermal spray systems does not occur when welding with the CSC-MIG. Precipitation of a reaction layer around the reinforcing phase was identified as WC; the average thickness of which increases from 3.8 to 7.2 μm for the low and high heat input condition, respectively. Precipitation of newly formed WC particles was observed; their size distribution increased from D 50 of 2.4 μm in the low heat input weldment to 6.75 μm in the high heat input weldment. The level of dilution of the reinforcing phase increases significantly with heat input. The hardness of the deposited coatings decreases from 587 HV10 to 410 HV10 when the energy input was increased from 10.1 to 108.7 J/mm.

  6. Time-Dependent Crack Growth Thresholds of Ni-Base Superalloys

    NASA Astrophysics Data System (ADS)

    Chan, Kwai S.

    2014-07-01

    A micromechanical model has been developed for predicting the time-dependent crack growth threshold and its variability by considering oxide formation or cavity formation ahead of an elastic crack subjected to a sustained load at a stress intensity factor, K, at elevated temperatures in air. It is demonstrated that stress relaxation associated with a volume-expansion process such as the formation of creep cavities or oxides with a positive transformation strain can induce residual stresses at the tip of the elastic crack. The near-tip residual stresses must be overcome by the external load, thereby instigating a growth threshold, K th, for the onset of time-dependent crack growth. This micromechanical framework provides the basis for developing appropriate predictive models for the time-dependent crack growth thresholds associated with several damage processes, including (1) oxidation-assisted intergranular crack growth, (2) K-controlled creep crack growth along an intergranular path, and (3) stress corrosion cracking. The micromechanical threshold models have been utilized to predict the time-dependent crack growth thresholds of a variety of Ni-base superalloys. The material parameters that contribute to the variability of the time-dependent crack growth thresholds have been identified and related to variations of mixed oxides or creep cavities formed near the crack tip. A size scale effect is also predicted for the transformation toughening phenomenon, which is largest at or below K th but diminishes at increasing K levels above the threshold. Finally, the micromechanical models are utilized to identify means for suppressing time-dependent crack growth in Ni-base alloys.

  7. Microstructural characterization of a new mechanically alloyed Ni-base ODS superalloy powder

    SciTech Connect

    Seyyed Aghamiri, S.M.; Shahverdi, H.R.; Ukai, S.; Oono, N.; Taya, K.; Miura, S.; Hayashi, S.; Okuda, T.

    2015-02-15

    The microstructure of a new Ni-base oxide dispersion strengthened superalloy powder was studied for high temperature gas turbine applications after the mechanical alloying process. In this study, an atomized powder with a composition similar to the CMSX-10 superalloy was mechanically alloyed with yttria and Hf powders. The mechanically alloyed powder included only the supersaturated solid solution γ phase without γ′ and yttria provided by severe plastic deformation, while after the 3-step aging, the γ′ phase was precipitated due to the partitioning of Al and Ta to the γ′ and Co, Cr, Re, W, and Mo to the γ phase. Mechanical alloying modified the morphology of γ′ to the new coherent γ–γ′ nanoscale lamellar structure to minimize the elastic strain energy of the precipitation, which yielded a low lattice misfit of 0.16% at high temperature. The γ′ lamellae aligned preferentially along the elastically soft [100] direction. Also, the precipitated oxide particles were refined in the γ phase by adding Hf from large incoherent YAlO{sub 3} to fine semi-coherent Y{sub 2}Hf{sub 2}O{sub 7} oxide particles with the average size of 7 nm and low interparticle spacing of 76 nm. - Highlights: • A new Ni-base ODS superalloy powder was produced by mechanical alloying. • The nanoscale γ–γ′ lamellar structure was precipitated after the aging treatment. • Fine semi-coherent Y{sub 2}Hf{sub 2}O{sub 7} oxide particles were precipitated by addition of Hf.

  8. Secondary Reaction Zone Formations in coated Ni-base Single Crystal Superalloys

    NASA Astrophysics Data System (ADS)

    Suzuki, A.; Rae, C. M. F.

    2009-05-01

    Ruthenium (Ru) has been added to the latest 4th Generation Ni-base superalloys to improve phase stability and modify creep life. Various coatings are routinely applied to these advanced alloys to protect the turbine blade at elevated temperature, however, this creates several problems such as the precipitation of brittle Topologically Close-Packed (TCP) phases and the formation of Secondary Reaction Zones (SRZ). The SRZ forms under the plat-aluminized coating of turbine blades and consists of γ, γ and TCP phases growing into substrate by the migration of high-angle grain boundaries. Surface residual stress and chemical super-saturation of alloying elements are associated to SRZ formation. In the thin sections of high-pressure turbine blades this is critical in determining blade performance and longevity. It is essential to know how Ru additions affect coating and SRZ morphologies during exposure. In this study, we focus on the effects of three variables on the SRZ formation: Ru concentration, alloy composition in Ru-containing alloys and surface finish. A series of Platinum-Aluminised superalloys containing 2-5wt% Ru and having various surface finishes was studied after isothermal exposure at 1100°C for up to 500h. The alloys were classified into two groups by their distinctive SRZ morphology. At the lowest Ru levels sporadic formation of SRZ was observed, whilst a continuous SRZ was formed in the higher Ru alloys. EBSD analysis revealed that the latter group have a higher nucleation rate of individual SRZ grains and also showed more rapid SRZ growth. The precipitation of TCPs in the substrate also inhibited the growth of the SRZ towards the end of the exposure further reducing the penetration of the SRZ into the substrate. It is concluded that Ru-additions to Ni-base superalloys are effective in impeding TCP phase formation in the substrate, but increase both the extent and the rate of SRZ formation beneath coating.

  9. Organometallic single source precursors for chemical vapor deposition of metal chalcogenides

    NASA Astrophysics Data System (ADS)

    Seidler, Dean Jerry

    The group 14--16 compounds with the general formula (Bn2SnE)3, (Bn3Sn)2E, and Bn 2Sn(EBn)2, where E = S or Se, were synthesized and investigated as potential single-source precursors for the preparation of tin chalcogenides. Each precursor was pyrolyzed under an inert atmosphere. Decomposition took place at relatively mild conditions (<400°C). The cyclic molecules, (Bn2SnS)3 and (Bn2SnSe)3, produced tin sulfide and tin selenide, respectively. The samples were XRD phase pure, and combustion analysis indicated less than 1% carbon present in the final product. The acyclic precursors, (Bn3Sn)2S and (Bn 3Sn)2Se, yielded a mixture of the tin chalcogenide and elemental tin with carbon content <1%. The pyrolysis of Bn2Sn(SBn) 2 and Bn2Sn(SeBn)2 produced SnS2 and SnSe2, respectively, with carbon contamination <3%. The only volatile by-product detected from the pyrolysis of these compounds was bibenzyl, indicating all of the tin and chalcogen were left behind in the solid state product. Solid solutions could be generated by combining (Bn 2SnS)3 and (Bn2SnSe)3, and pyrolyzing the mixture. Combinations of Bn2Sn(SBn)2 and Bn 2Sn(SeBn)2 yielded products with some solid solution character; however, some phase separation was indicated in the XRD patterns. Bn3SnSBn and (tert-Bu2SnS)2 were pyrolyzed to produce bulk samples of SnS and also used as single-source precursors for the chemical vapor deposition of thin films of SnS on glass and halite substrates. The composition and morphology of the products, both as bulk materials and thin films, were influenced by the structure of the organometallic precursor, the nature of the leaving group attached to the metal (or chalcogen), and the nature of the film substrate.

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

    Nanocrystalline tin dioxide (SnO2) 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 SnO2 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 H2 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.Nanocrystalline tin dioxide (SnO2) 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 SnO2 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 H2 and CO gases, these layers led to highly sensitive, reversible and reproducible

  11. New methodologies for construction of hyperbranched organic and organometallic polymers

    NASA Astrophysics Data System (ADS)

    Xu, Kaitian

    2000-10-01

    A series of completely soluble hyperbranched polymers were synthesized by polycyclotrimerization of diynes for the first time. TaCl5-Ph 4Sn was found to be the effective catalyst and toluene to be the efficient solvent. A possible polycyclotrimerization mechanism via tantalacyclopentadiene intermediates is proposed. The polymerization processes including initiation, propagation and termination are analyzed. The unique backbiting reaction was found to be a plausible way to terminate the propagation chain. Conformations of the diynes greatly affect the occurrence of backbiting reaction and affect the solubility of resultant polymers to certain extent. Diynes with short spacers such as 1,5-hexadiyne (21 ); 1,6-heptadiyne (22); 1,7-octadiyne (23); and 1,8-nonadiyne (17); possess a conformation in which the two triple bonds locate closely. Such a conformation makes the backbiting termination to occur easily. Thus, soluble polymers are readily formed from these diynes. For the diynes of long spacers, a conformation with two far-separating triple bonds dramatically reduces the chance of backbiting reaction. Consequently, only partially soluble or insoluble polymers could be prepared. In the polycyclotrimerization of internal diynes, hexasubstituted benzene rings were formed. The steric effect of the terminal substituents plays an important role in the polymerization reaction. Internal diynes with bulky substituents such as 1,9-bis(trimethylsilyl)-1,8-nonadiyne (74), 1,6-bis(dimethylphenylsilyl)-1,5-hexadiyne (75), 1,8-bis(dimethylphenylsilyl)-1,7-octadiyne (76) gave little amount of polymers. Internal diynes with less bulky substituents and short spacers [e.g. 3,9-dodecadiyne (78) and 2,9-undecadiyne (79)] offered soluble polymers. In the study on hyperbranched organometallic polymers, a new methodology for the preparation of hyperbranched polysilynes was developed. Ceramization of the hyperbranched polymers produced mesoporous magnetoceramic materials. The compositions

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

    NASA Astrophysics Data System (ADS)

    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

  13. Molecular tectonics: heterometallic coordination networks based on a Pt(II) organometallic metallatecton.

    PubMed

    Zigon, Nicolas; Kyritsakas, Nathalie; Hosseini, Mir Wais

    2015-08-28

    Combinations of a neutral organometallic tecton based on a square planar Pt(ii) complex bearing two triphenylphosphine groups and two 4-ethynylpyridyl coordinating moieties in trans positions, with various metal halides (MX2, M = Co(ii), Ni(ii), Cd(ii), X = Cl(-) or Br(-)) lead to the formation of 2D grid type heterobimetallic coordination networks in the crystalline phase.

  14. Step structure of GaInAsSb grown by OMVPE (Organometallic Vapor Phase Epitaxy)

    SciTech Connect

    Charache, G.W.; Wang, C.A.

    1999-05-23

    The microscopic surface morphology of GaInAsSb grown by organometallic vapor phase epitaxy (OMVPE)on GaSb substrates has been studied by atomic force microscopy. The effects of growth temperature, alloy composition, and substrate misorientation on the step structure were investigated. The competition between thermodynamically driven phase separation and kinetically limited surface diffusion is discussed.

  15. Application of Organometallic Catalysis to the Commercial Production of L-DOPA.

    ERIC Educational Resources Information Center

    Knowles, W. S.

    1986-01-01

    Shows how asymmetric organometallic catalysts can be used to make complex organic molecules with extremely high enantioselectivity. The molecule considered is l-3, 4-dihydroxyphenylalanine (L-DOPA), an amino acid which was found to be effective in the treatment of Parkinson's disease. (JN)

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

    NASA Astrophysics Data System (ADS)

    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.

  17. Effect of solution treatment on the stress rupture property of MA ODS Ni-base superalloy at 760 C

    SciTech Connect

    Park, L.J.; Kim, Y.G.; Hong, S.H.; Haeberle, R.M.; Watwe, A.S.

    1995-10-01

    The strengthening of mechanically alloyed (MA) oxide dispersion strengthened (ODS) Ni-base superalloys is obtained through the precipitation hardening by a Ni{sub 3}(Al, Ti), which is known as {gamma}{prime} phase, at the intermediate temperature region of 760--850 C. The {gamma}{prime} precipitates are ordered FCC (L1{sub 2}) structure and are coherent with the nickel-rich {gamma} matrix having FCC structure. The size, volume fraction and distribution of the {gamma}{prime} precipitates are sensitively related to the heat treatment for precipitation and these parameters can significantly affect the mechanical properties of ODS Ni-base superalloys. The aim of this study was to investigate the effect of solution heat treatment temperature on the {gamma}{prime} precipitate size and stress rupture property of MA ODS Ni-base superalloy. The deformation mechanism of ODS Ni-base superalloy was discussed by observing the interaction between dislocations and {gamma}{prime} precipitates at 760 C.

  18. Investigation on corrosion behavior of Ni-based alloys in molten fluoride salt using synchrotron radiation techniques

    NASA Astrophysics Data System (ADS)

    Liu, Min; Zheng, Junyi; Lu, Yanling; Li, Zhijun; Zou, Yang; Yu, Xiaohan; Zhou, Xingtai

    2013-09-01

    Ni-based alloys have been selected as the structural materials in molten-salt reactors due to their high corrosion resistance and excellent mechanical properties. In this paper, the corrosion behavior of some Ni-based superalloys including Inconel 600, Hastelloy X and Hastelloy C-276 were investigated in molten fluoride salts at 750 °C. Morphology and microstructure of corroded samples were analyzed using scanning electron microscope (SEM), synchrotron radiation X-ray microbeam fluorescence (μ-XRF) and synchrotron radiation X-ray diffraction (SR-XRD) techniques. Results from μ-XRF and SR-XRD show that the main depleted alloying element of Ni-based alloys in molten fluoride salt is Cr. In addition, the results indicate that Mo can enhance the corrosion resistance in molten FLiNaK salts. Among the above three Ni-based alloys, Hastelloy C-276 exhibits the best corrosion resistance in molten fluoride salts 750 °C. Higher-content Mo and lower-content Cr in Hastelloy C-276 alloy were responsible for the better anti-corrosive performance, compared to the other two alloys.

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

    NASA Astrophysics Data System (ADS)

    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.

  20. The Development and Study of Surface Bound Ruthenium Organometallic Complexes

    NASA Astrophysics Data System (ADS)

    Abbott, Geoffrey Reuben

    The focus of this project has been on the use of mono-diimine ruthenium organometallic complexes, of the general structure [H(Ru)(CO)(L)2(L') 2][PF6] (L=PPh3, DPPENE and L'=Bpy, DcBpy, MBpyC, Phen, AminoPhen) bound to surfaces as luminescent probes. Both biological and inorganic/organic hybrid surfaces have been studied. The complexes were characterized both bound and unbound using standard analytical techniques such as NMR, IR and X-ray crystallography, as well as through several photophysical methods as well. Initially the study focused on how the photophyscial properties of the complexes were affected by incorporation into biological membranes. It was found that by conjugating the probes to a more rigid cholesterol moiety that luminescence was conserved, compared to conjugation with a far more flexible lipid moiety, where luminescence was either lost or reduced. Both the cholesterol and lipid conjugates were able to insert into a lipid membrane, and in the more rigid environment some of the lipid conjugates regained some of their luminescence, but often blue shifted and reduced, depending on the conjugation site. Silica Polyamine Composites (SPCs) were a hybrid material developed in the Rosenberg Lab as useful metal separation materials, that could be easily modified, and had several benefits over current commercially available polymers, or inorganic materials. These SPCs also provided an opportunity for the development of a heterogeneous platform for luminescent complexes as either catalysts or sensors. Upon binding of the luminescent Ru complexes to the surface no loss, or major change in luminescence was seen, however, when bound to the rigid surface a significant increase in excited state lifetime was measured. It is likely that through binding and interacting with the surface that the complexes lost non-radiative decay pathways, resulting in the increase in lifetime, however, these interactions do not seem to affect the energy level of the MLCT band in a

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

    NASA Astrophysics Data System (ADS)

    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

  2. Preliminary Investigations of Joining Technologies for Attaching Refractory Metals to Ni-Based Superalloys

    NASA Technical Reports Server (NTRS)

    Gould, Jerry E.; Ritzert, Frank J.; Loewenthal, William S.

    2006-01-01

    In this study, a range of joining technologies has been investigated for creating attachments between refractory metal and Ni-based superalloys. Refractory materials of interest include Mo-47%Re, T-111, and Ta-10%W. The Ni-based superalloys include Hastelloy X and MarM 247. During joining with conventional processes, these materials have potential for a range of solidification and intermetallic formation-related defects. For this study, three non-conventional joining technologies were evaluated. These included inertia welding, electro-spark deposition (ESD) welding, and magnetic pulse welding (MPW). The developed inertia welding practice closely paralleled that typically used for the refractory metals alloys. Metallographic investigations showed that forging during inertia welding occurred predominantly on the nickel base alloy side. It was also noted that at least some degree of forging on the refractory metal side of the joint was necessary to achieve consistent bonding. Both refractory metals were readily weldable to the Hastelloy X material. When bonding to the MarM 247, results were inconsistent. This was related to the higher forging temperatures of the MarM 247, and subsequent reduced deformation on that material during welding. ESD trials using a Hastelloy X filler were successful for all material combinations. ESD places down very thin (5- to 10- m) layers per pass, and interactions between the substrates and the fill were limited (at most) to that layer. For the refractory metals, the fill only appeared to wet the surface, with minimal dilution effects. Microstructures of the deposits showed high weld metal integrity with maximum porosity on the order of a few percent. Some limited success was also obtained with MPW. In these trials, only the T-111 tubes were used. Joints were possible for the T-111 tube to the Hastelloy X bar stock, but the stiffness of the tube (resisting collapse) necessitated the use of very high power levels. These power levels

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

  5. 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.

    PubMed

    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. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Grain Selection During Casting Ni-Base, Single-Crystal Superalloys with Spiral Grain Selector

    NASA Astrophysics Data System (ADS)

    Gao, S. F.; Liu, L.; Wang, N.; Zhao, X. B.; Zhang, J.; Fu, H. Z.

    2012-10-01

    The behavior of grain selection in a spiral grain selector during investment casting of a Ni-base, single-crystal (SX) superalloy, DD3, has been investigated by electron backscattered diffraction (EBSD) techniques and optical microscopy. The results indicated that the main function of starter block is to optimize the crystal orientation. During the process of grain selection in spiral passage, the grain near the inner wall of spiral passage was usually selected as the final single crystal. It was found that the dendrites near the inner wall could develop new tertiary dendritic arms that paralleled the primary dendrites from the secondary dendritic arms to overgrow the dendrites far away from the inner wall. The crystal orientation that was examined by X-ray diffraction revealed that (1) the crystal orientation did not change obviously with increasing spiral thickness or angle and (2) the crystal orientation could be optimized by increasing the withdrawal rate and ceramic mold temperature. The influence of pouring temperature on crystal orientation was also discussed.

  7. Toward Predictive Understanding of Fatigue Crack Nucleation in Ni-Based Superalloys

    NASA Astrophysics Data System (ADS)

    Jiang, Jun; Dunne, Fionn P. E.; Britton, T. Ben

    2017-05-01

    Predicting when and where materials fail is a holy grail for structural materials engineering. Development of a predictive capability in this domain will optimize the employment of existing materials, as well as rapidly enhance the uptake of new materials, especially in high-risk, high-value applications, such as aeroengines. In this article, we review and outline recent efforts within our research groups that focus on utilizing full-field measurement and calculation of micromechanical deformation in Ni-based superalloys. In paticular, we employ high spatial resolution digital image correlation (HR-DIC) to measure surface strains and a high-angular resolution electron backscatter diffraction technique (HR-EBSD) to measure elastic distortion, and we combine these with crystal plasticity finite element (CPFE) modeling. We target our studies within a system of samples that includes single, oligo, and polycrystals where the boundary conditions, microstructure, and loading configuration are precisely controlled. Coupling of experiment and simulation in this manner enables enhanced understanding of crystal plasticity, as demonstrated with case studies in deformation compatibility; spatial distributions of slip evolution; deformation patterning around microstructural defects; and ultimately development of predictive capability that probes the location of microstructurally sensitive fatigue cracks. We believe that these studies present a careful calibration and validation of our experimental and simulation-based approaches and pave the way toward new understanding of crack formation in engineering alloys.

  8. Desulfurization of Ni-based super alloys by combined heating and glow discharge

    SciTech Connect

    Outlaw, R.A.; Rezaie-Serej, S.; Allen, W.P.; Latanision, R.M.

    1996-04-15

    The service lifetime of blades and vanes in aircraft gas turbines can be influenced by the degradation of the interface of the Ni-based superalloy and the overlying aluminide coating during cyclic oxidation. Advanced superalloys and coatings rely on formation of a thin and continuous Al{sub 2}O{sub 3} film to protect the base alloy from further oxidative attack at temperatures above 980 C. In order that the Al{sub 2}O{sub 3} scale be protective, it must remain adherent to the underlying alloy under thermal cycling conditions. Recent experimental work indicates that the interfacial binding between Ni and the overlying Al{sub 2}O{sub 3} scale is initially strong, but has also been shown that segregation of indigenous sulfur to the metal/oxide interface induces premature scale spallation, apparently through a reduction in the interfacial adhesive strength with a concomitant reduction in component lifetime. Removal of the sulfur is the best solution to this problem.

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

    PubMed Central

    Li, Xu; Wang, Jun; Zhang, Jiao; Han, Yanfeng; Li, Xi

    2015-01-01

    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.

  10. Kinetics and Mechanisms of γ′ Reprecipitation in a Ni-based Superalloy

    PubMed Central

    Masoumi, F.; Shahriari, D.; Jahazi, M.; Cormier, J.; Devaux, A.

    2016-01-01

    The reprecipitation mechanisms and kinetics of γ′ particles during cooling from supersolvus and subsolvus temperatures were studied in AD730TM Ni-based superalloy using Differential Thermal Analysis (DTA). The evolution in the morphology and distribution of reprecipitated γ′ particles was investigated using Field Emission Gun Scanning Electron Microscopy (FEG-SEM). Depending on the cooling rate, γ′ particles showed multi or monomodal distribution. The irregularity growth characteristics observed at lower cooling rates were analyzed in the context of Mullins and Sekerka theory, and allowed the determination of a critical size of γ′ particles above which morphological instability appears. Precipitation kinetics parameters were determined using a non-isothermal JMA model and DTA data. The Avrami exponent was determined to be in the 1.5–2.3 range, suggesting spherical or irregular growth. A methodology was developed to take into account the temperature dependence of the rate coefficient k(T) in the non-isothermal JMA equation. In that regard, a function for k(T) was developed. Based on the results obtained, reprecipitation kinetics models for low and high cooling rates are proposed to quantify and predict the volume fraction of reprecipitated γ′ particles during the cooling process. PMID:27338868

  11. Effect of annealing on magnetic properties and structure of Fe-Ni based magnetic microwires

    NASA Astrophysics Data System (ADS)

    Zhukova, V.; Korchuganova, O. A.; Aleev, A. A.; Tcherdyntsev, V. V.; Churyukanova, M.; Medvedeva, E. V.; Seils, S.; Wagner, J.; Ipatov, M.; Blanco, J. M.; Kaloshkin, S. D.; Aronin, A.; Abrosimova, G.; Orlova, N.; Zhukov, A.

    2017-07-01

    We studied the magnetic properties and domain wall (DW) dynamics of Fe47.4Ni26.6Si11B13C2 and Fe77.5Si7.5B15 microwires. Both samples present rectangular hysteresis loop and fast magnetization switching. Considerable enhancement of DW velocity is observed in Fe77.5Si7.5B15, while DW velocity of samples Fe47.4Ni26.6Si11B13C2 is less affected by annealing. The other difference is the magnetic field range of the linear region on dependence of domain wall velocity upon magnetic field: in Fe47.4Ni26.6Si11B13C2 sample is considerably shorter and drastically decreases after annealing. We discussed the influence of annealing on DW dynamics considering different magnetoelastic anisotropy of studied microwires and defects within the amorphous state in Fe47.4Ni26.6Si11B13C2. Consequently we studied the structure of Fe47.4Ni26.6Si11B13C2 sample using X-ray diffraction and the atom probe tomography. The results obtained using the atom probe tomography supports the formation of the B-depleted and Si-enriched precipitates in the metallic nucleus of Fe-Ni based microwires.

  12. The Portevin-Le Chatelier Effect in the Ni-Based Superalloy IN100

    NASA Astrophysics Data System (ADS)

    Fernandez-Zelaia, Patxi; Adair, Benjamin S.; Barker, Vincent M.; Antolovich, Stephen D.

    2015-12-01

    The Portevin-Le Chatelier (PLC) effect has been studied in the Ni-based superalloy IN100 which is currently used as a disk material in jet engines. A series of tensile tests was carried out at 588 K, 755 K, and 922 K (315 °C, 482 °C, and 649 °C) at plastic strain rates ranging from a low of 6.21 × 10-6 s-1 to a high of 4.92 × 10-2 s-1. The activation energy was determined using the slope of a line on a strain rate/temperature graph which divided the area of the graph into two regions: (1) "PLC behavior observed," and (2) "No PLC behavior observed." A new statistical approach was developed to objectively differentiate between a true PLC effect and experimental uncertainty ( i.e., "noise"). The value of the activation energy was found to be 1.14 eV/atom, which strongly suggests that the rate controlling process was bulk diffusion of C in the lattice. A qualitative model, based on the Orowan equation and slip band dislocation mechanics, was proposed, which unifies the seemingly disparate ideas of the process being controlled by a single atom/dislocation interaction while at the same time exhibiting significant strains during PLC load drops.

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

    SciTech Connect

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  15. On the Occurrence of Liquation During Linear Friction Welding of Ni-Based Superalloys

    NASA Astrophysics Data System (ADS)

    Masoumi, F.; Shahriari, D.; Jahazi, M.; Cormier, J.; Flipo, B. C. D.

    2017-06-01

    A combination of experimental and analytical methods was used to study the possible occurrence of liquation during LFW of the newly developed AD730TM Ni-based superalloy. LFWed joints were produced using a semi-industrial size facility and the interfaces of the joints as well as the ejected flash were examined using optical and Field Emission Gun Scanning Electron Microscopy (FEG-SEM). Physical simulation of the LFW thermal cycle, using thermomechanical simulator Gleeble™ 3800, showed that incipient melting started from 1473 K (1200 °C). The analytical model, calibrated by experiments, predicted that the highest temperature of the interface was about 1523 K (1250 °C). The constitutive equations based on lattice and pipe diffusion models were developed to quantify the self-diffusivity of the elements and control the extent of liquation by considering the effect of LFW process parameters. Analytical results show that the application of compressive stresses during LFW results in 25 times increase in the diffusion of Ni atoms at the weld interface. Therefore, no presence of re-solidified phases, i.e., occurrence of liquation, was observed in the microstructure of the weld zone or the flash in the present study. Based on the obtained results, a methodology was developed for designing the optimum pressure above which no liquation, and hence cracking, will be observable.

  16. Investigations of White Layer Formation During Machining of Powder Metallurgical Ni-Based ME 16 Superalloy

    NASA Astrophysics Data System (ADS)

    Veldhuis, S. C.; Dosbaeva, G. K.; Elfizy, A.; Fox-Rabinovich, G. S.; Wagg, T.

    2010-10-01

    Surface integrity of machined parts made from the advanced Ni-based superalloys is important for modern manufacturing in the aerospace industry. Metallographic observations of the ME 16 alloy microstructure were made using optical metallography and a high-resolution scanning electron microscope with energy dispersive x-ray spectrometer (HR SEM/EDS). Tool life of cemented carbide inserts with TiAlN coating during machining (finishing turning operation) of ME 16 superalloy has been studied and wear patterns of the cutting tools were identified. Surface integrity of the machined part after completion of the turning operation was investigated. The morphology of machined parts has been examined and cross-sections of the machined surfaces have been analyzed. The formation of white layer on the surface of the machined part was studied for varied machining conditions. It was found that a 2-4 µm thick white layer forms during turning of the ME 16 superalloy. This layer was investigated using EDS and XRD. The studies show that the white layer is an oxygen-containing layer with a high amount of aluminum, enriched by chromium and tungsten. Under specific cutting conditions, the structure of white layer transforms into a γ-alumina. Formation of this thermal barrier ceramic white layer on the surface of the machined part negatively affects its surface integrity and cutting tool life.

  17. Influence of coarsened and rafted microstructures on the thermomechanical fatigue of a Ni-base superalloy

    DOE PAGES

    Kirka, M. M.; Brindley, K. A.; Neu, R. W.; ...

    2015-08-17

    The aging of the microstructure of Ni-base superalloys during service is mainly characterized by coarsening and rafting of the γ' precipitates. The influence of these different aged microstructures on thermomechanical fatigue (TMF) under either continuously cycled (CC) and creep-fatigue (CF) was investigated. Three different aged microstructures, generated through accelerated aging and pre-creep treatments, were studied: stress-free coarsened γ', rafted with orientation perpendicular to loading direction (N-raft), and rafted with orientation parallel to loading direction (P-raft). Under most conditions, the aged microstructures were less resistant to TMF than the virgin microstructure; however, there were exceptions. Both stress-free coarsened and N-raft microstructuresmore » resulted in a reduction in TMF life under both CC and CF conditions in comparison to the virgin material. P-raft microstructure also resulted in reduction in TMF life under CC conditions; however, an increase in life over that of the virgin material was observed under CF conditions. Finally, these differences are discussed and hypothesized to be related to the interactions of the dislocations in the γ channels with γ' precipitates.« less

  18. Influence of coarsened and rafted microstructures on the thermomechanical fatigue of a Ni-base superalloy

    SciTech Connect

    Kirka, M. M.; Brindley, K. A.; Neu, R. W.; Antolovich, S. D.; Shinde, S. R.; Gravett, P. W.

    2015-08-17

    The aging of the microstructure of Ni-base superalloys during service is mainly characterized by coarsening and rafting of the γ' precipitates. The influence of these different aged microstructures on thermomechanical fatigue (TMF) under either continuously cycled (CC) and creep-fatigue (CF) was investigated. Three different aged microstructures, generated through accelerated aging and pre-creep treatments, were studied: stress-free coarsened γ', rafted with orientation perpendicular to loading direction (N-raft), and rafted with orientation parallel to loading direction (P-raft). Under most conditions, the aged microstructures were less resistant to TMF than the virgin microstructure; however, there were exceptions. Both stress-free coarsened and N-raft microstructures resulted in a reduction in TMF life under both CC and CF conditions in comparison to the virgin material. P-raft microstructure also resulted in reduction in TMF life under CC conditions; however, an increase in life over that of the virgin material was observed under CF conditions. Finally, these differences are discussed and hypothesized to be related to the interactions of the dislocations in the γ channels with γ' precipitates.

  19. Hot Deformation Processing Map and Microstructural Evaluation of the Ni-Based Superalloy IN-738LC

    NASA Astrophysics Data System (ADS)

    Sajjadi, S. A.; Chaichi, A.; Ezatpour, H. R.; Maghsoudlou, A.; Kalaie, M. A.

    2016-04-01

    Hot deformation behavior of the Ni-based superalloy IN-738LC was investigated by means of hot compression tests over the temperature range of 1000-1200 °C and strain rate range of 0.01-1 s-1. The obtained peak flow stresses were related to strain rate and temperature through the hyperbolic sine equation with activation energy of 950 kJ/mol. Dynamic material model was used to obtain the processing map of IN-738LC. Analysis of the microstructure was carried out in order to study each domain's characteristic represented by the processing map. The results showed that dynamic recrystallization occurs in the temperature range of 1150-1200 °C and strain rate of 0.1 s-1 with the maximum power dissipation efficiency of 35%. The unstable domain was exhibited in the temperature range of 1000-1200 °C and strain rate of 1 s-1 on the occurrence of severe deformation bands and grain boundary cracking.

  20. Mechanically alloyed Ni-base alloys for heat-resistant applications

    SciTech Connect

    Wilson, R.K.; Fischer, J.J.

    1995-12-31

    INCONEL alloys MA 754 and MA 758 are nickel-base oxide dispersion-strengthened (ODS) alloys made by mechanical alloying (MA). Commercial use of Ma Ni-base alloys to date has been predominantly in aerospace applications of alloy MA 754 as turbine engine vanes. Both alloys are suitable for industrial heat treating components and other heat resistant alloy applications. Field trials and commercial experience in such applications of MA alloys are being gained while high temperature property characterization and new product form development continue. Hot isostatic pressing (HIP) is the standard consolidation method for billets from which large bar and plate are produced for industrial applications of MA. This paper describes production of standard mill shapes from HIP billets, and it presents information on current and potential uses of MA alloys in applications such as: skid rails for use in high temperature walking beam furnaces, heat treating furnace components, components for handling molten glass, and furnace tubes. The paper includes comparison of the properties obtained in alloy MA 754 (20% Cr) and alloy MA 758 (30% Cr).

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

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

    The microstructural characteristics of the Ni-based superalloy MAR-M246(Hf) which is used in manufacturing the components of the Space Shuttle's main engine have been studied. These superalloys need optimal heat treatment to get the best results. To find the optimum heat treatment the technique of differential thermal analysis and the optical photomicrographs are being planned to be utilized. In the first phase, the existing experimental equipment like cutting, grinding/polishing machines and metallurgical microscope have been set up to cut/polish and take the photomicrographs. In the beginning of this year an order was placed for the Leitz Mettalux-3 microscope with a hot stage for in-situ observation of the superalloy samples. The hot stage was tested for the first time, alloying the thermocouple with the Tantulum heating element and has not been installed finally by the supplier. A Perkin Elmer Differential Thermal Analyzer (DTA 1700) was procured in the first year of the project. Samples of MAR-M246(Hf), MAR-M247, Waspaloy, Udimet-41, CMSX-2 and CMSX-3 (polycrystalline and single crystals) have been studied using differential thermal analyzer.

  2. Electron phonon coupling in Ni-based binary alloys with application to displacement cascade modeling

    DOE PAGES

    Samolyuk, German D.; Stocks, George Malcolm; Stoller, Roger E.

    2016-04-01

    Energy transfer between lattice atoms and electrons is an important channel of energy dissipation during displacement cascade evolution in irradiated materials. On the assumption of small atomic displacements, the intensity of this transfer is controlled by the strength of electron–phonon (el–ph) coupling. The el–ph coupling in concentrated Ni-based alloys was calculated using electronic structure results obtained within the coherent potential approximation. It was found that Ni0.5Fe0.5, Ni0.5Co0.5 and Ni0.5Pd0.5 are ordered ferromagnetically, whereas Ni0.5Cr0.5 is nonmagnetic. Since the magnetism in these alloys has a Stoner-type origin, the magnetic ordering is accompanied by a decrease of electronic density of states atmore » the Fermi level, which in turn reduces the el–ph coupling. Thus, the el–ph coupling values for all alloys are approximately 50% smaller in the magnetic state than for the same alloy in a nonmagnetic state. As the temperature increases, the calculated coupling initially increases. After passing the Curie temperature, the coupling decreases. The rate of decrease is controlled by the shape of the density of states above the Fermi level. Introducing a two-temperature model based on these parameters in 10 keV molecular dynamics cascade simulation increases defect production by 10–20% in the alloys under consideration.« less

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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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. Effect of Ti content on creep properties of Ni-base single crystal superalloys

    NASA Astrophysics Data System (ADS)

    Choi, Baig Gyu; Kim, In Soo; Hong, Hyun Uk; Do, Jeonghyeon; Jung, Joong Eun; Jo, Chang Yong

    2017-09-01

    The effect of Ti content on the creep properties and microstructures of experimental Ni-base single crystal superalloys has been investigated. The experimental alloys were designed to provide better high temperature properties than the commercial single crystal alloy CMSX-4. The creep properties of the experimental alloys, Alloy 2 and Alloy 3, were superior to those of CMSX-4. Alloy 3 showed a longer creep life than Alloy 2 at 900 °C and 950 °C, while it has similar creep life with Alloy 2 at 982 °C. Transmission electron microscopy micrographs of the experimental alloys after the creep test showed distinct deformation features as a function of temperature and Ti content. The dissociation of dislocations into partial dislocations with stacking faults in Alloy 3 was found to improve resistance to creep deformation at 950 °C. The effect of Ti on the creep deformation mechanism was not evident at 982 °C, which resulted in similar creep properties in both experimental alloys. The transition of the γ' cutting mechanism from dislocations coupled with stacking faults to anti-phase boundary coupled pairs occurred both in Alloy 2 and Alloy 3. However, the transition temperature was higher in Alloy 3 than in Alloy 2 because of the difference in Ti contents.

  6. Kinetics and Mechanisms of γ‧ Reprecipitation in a Ni-based Superalloy

    NASA Astrophysics Data System (ADS)

    Masoumi, F.; Shahriari, D.; Jahazi, M.; Cormier, J.; Devaux, A.

    2016-06-01

    The reprecipitation mechanisms and kinetics of γ‧ particles during cooling from supersolvus and subsolvus temperatures were studied in AD730TM Ni-based superalloy using Differential Thermal Analysis (DTA). The evolution in the morphology and distribution of reprecipitated γ‧ particles was investigated using Field Emission Gun Scanning Electron Microscopy (FEG-SEM). Depending on the cooling rate, γ‧ particles showed multi or monomodal distribution. The irregularity growth characteristics observed at lower cooling rates were analyzed in the context of Mullins and Sekerka theory, and allowed the determination of a critical size of γ‧ particles above which morphological instability appears. Precipitation kinetics parameters were determined using a non-isothermal JMA model and DTA data. The Avrami exponent was determined to be in the 1.5–2.3 range, suggesting spherical or irregular growth. A methodology was developed to take into account the temperature dependence of the rate coefficient k(T) in the non-isothermal JMA equation. In that regard, a function for k(T) was developed. Based on the results obtained, reprecipitation kinetics models for low and high cooling rates are proposed to quantify and predict the volume fraction of reprecipitated γ‧ particles during the cooling process.

  7. Atomic-scale properties of Ni-based FCC ternary, and quaternary alloys

    DOE PAGES

    Tamm, Artur; Aabloo, Alvo; Klintenberg, Mattias; ...

    2015-08-26

    The aim of our study is to characterize some atomic-scale properties of Ni-based FCC multicomponent alloys. For this purpose, we use Monte Carlo method combined with density functional theory calculations to study short-range order (SRO), atomic displacements, electronic density of states, and magnetic moments in equimolar ternary NiCrCo, and quaternary NiCrCoFe alloys. The salient features for the ternary alloy are a negative SRO parameter between Ni Cr and a positive between Cr Cr pairs as well as a weakly magnetic state. For the quaternary alloy we predict negative SRO parameter for Ni Cr and Ni Fe pairs and positive formore » Cr Cr and Fe Fe pairs. Atomic displacements for both ternary and quaternary alloys are negligible. In contrast to the ternary, the quaternary alloy shows a complex magnetic structure. The electronic structure of the ternary and quaternary alloys shows differences near the Fermi energy between a random solid solution and the predicted structure with SRO. Despite that, the calculated EXAFS spectra does not show enough contrast to discriminate between random and ordered structures. Finally, the predicted SRO has an impact on point-defect energetics, electron phonon coupling and thermodynamic functions and thus, SRO should not be neglected when studying properties of these two alloys.« less

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    PubMed

    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.

  11. Atomic-scale properties of Ni-based FCC ternary, and quaternary alloys

    SciTech Connect

    Tamm, Artur; Aabloo, Alvo; Klintenberg, Mattias; Stocks, Malcolm; Caro, Alfredo

    2015-08-26

    The aim of our study is to characterize some atomic-scale properties of Ni-based FCC multicomponent alloys. For this purpose, we use Monte Carlo method combined with density functional theory calculations to study short-range order (SRO), atomic displacements, electronic density of states, and magnetic moments in equimolar ternary NiCrCo, and quaternary NiCrCoFe alloys. The salient features for the ternary alloy are a negative SRO parameter between Ni Cr and a positive between Cr Cr pairs as well as a weakly magnetic state. For the quaternary alloy we predict negative SRO parameter for Ni Cr and Ni Fe pairs and positive for Cr Cr and Fe Fe pairs. Atomic displacements for both ternary and quaternary alloys are negligible. In contrast to the ternary, the quaternary alloy shows a complex magnetic structure. The electronic structure of the ternary and quaternary alloys shows differences near the Fermi energy between a random solid solution and the predicted structure with SRO. Despite that, the calculated EXAFS spectra does not show enough contrast to discriminate between random and ordered structures. Finally, the predicted SRO has an impact on point-defect energetics, electron phonon coupling and thermodynamic functions and thus, SRO should not be neglected when studying properties of these two alloys.

  12. Theoretical study of the Pb adsorption on Ni, Cr, Fe surfaces and on Ni based alloys

    NASA Astrophysics Data System (ADS)

    Bonnet, Marie-Laure; Costa, Dominique; Protopopoff, Elie; Marcus, Philippe

    2017-12-01

    Adsorption of Pb atoms on the Ni(111), Ni(100), Fe(110), and Cr(110) metallic surfaces was studied theoretically within an ab initio density functional theory approach (DFT). (√3 × √3)R30° super structures for Ni(111), and (2 × 2) for the other surfaces, corresponding to the saturation state, were considered. The preferred adsorption sites are found to be ternary sites for Ni(111), Fe(110), Cr(110) and quaternary sites for Ni(100). Adsorption on Fe and Cr is less exothermic than on Ni, by 0.16 and 0.33 eV/mol respectively. Adsorption on model surfaces of Ni based alloys was also investigated. It was found that the energy of adsorption depends mostly on the chemical composition of the ternary site, and can be described by a linear combination of the energies of adsorption on the pure metals. The nature of the second nearest neighbour of the adsorbed Pb atom has no significant influence on the adsorption energy. Average energies of adsorption were calculated in two cases: the limit of low coverage, and the saturation. The energies of adsorption of Pb at saturation on nickel base alloy surface representative of alloy 600 (Ni-15Cr-8Fe) and alloy 690 (Ni-30Cr-8Fe) were calculated to be 0.07 and 0.11 eV lower than on pure Ni respectively.

  13. Local Evolution of the Elastocaloric Effect in TiNi-Based Films

    NASA Astrophysics Data System (ADS)

    Ossmer, H.; Chluba, C.; Gueltig, M.; Quandt, E.; Kohl, M.

    2015-06-01

    Strain and temperature profiles of magnetron-sputtered ferroelastic TiNi-based films of 20 μm thickness are investigated during tensile load cycling with respect to strain, strain rate, and cycle number in order to assess their potential for elastocaloric cooling. Two different ferroelastic film specimens are considered, binary TiNi and quaternary TiNiCuCo films, which strongly differ regarding their phase transformation hysteresis and fatigue behavior. In situ digital image correlation and infrared thermography measurements reveal a correlated response of strain and temperature bands that is determined by mesoscale stress and temperature fields on the kinetics of phase transformation. In the case of binary TiNi films, this response is also strongly affected by cycling-induced fatigue causing vanishing band formation and decreasing elastocaloric effect size. In contrast, TiNiCuCo films show negligible fatigue and retain the local characteristics of the elastocaloric effect. Compared to TiNi films, they exhibit not only a reduced temperature change, but also a reduced work input for pseudoelastic cycling resulting in an improved material's coefficient of performance of 15.

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

    NASA Technical Reports Server (NTRS)

    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.

  15. Microstructure evolution and mechanical property of pulsed laser welded Ni-based superalloy

    NASA Astrophysics Data System (ADS)

    Ma, Guangyi; Wu, Dongjiang; Niu, Fangyong; Zou, Helin

    2015-09-01

    For evaluating the microstructure evolution and mechanical property of Ni-based Hastelloy C-276 weld joint by the pulsed laser welding, the influence of pulsed laser welding on the microstructure and mechanical property of the weld joint is investigated by the analysis of the microstructure morphology, microhardness, phase structure and tensile property. The results indicate that, in the fusion zone three sections are divided on the basis of the patterns of grain structures. In the weld joint, the element segregation is found, but the trend of brittle phase's formation is weakened. The weld microhardness presents just a little higher than that of base metal, and there is no obvious the softened heat affected zone. Meanwhile in the weld joint, the phase structure is still the face-center cubic with the tiny shift of peak positions and widened Full Width at Half-Maximum. The yield strength of weld joint is the same as that of base metal, and the tensile strength is nearly 90% of that of base metal. The decreased tensile strength is mainly attributed to the dislocation piling-up.

  16. Synthesis and Characterization of Neopentylaluminum Compounds.

    DTIC Science & Technology

    1987-08-05

    Mols, 0. ]lsley, W. H.; Oliver, J. P. Organometallics 1286, 1, 1812. 3. Lehmkuhl, H. Justus Liebigs Ann. Chem. 168, 719, 40. 4. Nyathl, J. Z.; Ressner...Manipulation of Air-Sensitive Compounds" John Wiley & Sons, New York, 1986, p 38. 10. Pfohl, W. Justus Liebigs Ann. Chem . 1260, 629, 207. 11. Hoffmann, E...G. Justus Liebigs Ann. Chem. 1260, 629, 104. 12. Malpass, D. B.; Watson, S. C. U. S. Patents 4,170,604 and 4,101,568. 13. Pitzer, K. S.; Gutowsky, H

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

    SciTech Connect

    Pindwal, Aradhana

    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.

  18. A new powerful association for immunoassay: organometallic label conjugated to solvent separation method.

    PubMed

    Mariet, F; Brossier, P

    1990-05-01

    The convenient use of solvents as a method to separate free (F) and bound (B) fractions in drug immunoassays which utilize organometallic moieties as labels, has been developed. Two types of drugs labelled with an organometallic complex and denominated metallohaptens (or metallotracers) are studied as model assays: desipramine (tricyclic antidepressant) and phenobarbital (antiepileptic agent). Different organic solvents have potentialities to extract these metallohaptens. To illustrate this solvent procedure we describe antiserum dilution curves and we compare the results with those obtained for the same samples using radiotracers in conjunction with dextran coated charcoal as separation agent. This immunoassay method which associates a metallotracer and B/F solvent separation appears to be fast, cheap, without the step of centrifugation.

  19. Antimicrobial Organometallic Dendrimers with Tunable Activity against Multidrug-Resistant Bacteria.

    PubMed

    Abd-El-Aziz, Alaa S; Agatemor, Christian; Etkin, Nola; Overy, David P; Lanteigne, Martin; McQuillan, Katherine; Kerr, Russell G

    2015-11-09

    Multidrug-resistant pathogens are an increasing threat to public health. In an effort to curb the virulence of these pathogens, new antimicrobial agents are sought. Here we report a new class of antimicrobial organometallic dendrimers with tunable activity against multidrug-resistant Gram-positive bacteria that included methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococcus faecium. Mechanistically, these redox-active, cationic organometallic dendrimers induced oxidative stress on bacteria and also disrupted the microbial cell membrane. The minimum inhibitory concentrations, which provide a quantitative measure of the antimicrobial activity of these dendrimers, were in the low micromolar range. AlamarBlue cell viability assay also confirms the antimicrobial activity of these dendrimers. Interestingly, these dendrimers were noncytotoxic to epidermal cell lines and to mammalian red blood cells, making them potential antimicrobial platforms for topical applications.

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

    PubMed

    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. (Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes)

    SciTech Connect

    Atwood, J.

    1990-01-01

    During the course of Grant ER13775 we have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. The spectrometer combined conventional stopped-flow techniques with an infrared optical system comprised of a carbon monoxide laser, an IRTRAN flow-through cell and a mercury-cadium-telluride detector. In this summary we will highlight our results on reactions: (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve additional of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions. 12 refs.

  2. Molecular Models of Ruthenium(II) Organometallic Complexes

    ERIC Educational Resources Information Center

    Coleman, William F.

    2007-01-01

    This article presents the featured molecules for the month of March, which appear in the paper by Ozerov, Fafard, and Hoffman, and which are related to the study of the reactions of a number of "piano stool" complexes of ruthenium(II). The synthesis of compound 2a offers students an alternative to the preparation of ferrocene if they are only…

  3. Molecular Models of Ruthenium(II) Organometallic Complexes

    ERIC Educational Resources Information Center

    Coleman, William F.

    2007-01-01

    This article presents the featured molecules for the month of March, which appear in the paper by Ozerov, Fafard, and Hoffman, and which are related to the study of the reactions of a number of "piano stool" complexes of ruthenium(II). The synthesis of compound 2a offers students an alternative to the preparation of ferrocene if they are only…

  4. Access to organometallic arylcobaltcorrins through radical synthesis: 4-ethylphenylcobalamin, a potential "antivitamin B(12)".

    PubMed

    Ruetz, Markus; Gherasim, Carmen; Gruber, Karl; Fedosov, Sergey; Banerjee, Ruma; Kräutler, Bernhard

    2013-02-25

    Locked B(12): 4-Ethylphenylcobalamin, a novel organometallic arylcobalamin, has been synthesized in a radical reaction. This vitamin B(12) antimetabolite features a strong Co-C bond, and represents a "locked" form of vitamin B(12) . It may be used in animal studies to induce functional vitamin B(12) deficiency artificially to help clarify still controversial issues related to the pathophysiology of vitamin B(12) deficiency.

  5. The solid-state synthesis of metal nanoparticles from organometallic precursors.

    PubMed

    Wostek-Wojciechowska, Dorota; Jeszka, Jeremiasz K; Amiens, Catherine; Chaudret, Bruno; Lecante, Pierre

    2005-07-01

    Nanoparticles (NPs), average size of 2-5 nm, of ruthenium, cobalt, and rhodium have been prepared by an original method, namely the solid-state decomposition under dihydrogen of an organometallic precursor either dispersed in polymer films or directly as nanocrystals. The NPs dispersion, size, and morphology are investigated by transmission electron microscopy, and their structure by wide angle X-ray scattering. Infrared spectroscopy, after adsorption of carbon monoxide on the metal NPs surfaces, evidences a nonoxidized surface of high reactivity.

  6. Peculiarities of the optical properties of organometallic perovskites with variable content of iodine and bromine

    NASA Astrophysics Data System (ADS)

    Sekerbayev, K. S.; Taurbayev, Ye. T.; Bazylenko, T. Yu.; Taurbayev, T. I.; Timoshenko, V. Yu.

    2017-05-01

    We have studied the optical properties of thin films of organometallic halide perovskites with variable content of iodine and bromine, which were obtained by two-stage deposition from solution. The results are indicative of an increased contribution of excitons to light absorption at the bandgap edge in bromine-containing perovskites as compared to the iodine-containing ones. The possibilities of using perovskites with preset halogen composition in cascade solar cells are discussed.

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

    PubMed

    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.

  8. Progress toward cascade cells made by OM-VPE. [organometallic vapor phase epitaxy

    NASA Technical Reports Server (NTRS)

    Borden, P. G.; Larue, R. A.; Ludowise, M. J.

    1982-01-01

    Organometallic Vapor Phase Epitaxy (COM-VPE) was used to make a sophisticated monolithic cascade cell, with a peak AMO efficiency of 16.6%, not corrected for 14% grid coverage. The cell has 9 epitaxial layers. The top cell is 1.35 microns thick with a 0.1 micron thich emitter. Both cells are heteroface n-p structures. The cascade cell uses metal interconnects. Details of growth and processing are described.

  9. Measuring grain boundary character distributions in Ni-base alloy 725 using high-energy diffraction microscopy

    DOE PAGES

    Bagri, Akbar; Hanson, John P.; Lind, J. P.; ...

    2016-10-25

    We use high-energy X-ray diffraction microscopy (HEDM) to characterize the microstructure of Ni-base alloy 725. HEDM is a non-destructive technique capable of providing three-dimensional reconstructions of grain shapes and orientations in polycrystals. The present analysis yields the grain size distribution in alloy 725 as well as the grain boundary character distribution (GBCD) as a function of lattice misorientation and boundary plane normal orientation. We find that the GBCD of Ni-base alloy 725 is similar to that previously determined in pure Ni and other fcc-base metals. We find an elevated density of Σ9 and Σ3 grain boundaries. We also observe amore » preponderance of grain boundaries along low-index planes, with those along (1 1 1) planes being the most common, even after Σ3 twins have been excluded from the analysis.« less

  10. Measuring Grain Boundary Character Distributions in Ni-Base Alloy 725 Using High-Energy Diffraction Microscopy

    NASA Astrophysics Data System (ADS)

    Bagri, Akbar; Hanson, John P.; Lind, Jonathan; Kenesei, Peter; Suter, Robert M.; Gradečak, Silvija; Demkowicz, Michael J.

    2017-01-01

    We use high-energy X-ray diffraction microscopy (HEDM) to characterize the microstructure of Ni-base alloy 725. HEDM is a non-destructive technique capable of providing three-dimensional reconstructions of grain shapes and orientations in polycrystals. The present analysis yields the grain size distribution in alloy 725 as well as the grain boundary character distribution (GBCD) as a function of lattice misorientation and boundary plane normal orientation. We find that the GBCD of Ni-base alloy 725 is similar to that previously determined in pure Ni and other fcc-base metals. We find an elevated density of Σ9 and Σ3 grain boundaries. We also observe a preponderance of grain boundaries along low-index planes, with those along (1 1 1) planes being the most common, even after Σ3 twins have been excluded from the analysis.

  11. Measuring grain boundary character distributions in Ni-base alloy 725 using high-energy diffraction microscopy

    SciTech Connect

    Bagri, Akbar; Hanson, John P.; Lind, J. P.; Kenesei, Peter; Suter, Robert; Gradecak, Silvija; Demkowicz, Michael J.

    2016-10-25

    We use high-energy X-ray diffraction microscopy (HEDM) to characterize the microstructure of Ni-base alloy 725. HEDM is a non-destructive technique capable of providing three-dimensional reconstructions of grain shapes and orientations in polycrystals. The present analysis yields the grain size distribution in alloy 725 as well as the grain boundary character distribution (GBCD) as a function of lattice misorientation and boundary plane normal orientation. We find that the GBCD of Ni-base alloy 725 is similar to that previously determined in pure Ni and other fcc-base metals. We find an elevated density of Σ9 and Σ3 grain boundaries. We also observe a preponderance of grain boundaries along low-index planes, with those along (1 1 1) planes being the most common, even after Σ3 twins have been excluded from the analysis.

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

    NASA Astrophysics Data System (ADS)

    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.

  13. Synthesis of Some "Cobaloxime" Derivatives: A Demonstration of "Umpolung" in the Reactivity of an Organometallic Complex

    NASA Astrophysics Data System (ADS)

    Jameson, Donald L.; Grzybowski, Joseph J.; Hammels, Deb E.; Castellano, Ronald K.; Hoke, Molly E.; Freed, Kimberly; Basquill, Sean; Mendel, Angela; Shoemaker, William J.

    1998-04-01

    This article describes a four-reaction sequence for the synthesis of two organometallic "cobaloxime" derivatives. The concept of "Umpolung" or reversal of reactivity is demonstrated in the preparation of complexes. The complex Co(dmgH)2(4-t-BuPy)Et is formed by the reaction of a cobalt (I) intermediate (cobalt in the role of nucleophile) with ethyl iodide. The complex Co(dmgH)2(4-t-BuPy)Ph is formed by the reaction of PhMgBr with a cobalt (III) intermediate (cobalt in the role of electrophile). All the products contain cobalt in the diamagnetic +3 oxidation state and are readily characterized by proton and carbon NMR. The four reaction sequence may be completed in two 4-hour lab periods. Cobaloximes are well known as model complexes for Vitamin B-12 and the experiment exposes students to aspects of classical coordination chemistry, organometallic chemistry and bioinorganic chemistry. The experiment also illustrates an important reactivity parallel between organic and organometallic chemistry.

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

    SciTech Connect

    Cahoon, James Francis

    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.

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

    SciTech Connect

    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.

  16. Gamma prime precipitation mechanisms and solute partitioning in Ni-base alloys

    NASA Astrophysics Data System (ADS)

    Rojhirunsakool, Tanaporn

    Nickel-base superalloys have been emerged as materials for gas turbines used for jet propulsion and electricity generation. The strength of the superalloys depends mainly from an ordered precipitates of L12 structure, so called gamma prime (gamma') dispersed within the disorder gamma matrix. The Ni-base alloys investigated in this dissertation comprise both model alloy systems based on Ni-Al-Cr and Ni-Al-Co as well as the commercial alloy Rene N5. Classical nucleation and growth mechanism dominates the gamma' precipitation process in slowed-cooled Ni-Al-Cr alloys. The effect of Al and Cr additions on gamma' precipitate size distribution as well as morphological and compositional development of gamma' precipitates were characterized by coupling transmission electron microscopy (TEM) and 3D atom probe (3DAP) techniques. Rapid quenching Ni-Al-Cr alloy experiences a non-classical precipitation mechanism. Structural evolution of the gamma' precipitates formed and subsequent isothermal annealing at 600 °C were investigated by coupling TEM and synchrotron-based high-energy xray diffraction (XRD). Compositional evolution of the non-classically formed gamma' precipitates was determined by 3DAP and Langer, Bar-on and Miller (LBM) method. Besides homogeneous nucleation, the mechanism of heterogeneous gamma' precipitation involving a discontinuous precipitation mechanism, as a function of temperature, was the primary focus of study in case of the Ni-Al-Co alloy. This investigation coupled SEM, SEM-EBSD, TEM and 3DAP techniques. Lastly, solute partitioning and enrichment of minor refractory elements across/at the gamma/ gamma' interfaces in the commercially used single crystal Rene N5 superalloy was investigated by using an advantage of nano-scale composition investigation of 3DAP technique.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

    Liang, Cai; Gooneratne, Chinthaka P.; Wang, Qing Xiao; Liu, Yang; Gianchandani, Yogesh; Kosel, Jurgen

    2014-01-01

    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. PMID:25587418

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

    PubMed

    Liang, Cai; Gooneratne, Chinthaka P; Wang, Qing Xiao; Liu, Yang; Gianchandani, Yogesh; Kosel, Jurgen

    2014-09-01

    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.

  20. Electron phonon coupling in Ni-based binary alloys with application to displacement cascade modeling

    SciTech Connect

    Samolyuk, German D.; Stocks, George Malcolm; Stoller, Roger E.

    2016-04-01

    Energy transfer between lattice atoms and electrons is an important channel of energy dissipation during displacement cascade evolution in irradiated materials. On the assumption of small atomic displacements, the intensity of this transfer is controlled by the strength of electron–phonon (el–ph) coupling. The el–ph coupling in concentrated Ni-based alloys was calculated using electronic structure results obtained within the coherent potential approximation. It was found that Ni0.5Fe0.5, Ni0.5Co0.5 and Ni0.5Pd0.5 are ordered ferromagnetically, whereas Ni0.5Cr0.5 is nonmagnetic. Since the magnetism in these alloys has a Stoner-type origin, the magnetic ordering is accompanied by a decrease of electronic density of states at the Fermi level, which in turn reduces the el–ph coupling. Thus, the el–ph coupling values for all alloys are approximately 50% smaller in the magnetic state than for the same alloy in a nonmagnetic state. As the temperature increases, the calculated coupling initially increases. After passing the Curie temperature, the coupling decreases. The rate of decrease is controlled by the shape of the density of states above the Fermi level. Introducing a two-temperature model based on these parameters in 10 keV molecular dynamics cascade simulation increases defect production by 10–20% in the alloys under consideration.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Enhancing Sulfur Tolerance of Ni-Based Cermet Anodes of Solid Oxide Fuel Cells by Ytterbium-Doped Barium Cerate Infiltration.

    PubMed

    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.

  4. Investigation of porous Ni-based metal-organic frameworks containing paddle-wheel type inorganic building units via high-throughput methods.

    PubMed

    Maniam, Palanikumar; Stock, Norbert

    2011-06-06

    In the search of Ni based metal-organic frameworks (MOFs) containing paddle-wheel type building units, three chemical systems Ni(2+)/H(n)L/base/solvent with H(n)L = H(3)BTC (1,3,5-benzenetricarboxylic acid), H(3)BTB (4,4',4'',-benzene-1,3,5-triyl-tris(benzoic acid)), and H(2)BDC (terephthalic acid) were investigated using high-throughput (HT) methods. In addition to the conventional heating, for the first time HT microwave assisted synthesis of MOFs was carried out. Six new compounds were discovered, and their fields of formation were established. In the first system, H(3)BTC was employed and a comprehensive HT-screening of compositional and process parameters was conducted. The synthesis condition for the Ni paddle-wheel unit was determined and two compounds [Ni(3)(BTC)(2)(Me(2)NH)(3)]·(DMF)(4)(H(2)O)(4) (1a) and [Ni(6)(BTC)(2)(DMF)(6)(HCOO)(6)] (1b) were discovered (Me(2)NH = dimethylamine, DMF = dimethylformamide). In the second system, the use of the extended tritopic linker H(3)BTB and the synthesis conditions for the paddle-wheel units led to the porous MOF, [Ni(3)(BTB)(2)(2-MeIm)(1.5)(H(2)O)(1.5)]·(DMF)(9)(H(2)O)(6.5) (2), (2-MeIm = 2-methylimidazole). This compound shows a selective adsorption of H(2)O and H(2) with a strong hysteresis. In the third system, H(2)BDC was used, and the base (DABCO) was incorporated as a bridging ligand into all structures. Thus, two pillared layered porous MOFs [Ni(2)(BDC)(2)(DABCO)]·(DMF)(4)(H(2)O)(1.5) (3a) and [Ni(2)(BDC)(2)(DABCO)]·(DMF)(4)(H(2)O)(4) (3b) as well as a layered compound [Ni(BDC)(DABCO)]·(DMF)(1.5)(H(2)O)(2) (3c) were isolated. The 3a and 3b polymorphs of the [Ni(2)(BDC)(2)(DABCO)] framework can be selectively synthesized. The combination of microwave assisted heating, low overall concentration, stirring of the reaction mixtures, and an excess of DABCO yields a highly crystalline pure phase of 3b. The fields of formation of all compounds were established, and scale-up was successfully performed for 1b, 2

  5. Microstructure and corrosion resistance of Ni-based alloy laser coatings with nanosize CeO2 addition.

    PubMed

    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.

  6. Microstructure and corrosion resistance of Ni-based alloy laser coatings with nanosize CeO2 addition

    PubMed Central

    Hong Zhang, Shi; Xi Li, Ming; Hong Yoon, Jae; Yul Cho, Tong; Zhu He, Yi; Gyu Lee, Chan

    2008-01-01

    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. PMID:27877999

  7. Microstructure and corrosion resistance of Ni-based alloy laser coatings with nanosize CeO2 addition

    NASA Astrophysics Data System (ADS)

    Zhang, Shi Hong; Li, Ming Xi; Yoon, Jae Hong; Cho, Tong Yul; Zhu He, Yi; Lee, Chan Gyu

    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, 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.

  8. Room temperature synthesis of Ni-based alloy nanoparticles by radiolysis.

    SciTech Connect

    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

  9. MICROSTRUCTURE OF LONG-TERM AGED IN617 NI-BASE SUPERALLOY

    SciTech Connect

    Wu, Quanyan; Shingledecker, John P; Vasudevan, Vijay; Swindeman, Robert W

    2008-01-01

    The microstructure of the Ni-base superalloy IN617 that had undergone prolonged aging (approximately 65,000 hours) at a series of temperatures from 482 C to 871 C has been characterized by microhardness measurements, optical microscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Cr23C6, Mo-rich eta-M6C, and Ti(C,N) constitute the major primary coarse precipitates both within the grains and along the grain boundaries. The secondary carbides were mostly fine Cr23C6, which had a cube-on-cube orientation relationship (OR) with the fcc matrix, and at long times were present in cuboidal and plate-shape forms within the grains and as films along the grain boundaries. Fine, eta-M6C carbides were also observed at low to intermediate temperatures with an OR given by [011] carbide//[011] matrix, carbide// matrix. The coarse eta-M6C carbides increased in extent at 871 C, whereas the counterpart fine carbides were absent. The phase was found to be present at all aging temperatures up to 871 C, with a volume fraction ranging from very low to approximately 5 pct at 593 C, where the peak in microhardness occurs. The observations have also suggested that the presence of a very small amount of at temperatures as high as 871 C at long times may be associated with a reaction between the fine eta-carbides and the matrix. Ultrafine precipitates of the intermetallic phase Ni2(Cr,Mo) with the Pt2Mo-type structure was observed in addition to in samples aged for 28,300 hours at the lowest aging temperature of 482 C. These precipitates were absent in samples aged at higher temperatures. The various observations made have suggested that the long-term thermal stability of the IN617 alloy is reasonably good over a wide temperature range of 538 C to 704 C, whereas at higher temperatures (871 C), the substantial decrease in the volume fraction of and coarsening and clustering of the carbides lead to a large drop in the microhardness. A modified time

  10. Subpicosecond reverse saturable absorption in organic and organometallic solutions

    NASA Astrophysics Data System (ADS)

    Pittman, M.; Plaza, P.; Martin, M. M.; Meyer, Y. H.

    1998-12-01

    Solutions of several carbocyanines, phthalocyanines and naphthalocyanines were studied by time-resolved transient spectroscopy with subpicosecond white-light continuum. The excited-state absorption cross-sections of all compounds were determined from the differential spectra obtained at short delay time after excitation, by a global spectral analysis. All these molecules exhibit an excited-state absorption cross-section higher than that of the ground state at 610 nm. This spectral property gives rise to a reverse saturable absorption (RSA) effect under high laser fluences at this wavelength. Nonlinear transmission of these molecules was measured under increasing laser fluences. A three-level molecular model was used to simulate the measured nonlinear transmission and the best fits were obtained with molecular parameters in good agreement with those deduced from the analysis of the transient spectra. The use of RSA for the energy stabilization of ultrashort laser pulses was demonstrated, and a stabilization coefficient was defined as an efficient tool for characterizing nonlinear behavior of such compounds.

  11. Organometallic rotaxane dendrimers with fourth-generation mechanically interlocked branches

    PubMed Central

    Wang, Wei; Chen, Li-Jun; Wang, Xu-Qing; Sun, Bin; Li, Xiaopeng; Zhang, Yanyan; Shi, Jiameng; Yu, Yihua; Zhang, Li; Liu, Minghua; Yang, Hai-Bo

    2015-01-01

    Mechanically interlocked molecules, such as catenanes, rotaxanes, and knots, have applications in information storage, switching devices, and chemical catalysis. Rotaxanes are dumbbell-shaped molecules that are threaded through a large ring, and the relative motion of the two components along each other can respond to external stimuli. Multiple rotaxane units can amplify responsiveness, and repetitively branched molecules—dendrimers—can serve as vehicles for assembly of many rotaxanes on single, monodisperse compounds. Here, we report the synthesis of higher-generation rotaxane dendrimers by a divergent approach. Linkages were introduced as spacer elements to reduce crowding and to facilitate rotaxane motion, even at the congested periphery of the compounds up to the fourth generation. The structures were characterized by 1D multinuclear (1H, 13C, and 31P) and 2D NMR spectroscopy, MALDI-TOF-MS, gel permeation chromatography (GPC), and microscopy-based methods including atomic force microscopy (AFM) and transmission electron microscopy (TEM). AFM and TEM studies of rotaxane dendrimers vs. model dendrimers show that the rotaxane units enhance the rigidity and reduce the tendency of these assemblies to collapse by self-folding. Surface functionalization of the dendrimers with ferrocenes as termini produced electrochemically active assemblies. The preparation of dendrimers with a well-defined topological structure, enhanced rigidity, and diverse functional groups opens previously unidentified avenues for the application of these materials in molecular electronics and materials science. PMID:25902491

  12. An Advanced Organometallic Lab Experiment with Biological Implications: Synthesis and Characterization of Fe[subscript 2](µ-S[subscript 2])(C0)[subscript 6

    ERIC Educational Resources Information Center

    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…

  13. An Advanced Organometallic Lab Experiment with Biological Implications: Synthesis and Characterization of Fe[subscript 2](µ-S[subscript 2])(C0)[subscript 6

    ERIC Educational Resources Information Center

    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

    NASA Astrophysics Data System (ADS)

    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

    NASA Astrophysics Data System (ADS)

    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. Using effective group potential methodology for predicting organometallic complex properties.

    PubMed

    Alary, Fabienne; Heully, Jean-Louis; Poteau, Romuald; Maron, Laurent; Trinquier, Georges; Daudey, Jean-Pierre

    2003-09-10

    Using the Effective Group Potentials (EGP) method, optimal geometries, harmonic vibrational frequencies, and relative energies of different sets of metal complexes are calculated. All of the systems under consideration contain the cyclopentadienyl (Cp) ligand. They are as follows: (i). Group V metal Atom complexes showing one Cp ligand, (ii). a tetrameric Al-Cp compound with four Cp ligands, (iii). homometallic lutetium hydrides containing six cyclopentadienyl rings. Various electron correlation treatments have been carried out. All of the results compare very satisfactorily with available experimental data and with all-electron ab initio calculations performed for this work or published in the literature. Furthermore, the performance of the EGP method was tested on a rather large complex for which experimental evidence exists, but no all-electron calculation has been reported so far.

  17. Half-sandwich iridium- and rhodium-based organometallic architectures: rational design, synthesis, characterization, and applications.

    PubMed

    Han, Ying-Feng; Jin, Guo-Xin

    2014-12-16

    CONSPECTUS: Over the last two decades, researchers have focused on the design and synthesis of supramolecular coordination complexes, which contain discrete functional structures with particular shapes and sizes, and are similar to classic metal-organic frameworks. Chemists can regulate many of these systems by judiciously choosing the metal centers and their adjoining ligands. These resulting complexes have unusual properties and therefore many applications, including molecular recognition, supramolecular catalysis, and some applications as nanomaterials. In addition, researchers have extensively developed synthetic methodologies for the construction of discrete self-assemblies. One of the most important challenges for scientists in this area is to be able to synthesize target structures that can be controlled in both length and width. For this reason, it is important that we understand the factors leading to special shapes and sizes of such architectures, especially how starting building blocks and functional ligands affect the final conformations and cavity sizes of the resulting assemblies. Towards this goal, we have developed a wide range of different organometallic architectures by rationally designing metal-containing precursors and organic ligands. In this Account, we present our recent work, focusing on half-sandwich iridium- and rhodium-based organometallic assemblies that we obtained through rational design. We discuss their synthesis, structures, and applications for the encapsulation of guests and enzyme-mimicking catalysis. We first describe a series of self-assembled organometallic metallarectangles and metallacages, which we constructed from preorganized dinuclear half-sandwich molecular clips and suitable pyridyl ligands. We extended this strategy to tune the size of the obtained rectangles, creating large cavities by introduction of larger molecular clips. The cavity was found to exhibit selective and reversible CH2Cl2 adsorption properties while

  18. A comparative study of quantitative microsegregation analyses performed during the solidification of the Ni-base superalloy CMSX-10

    SciTech Connect

    Seo, Seong-Moon; Jeong, Hi-Won; Ahn, Young-Keun; Yun, Dae Won; Lee, Je-Hyun; Yoo, Young-Soo

    2014-03-01

    Quantitative microsegregation analyses were systematically carried out during the solidification of the Ni-base superalloy CMSX-10 to clarify the methodological effect on the quantification of microsegregation and to fully understand the solidification microstructure. Three experimental techniques, namely, mushy zone quenching (MZQ), planar directional solidification followed by quenching (PDSQ), and random sampling (RS), were implemented for the analysis of microsegregation tendency and the magnitude of solute elements by electron probe microanalysis. The microprobe data and the calculation results of the diffusion field ahead of the solid/liquid (S/L) interface of PDSQ samples revealed that the liquid composition at the S/L interface is significantly influenced by quenching. By applying the PDSQ technique, it was also found that the partition coefficients of all solute elements do not change appreciably during the solidification of primary γ. All three techniques could reasonably predict the segregation behavior of most solute elements. Nevertheless, the RS approach has a tendency to overestimate the magnitude of segregation for most solute elements when compared to the MZQ and PDSQ techniques. Moreover, the segregation direction of Cr and Mo predicted by the RS approach was found to be opposite from the results obtained by the MZQ and PDSQ techniques. This conflicting segregation behavior of Cr and Mo was discussed intensively. It was shown that the formation of Cr-rich areas near the γ/γ′ eutectic in various Ni-base superalloys, including the CMSX-10 alloy, could be successfully explained by the results of microprobe analysis performed on a sample quenched during the planar directional solidification of γ/γ′ eutectic. - Highlights: • Methodological effect on the quantification of microsegregation was clarified. • The liquid composition at the S/L interface was influenced by quenching. • The segregation direction of Cr varied depending on the

  19. Research into oil-based high-dispersion graphite lubricants for extrusion of Ni-based alloys

    NASA Astrophysics Data System (ADS)

    Petrov, Alexander N.; Petrov, Mikhail A.; Petrov, Pavel A.

    2016-10-01

    The presented paper deals with oil-based high-dispersion graphite lubricants for hot extrusion Ni-based alloys. This paper emphasize an influence of the lubricant's flash point and oil burning on composition changing of the lubricants. It was found out that oil-based lubricants increase heat shielding properties of the die during extrusion. The temperature of a die surface was estimated on the base of production tests on the mechanical press with nominal force of 1,6MN. The practical recommendations were presented and should help to choose lubricants properly in accordance to the analysis.

  20. Comparative thermal stability characteristics and isothermal oxidation behavior of an aluminized and a Pt-aluminized Ni-base superalloy

    SciTech Connect

    Tawancy, H.M.; Sridhar, N.; Abbas, N.M.; Rickerby, D.

    1995-11-01

    It is the objective of this paper to compare the thermal stability characteristics and isothermal oxidation behavior of an aluminide coating and a Pt-aluminide coating of the same Al content on a Ni-base superalloy. Addition of Pt to an aluminide coating was found to improve its thermal stability as well as its capability for selective oxidation of Al resulting in a purer scale of slower growth rate. This was correlated with the greater diffusional stability of the Pt-aluminide coating restricting the transport of substrate elements into the outer coating layers.

  1. Quantum transport behavior of Ni-based dinuclear complexes in presence of zigzag graphene nanoribbon as electrode

    NASA Astrophysics Data System (ADS)

    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.

  2. Microstructure and Abrasive-wear Behavior Under High Temperature of Laser Clad Ni-based WC Ceramic Coating

    NASA Astrophysics Data System (ADS)

    Wang, X. H.; Liu, A. M.

    The laser cladding is used on the surface of 4Cr14Ni14NW2Mo heat-resisting steel, Ni-based WC coating can be formed. Observing and analying the microstructure, measuring the hardness of the cladding layer cross section, checking the abrsrssive- wear under high temperature in different temperature. The results showed that the microstructure of Ni21+20%Wc+0.5%CeO2 cladding layer is small and it presents the best abrasive-wear behavior under high temperature in these investigated coatings. Wear mechanism of the laser cladding layer changes with temperature changes.

  3. The Mean vs Life-Limiting Fatigue Response of a Ni-Base Superalloy, Part 1: Mechanisms (Preprint)

    DTIC Science & Technology

    2008-09-01

    34’"L’\\" ~~·~~~:~~~?~i.. ~ ~I~~~.~.’ ,~.- .":_~ ••-:;’~.:-- 10JJITl 3 4 S 6 Grain diameter (",m) Figure 1: Microstructure of the INIOO...DATES COVERED (From - To) September 2008 Journal Article Preprint 4 . TITLE AND SUBTITLE THE MEAN VS LIFE-LIMITING FATIGUE RESPONSE OF A Ni-BASE...SUPERALLOY, PART 1: MECHANISMS (PREPRINT) 5a. CONTRACT NUMBER In-house 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 62102F 6 . AUTHOR(S

  4. Observation of Localized Corrosion of Ni-Based Alloys Using Coupled Orientation Imaging Microscopy and Atomic Force Microscopy

    SciTech Connect

    Bedrossian, P.J.

    1999-11-24

    We present a method for assessing the relative vulnerabilities of distinct classes of grain boundaries to localized corrosion. Orientation imaging microscopy provides a spatial map which identifies and classifies grain boundaries at a metal surface. Once the microstructure of a region of a sample surface has been characterized, a sample can be exposed to repeated cycles of exposure to a corrosive environment alternating with topographic measurement by an atomic force microscope in the same region in which the microstructure had been mapped. When this procedure is applied to Ni and Ni-based alloys, we observe enhanced attack at random grain boundaries relative to special boundaries and twins in a variety of environments.

  5. Shape-Controlled Synthesis of Ni-Based Nanoparticles and Patterning for Carbon Nanofiber Growth

    NASA Astrophysics Data System (ADS)

    Sarac, Mehmet Fahri

    nickel phosphide were investigated. Ni3C1-x NPs were synthesized through thermolysis of nickel acetylacetonate, with oleylamine as a reducing agent and 1-octadecene (ODE) as the solvent. Trioctylephosphine (TOP) was added as ligand and inhibited the formation of dendritic shapes, as well as inhibiting the incorporation of carbon. This was found to create Ni NPs which were spherical, while comparable findings have been observed from the use of octadecane (ODA) and trioctylphosphine oxide (TOPO) as solvents, but these have been observed to have fewer, larger branches than when using ODE, while producing Ni rather than Ni3C 1-x NPs at 230 °C. Incorporating carbon from TOPO or ODA in Ni NPs required higher temperatures, while conversion of the dendritic NPs through this approach led to several voids in branches (rather than larger single voids for the spherical NPs). These studies have generated important knowledge about the synthesis of Ni-based NPs and of their catalysis of VACNF growth. We have shown that ligands encapsulating Ni NPs have a critical role in preventing the NPs from agglomerating during the growth of VACNFs, giving a monodisperse VACNF diameter distribution. The ligands were converted into protective graphitic shells, but if the ligands are intentionally removed after deposition onto the substrate but before initiating VACNF growth, then a polydisperse VACNF diameter distribution are obtained, with a larger average diameter. We have also demonstrated VACNF growth on several metal substrates, where addition of Si micropowder allows the growth of Si-enriched coatings that make the VACNFs mechanically rigid. Recommendations for ongoing research include investigating the conversion chemistry of Ni NPs into nickel chalcogenides or other transition bimetallic NPs and to explore application for nanomaterials in catalysis, plasmonics, electronics, and medicine.

  6. Selective growth of GaAs by organometallic vapor phase epitaxy at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    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.

  7. Supported organometallic complexes, surface chemistry, spectroscopy, and catalysis. Progress report, September 15, 1992--November 14, 1993

    SciTech Connect

    Marks, T.J.

    1993-04-01

    Goal 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. Nature of adsorbed species is probed by a battery of chemical and physicochemical techniques, to understand the nature of the molecule-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. Modular self-assembly, characterization, and host-guest chemistry of nanoscale organometallic architectures

    SciTech Connect

    Manna, J.; Kuehl, C.J.; Stang, P.J.; Muddiman, D.C.; Smith, R.D.

    1997-12-31

    The supramolecular synthesis and chemistry of organic macrocycles has been the focus of considerable study for over thirty years. In contrast, the chemistry of analogous inorganic and organometallic macrocycles is in it infancy; little is know about the stability, spectroscopic and physical properties, and chemistry of these species. We will report on the design of several unique supramolecular macrocycles and the characterization of these species by a range of spectroscopic techniques, including electrospray-ionization Fourier transform ion cyclotron resonance spectrometry. Preliminary data concerning the host-guest chemistry of these macrocycles will also be presented.

  9. Combined quantum mechanical/molecular mechanics modeling for large organometallic and metallobiochemical systems

    NASA Astrophysics Data System (ADS)

    Leong, Max Kangchien

    A method of combined quantum mechanics/molecular mechanics has been developed to model larger organometallic and metallobiochemical systems where neither quantum mechanics nor molecular mechanics, applied separately, can solve the problem. An electronically transparent interface, which allows charge transfers between the quantum and classical fragments, is devised and realized by employing a special iterative procedure of double (intrafragment and interfragment) self-consistent calculations. The combined QM/MM scheme was successfully applied to model iron picket-fence porphyrin, vitamin B12, aquocobalamin, and vitamin B12 coenzyme molecules.

  10. 2001 Gordon Research Conference on Organometallic Chemistry. Final progress report [agenda and attendee list

    SciTech Connect

    Burns, Carol

    2001-07-27

    The Gordon Research Conference on Organometallic Chemistry was held at Salve Regina University, Newport, Rhode Island, July 22-27, 2001. The conference had 133 participants. The attendees represented the spectrum of endeavor in this field, coming from academia, industry, and government laboratories, and included US and foreign scientists, senior researchers, young investigators, and students. Emphasis was place on current unpublished research and discussion of the future target areas in this field. There was a conscious effort to stimulate lively discussion about the key issues in the field today. Time for formal presentations was limited in the interest of group discussions; poster sessions were held.

  11. Simulation and testing of a vertical organometallic vapor phase epitaxy reactor

    NASA Astrophysics Data System (ADS)

    Sani, R. A.; Barmawi, M.; Mindara, J. Y.

    1998-02-01

    The purpose of the study is to design a single wafer vertical organo-metallic vapor phase epitaxy (OMVPE) reactor which gives a uniform deposition around the symmetry axis. The vertical reactor under the consideration consist of a diffuser and a system of coaxial cylinders to laminarize the flow which may lead to a uniform deposition without rotating the susceptor. The simulation shows that for a susceptor with a radius of 2.5 cm, a uniformity can be achieved in a region of a radius of 2 cm within 1% for certain operating condition. The result is compared with the experimental measurement of TiO2 deposition from TTIP.

  12. Luminescent Cyclometalated Platinum Complexes with π-Bonded Catecholate Organometallic Ligands.

    PubMed

    Moussa, Jamal; Loch, Aruny; Chamoreau, Lise-Marie; Degli Esposti, Alessandra; Bandini, Elisa; Barbieri, Andrea; Amouri, Hani

    2017-02-20

    A series of cyclometalated platinum(II) complexes of the type [(ppy)Pt(LM)](n+) (n = 0, 1) with π-bonded catecholates acting as organometallic ligands (LM) have been prepared and characterized by analytical techniques. In addition, the structures of two complexes of the series were determined by single-crystal X-ray diffraction. The packing shows the formation of a 1D supramolecular assembly generated by dPt-πCp* interactions among individual units. All complexes are luminescent in the solid state and in solution media. The results of photophysics have been rationalized by means of density functional theory (DFT) and time-dependent DFT investigations.

  13. Exploration geochemical technique for the determination of preconcentrated organometallic halides by ICP-AES

    USGS Publications Warehouse

    Motooka, J.M.

    1988-01-01

    An atomic absorption extraction technique which is widely used in geochemical exploration for the determination of Ag, As, Au, Bi, Cd, Cu, Mo, Pb, Sb, and Zn has been modified and adapted to a simultaneous inductively coupled plasma-atomic emission instrument. the experimental and operating parameters are described for the preconcentration of the metals into their organometallic halides and for the determination of the metals. Lower limits of determination are equal to or improved over those for flame atomic absorption (except Au) and ICP results are very similar to the accepted AA values, with precision for the ICP data in excess of that necessary for exploration purposes.

  14. Investigation of fragmentation processes following core photoionization of organometallic molecules in the vapor phase

    NASA Astrophysics Data System (ADS)

    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.

  15. Organometallic synthesis, reactivity and catalysis in the solid state using well-defined single-site species

    PubMed Central

    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/catalysis and single-crystal-to-single-crystal transformations. PMID:25666064

  16. Phenylethynylcobalamin: a light-stable and thermolysis-resistant organometallic vitamin B(12) derivative prepared by radical synthesis.

    PubMed

    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.

  17. Organometallic NLO Polymers. 3. Copolymerization of Bridged Bis(ferrocenyl) and Bis(cyanoacetate) Monomers Via the Knoevenagel Condensation

    DTIC Science & Technology

    1992-05-10

    Organometallics 1990,9, 853. (b) Wright, M. E.; Toplikar, F_. G. in "Advances in New Materials , Contemporary Topics in Polymer Sicence ,", Salamone, J. C., Riffle...Lindsay and coworkers recently presented the synthesis of a new class of main-chain organic NLO polymers.4 For this new class of NLO materials the polymer...backbone will be aligned into a accordion shape.5 To date, this approach has not been used in the area of organometallic polymeric NLO materials .6

  18. (Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report)

    SciTech Connect

    Atwood, J.

    1990-01-01

    We have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. In this summary we highlight our results on reactions (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve addition of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions.

  19. [Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report

    SciTech Connect

    Atwood, J.

    1990-12-31

    We have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. In this summary we highlight our results on reactions (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve addition of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions.

  20. 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.

    PubMed

    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.

  1. Effects of a High Magnetic Field on the Microstructure of Ni-Based Single-Crystal Superalloys During Directional Solidification

    NASA Astrophysics Data System (ADS)

    Xuan, Weidong; Lan, Jian; Liu, Huan; Li, Chuanjun; Wang, Jiang; Ren, Weili; Zhong, Yunbo; Li, Xi; Ren, Zhongming

    2017-08-01

    High magnetic fields are widely used to improve the microstructure and properties of materials during the solidification process. During the preparation of single-crystal turbine blades, the microstructure of the superalloy is the main factor that determines its mechanical properties. In this work, the effects of a high magnetic field on the microstructure of Ni-based single-crystal superalloys PWA1483 and CMSX-4 during directional solidification were investigated experimentally. The results showed that the magnetic field modified the primary dendrite arm spacing, γ' phase size, and microsegregation of the superalloys. In addition, the size and volume fractions of γ/ γ' eutectic and the microporosity were decreased in a high magnetic field. Analysis of variance (ANOVA) results showed that the effect of a high magnetic field on the microstructure during directional solidification was significant ( p < 0.05). Based on both experimental results and theoretical analysis, the modification of microstructure was attributed to thermoelectric magnetic convection occurring in the interdendritic regions under a high magnetic field. The present work provides a new method to optimize the microstructure of Ni-based single-crystal superalloy blades by applying a high magnetic field.

  2. Microstructure chemistry and mechanical properties of Ni-based superalloy Rene N4 under irradiation at room temperature

    SciTech Connect

    Sun, C.; Kirk, M.; Li, M.; Hattar, Khalid Mikhiel; Wang, Y.; Anderoglu, O.; Valdez, J.; Uberuaga, B. P.; Dickerson, R.; Maloy, S. A.

    2015-06-14

    Nickel superalloys with cubic L12 structured γ' (Ni3(Al, Ti)) precipitates exhibit high strength at high temperatures and excellent corrosion resistance when exposed to water. Unlike prior studies on irradiation damage of other Ni-based superalloys, our study on Rene N4 involves much larger γ' precipitates, ~450 nm in size, a size regime where the irradiation-induced disordering and dissolution kinetics and the corresponding mechanical property evolution are unknown. Under heavy ion irradiation at room temperature, the submicron-sized γ' precipitates were fully disordered at ~0.3 dpa and only later partially dissolved after 75 dpa irradiation. Nanoindentation experiments indicate that the mechanical properties of the alloy change significantly, with a dramatic decrease in hardness, with irradiation dose. Three contributions to the change in hardness were examined: defect clusters, disordering and dissolution. Moreover, the generation of defect clusters in the matrix and precipitates slightly increased the indentation hardness, while disordering of the submicron-sized γ' precipitates resulted in a dramatic decrease in the total hardness, which decreased further during the early stages of the intermixing between γ' precipitates and matrix (<18 dpa). As a result, controlling the long-range-ordering and chemical intermixing can be used to tailor the mechanical properties of Ni-based superalloys under irradiation.

  3. Assessing the Effects of Radiation Damage on Ni-base Alloys for the Prometheus Space Reactor System

    SciTech Connect

    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.

  4. Statistical study of ductility-dip cracking induced plastic deformation in polycrystalline laser 3D printed Ni-based superalloy

    DOE PAGES

    Qian, Dan; Xue, Jiawei; Zhang, Anfeng; ...

    2017-06-06

    Ductility-dip cracking in Ni-based superalloy, resulting from heat treatment, is known to cause disastrous failure, but its mechanism is still not completely clear. A statistical study of the cracking behavior as a function of crystal orientation in a laser 3D-printed DL125L Ni-based superalloy polycrystal is investigated here using the synchrotron X-ray microdiffraction. The dislocation slip system in each of the forty crystal grains adjacent to the 300 μm long crack has been analyzed through Laue diffraction peak shapes. In all these grains, edge-type geometrically necessary dislocations (GNDs) dominate, and their dislocation line directions are almost parallel to the crack plane.more » Based on Schmid's law, the equivalent uniaxial tensile force direction is revealed normal to the trace of the crack. A qualitative mechanism is thus proposed. Thermal tensile stress perpendicular to the laser scanning direction is elevated due to a significant temperature gradient, and thus locations in the materials where the thermal stress exceeds the yield stress undergo plastic deformation mediated by GND activations. As the dislocations slip inside the crystal grains and pile up at the grain boundaries, local strain/stress keeps increasing, until the materials in these regions fail to sustain further deformation, leading to voids formation and cracks propagation.« less

  5. Assessing the Effects of Radiation Damage on Ni-base Alloys for the Prometheus Space Reactor System

    SciTech Connect

    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.

  6. Ni-based composite microstructures fabricated by femtosecond laser reductive sintering of NiO/Cr mixed nanoparticles

    NASA Astrophysics Data System (ADS)

    Tamura, Kenki; Mizoshiri, Mizue; Sakurai, Junpei; Hata, Seiichi

    2017-06-01

    Ni-based composite micropatterns were fabricated by the femtosecond laser reductive sintering of NiO/Cr mixed nanoparticles. A NiO/Cr mixed nanoparticle solution including ethylene glycol and polyvinylpyrrolidone was irradiated with focused femtosecond laser pulses. The X-ray diffraction spectra of the fabricated micropatterns indicated that NiO nanoparticles were well reduced under atmospheric conditions in the laser scanning speed range of 5-15 mm/s. In contrast, micropatterns including NiO were formed at a laser scanning speed of 1 mm/s, indicating that the reduced Ni was reoxidized by overheating. These results were supported by those of energy-dispersive X-ray spectrometry analysis and the electrical resistivity of the micropatterns. The compositions such as Ni, NiO, Cr2O3, and Ni-Cr in the fabricated micropatterns depended on laser scanning speed. The selective fabrication of a ferromagnetic free microgear from the substrate and an axis fixed on the substrate was demonstrated by controlling the laser scanning speed. The fabrication process for Ni-based composite microstructures is useful for the fabrication of ferromagnetic microdevices.

  7. Microstructure chemistry and mechanical properties of Ni-based superalloy Rene N4 under irradiation at room temperature

    DOE PAGES

    Sun, C.; Kirk, M.; Li, M.; ...

    2015-06-14

    Nickel superalloys with cubic L12 structured γ' (Ni3(Al, Ti)) precipitates exhibit high strength at high temperatures and excellent corrosion resistance when exposed to water. Unlike prior studies on irradiation damage of other Ni-based superalloys, our study on Rene N4 involves much larger γ' precipitates, ~450 nm in size, a size regime where the irradiation-induced disordering and dissolution kinetics and the corresponding mechanical property evolution are unknown. Under heavy ion irradiation at room temperature, the submicron-sized γ' precipitates were fully disordered at ~0.3 dpa and only later partially dissolved after 75 dpa irradiation. Nanoindentation experiments indicate that the mechanical properties ofmore » the alloy change significantly, with a dramatic decrease in hardness, with irradiation dose. Three contributions to the change in hardness were examined: defect clusters, disordering and dissolution. Moreover, the generation of defect clusters in the matrix and precipitates slightly increased the indentation hardness, while disordering of the submicron-sized γ' precipitates resulted in a dramatic decrease in the total hardness, which decreased further during the early stages of the intermixing between γ' precipitates and matrix (<18 dpa). As a result, controlling the long-range-ordering and chemical intermixing can be used to tailor the mechanical properties of Ni-based superalloys under irradiation.« less

  8. Interplay between experiments and calculations for organometallic clusters and caged clusters

    SciTech Connect

    Nakajima, Atsushi

    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”.

  9. The optical characterization of organometallic complex thin films by spectroscopic ellipsometry and photovoltaic diode application

    SciTech Connect

    Özaydın, C.; Güllü, Ö.; Pakma, O.; Ilhan, S.; Akkılıç, K.

    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.

  10. Precursor nuclearity effects in supported vanadium oxides prepared by organometallic grafting.

    SciTech Connect

    Wegener, S. L.; Kim, H.; Marks, T. J.; Stair, P. C.

    2011-01-01

    Despite widespread importance in catalysis, the active and selective sites of supported vanadium oxide (VO{sub x}) catalysts are not well understood. Such catalysts are of great current interest because of their industrial significance and potential for selective oxidation processes. However, the fact that the nature of the active and selective sites is ambiguous hinders molecular level understanding of catalytic reactions and the development of new catalysts. Furthermore, complete structural elucidation requires isolation and characterization of specific vanadium oxide surface species, the preparation of which presents a significant synthetic challenge. In this study, we utilize the structural uniformity inherent in organometallic precursors for the preparation of supported vanadium oxide catalysts. The resulting catalysts are characterized by UV-visible diffuse reflectance spectroscopy (UV-vis DRS), X-ray absorption spectroscopy (XAS), UV-Raman spectroscopy, and H{sub 2}-temperature programmed reduction (H{sub 2}-TPR). Significant structural and reactivity differences are observed in catalysts prepared from different organometallic precursors, indicating that the chemical nature of surface vanadia can be influenced by the nuclearity of the precursor used for grafting.

  11. Stability of an Electrodeposited Nanocrystalline Ni-Based Alloy Coating in Oil and Gas Wells with the Coexistence of H2S and CO2

    PubMed Central

    Sui, Yiyong; Sun, Chong; Sun, Jianbo; Pu, Baolin; Ren, Wei; Zhao, Weimin

    2017-01-01

    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. PMID:28772995

  12. The difficult search for organocerium(iv) compounds.

    PubMed

    Anwander, Reiner; Dolg, Michael; Edelmann, Frank T

    2017-09-15

    This Tutorial Review provides an overview of the historic and current development of the organometallic chemistry of cerium in its oxidation state 4+. Among the tetravalent lanthanide ions, only Ce(4+) forms stable coordination compounds (e.g. (NH4)2[Ce(NO3)6]). Important fields of applications for cerium(iv) compounds include organic synthesis, bioinorganic chemistry, materials science, and industrial catalysis. In sharp contrast, organometallic cerium(iv) compounds are still exceedingly rare. The history of organocerium(iv) compounds is an exciting story of ups and downs. The so-called cerocene (= bis(η(8)-cyclooctatetraenyl) cerium) has been known since 1976. Other early reports e.g. about Cp4Ce (Cp = η(5)-cyclopentadienyl), were later disproven. However, significant progress in this field has been made in recent years through the use of carefully designed ligands and more sophisticated synthesis protocols. Taking the case of organocerium(iv) chemistry, this Tutorial Review also tries to exemplarily show how difficult synthetic and theoretical problems can eventually be solved through newly designed synthesis strategies (e.g. as accomplished for cyclopentadienyl and carbene derivatives) and a rewarding collaboration between synthetic and theoretical chemists (cf. the cerocene problem).

  13. Reactivity of TEMPO toward 16- and 17-electron organometallic reaction intermediates: a time-resolved IR study.

    PubMed

    Lomont, Justin P; Nguyen, Son C; Harris, Charles B

    2013-07-31

    The (2,2,6,6-tetramethylpiperidin-1-yl)oxyl radical (TEMPO) has been employed for an extensive range of chemical applications, ranging from organometallic catalysis to serving as a structural probe in biological systems. As a ligand in an organometallic complex, TEMPO can exhibit several distinct coordination modes. Here we use ultrafast time-resolved infrared spectroscopy to study the reactivity of TEMPO toward coordinatively unsaturated 16- and 17-electron organometallic reaction intermediates. TEMPO coordinates to the metal centers of the 16-electron species CpCo(CO) and Fe(CO)4, and to the 17-electron species CpFe(CO)2 and Mn(CO)5, via an associative mechanism with concomitant oxidation of the metal center. In these adducts, TEMPO thus behaves as an anionic ligand, characterized by a pyramidal geometry about the nitrogen center. Density functional theory calculations are used to facilitate interpretation of the spectra and to further explore the structures of the TEMPO adducts. To our knowledge, this study represents the first direct characterization of the mechanism of the reaction of TEMPO with coordinatively unsaturated organometallic complexes, providing valuable insight into its reactions with commonly encountered reaction intermediates. The similar reactivity of TEMPO toward each of the species studied suggests that these results can be considered representative of TEMPO's reactivity toward all low-valent transition metal complexes.

  14. Transporting and shielding photosensitisers by using water-soluble organometallic cages: a new strategy in drug delivery and photodynamic therapy.

    PubMed

    Therrien, Bruno

    2013-06-24

    Skin photosensitivity remains one of the main limitations in photodynamic therapy. In this Concept article a strategy to overcome this limitation is described, in which the photosensitizer is hidden inside the hydrophobic cavity of a water-soluble organometallic cage. The metallacage not only protects the photosensitizer from light, it also facilitates its delivery to cancer cells.

  15. 10,000-Hour Cyclic Oxidation Behavior at 982 C (1800 F) of 68 High-Temperature Co-, Fe-, and Ni-Base Alloys

    NASA Technical Reports Server (NTRS)

    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.

  16. Stepwise formation of organometallic macrocycles and triangular prisms containing 2,2'-bisbenzimidazole ligands.

    PubMed

    Wu, Tong; Lin, Yue-Jian; Jin, Guo-Xin

    2013-01-07

    A series of organometallic macrocycles have been constructed by an efficient “bottom-up” assembly methodology at ambient temperature. Treatment of [Cp*MCl2]2 (1a: M = Ir, 1b: M = Rh) with pyrazine or 4,4′-bipyridine (bpy) (1:1; Cp* = pentamethylcyclopentadienyl) at room temperature resulted in the formation of binuclear complexes [Cp*MCl2]2(pyrazine) and [Cp*MCl2]2(bpy) (M = Ir or Rh), which were then further reacted with AgOTf (Tf = O2SCF3) and 2,2′-bisbenzimidazole ligand (BiBzIm). Four organometallic macrocyclic complexes formulated as [Cp*4Ir4(BiBzIm)2(pyrazine)2](OTf)4 (2a), [Cp*4Rh4(BiBzIm)2(pyrazine)2](OTf)4 (2b), [Cp*4Ir4(BiBzIm)2(bpy)2](OTf)4 (2c) and [Cp*4Rh4(BiBzIm)2(bpy)2](OTf)4 (2d) each bearing 2,2′-bisbenzimidazole ligand and the half-sandwich Ir, Rh fragments were finally obtained in good yields. In a similar process, if a rigid ligand L (3-pyridyl-bian) was used as the linker, two novel metallacycles (3a and 3b) which enchased a silver atom in the centre were obtained. Organometallic triangular prisms 4a were synthesized via methods similar to those of the rectangles. [Cp*IrCl2]2 reacted with tridentate ligand 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) to give the corresponding trinuclear complexes [Cp*IrCl2]3(tpt), then further reacted with AgOTf and 2,2′-bisbenzimidazole ligand, leading to the formation of the prism-like complexes formulated as [Cp*6M6(BiBzIm)6(tpt)2](OTf)6 (3a: M = Ir, 3b: M = Rh). All complexes were well characterized by 1H NMR and IR spectroscopy, as well as elemental analyses. The molecular structures of 2a, 2b, 2c, 3a, 3b and 4a were characterized by single-crystal X-ray crystallography. We found that the prism-like hexanuclear complexes 4a displayed interesting host–guest chemistry.

  17. The effect of protective coatings on the high temperature properties of a gamma prime-strengthened Ni-base superalloy

    NASA Astrophysics Data System (ADS)

    Castillo, R.; Willett, K. P.

    1984-01-01

    The present study examined the influence of chrome-aluminide coatings on the creep and stress rupture properties of a wrought Udimet-520 nickel-base superalloy used in gas turbine blade applications. Creep and stress rupture tests were conducted at 802 °C (1475 °F) on coated and uncoated wrought bars in the fully heat treated condition. The tests showed that the application of the chrome-aluminide coatings caused a marked deterioration in rupture strength and ductility. Masking procedures used to protect the turbine blade roots during coating of the Ni-base superalloy also affected the rupture strength or rupture ductility. The mechanical behavior in the coated creep resistant alloy was correlated with the microstructure and is discussed in terms of possible controlling processes.

  18. Formation of Secondary Reaction Zones in Diffusion Aluminide-Coated Ni-Base Single-Crystal Superalloys Containing Ruthenium

    NASA Astrophysics Data System (ADS)

    Das, Dipak K.; Murphy, Kenneth S.; Ma, Shuwei; Pollock, Tresa M.

    2008-07-01

    The formation of secondary reaction zones (SRZs) beneath aluminide coatings in several Ru-bearing single-crystal Ni-base superalloys has been investigated. The presence of significant amounts of Ru in the superalloys did not prevent the formation of the secondary reaction zone. However, the Ru content of the alloys affected the type of refractory element-rich phase formed during the transformation. As the Ru content increased, the phase involved in the transformation shifted from the orthorhombic P to the β-RuAl phase. A differential tendency to SRZ formation was observed between the dendritic and interdendritic regions of the alloys. Significant growth of the SRZ was also observed during the high-temperature oxidation exposure of the coated alloys. The effects of the alloying elements on SRZ formation are discussed.

  19. Analysis of the Chemistry of Ni-Base Turbine Disk Superalloys Using An Alloys-By-Design Modeling Approach

    NASA Astrophysics Data System (ADS)

    Crudden, David J.; Raeisinia, Babak; Warnken, Nils; Reed, Roger C.

    2013-05-01

    The chemistry of the Ni-base superalloys used for turbine disks is critiqued by making use of the recently developed Alloys-By-Design computer-based tools. Compositions within the Ni-Cr-Co-Al-Ti-Mo-W-Ta(-Zr-C-B) design space are evaluated virtually. The assessment is made on the basis of sub-models for yield strength, creep behavior, oxidation resistance, and density; microstructural factors such as γ^' volume fraction and γ^' solvus temperature are considered where needed. The trade-offs between the different factors are studied in a quantitative sense. Diagrams are developed for the different alloy properties to highlight the limitations and challenges that one encounters when designing new grades of alloy or when optimizing existing grades. Composition-property maps are constructed that allow for an informed approach when defining an alloy composition. Specifically, the impact of chromium, molybdenum, and tungsten additions when mechanical behavior and lifing considerations are of concern is demonstrated.

  20. Effect of Co on Discontinuous Precipitation Transformation with TCP Phase in Ni-based Alloy Containing Re

    NASA Astrophysics Data System (ADS)

    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.

  1. Highly efficient growth of vertically aligned carbon nanotubes on Fe-Ni based metal alloy foils for supercapacitors

    NASA Astrophysics Data System (ADS)

    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.

  2. Hardness and microstructural inhomogeneity at the epitaxial interface of laser 3D-printed Ni-based superalloy

    NASA Astrophysics Data System (ADS)

    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.

  3. Fabrication of High-Pressure Cold-Sprayed Coating on Ni-Based Superalloy for High-Temperature Corrosive Conditions

    NASA Astrophysics Data System (ADS)

    Singh, Harminder

    2015-11-01

    The surface behavior of the Ni-based superalloy (composition similar to UNS N06075) is altered in this study by depositing a 298- µm-thick coating for various erosive-corrosive and wear applications at a high temperature. The 50%Ni-50%Cr coating was developed by a high-pressure cold-spraying method. The coating microstructure was studied by various characterization techniques. The unmelted solid particles formed the coating structure, which is homogeneous, dense, hard, and free from cracks, oxides, and other defects. The coating composition and microstructure is suitable for providing protection to the substrate under high-temperature corrosive conditions. The developed coating performed well, with degradation rate of 0.47 mm/year, in the chlorine-based highly corrosive conditions of actual waste incinerator at 900°C.

  4. A synchrotron study of defect and strain inhomogeneity in laser-assisted three-dimensionally-printed Ni-based superalloy

    DOE PAGES

    Li, Yao; Qian, Dan; Xue, Jiawei; ...

    2015-11-02

    Synchrotron X-ray microdiffraction was employed to investigate the inhomogeneous distribution of defect and residual strain in the transitional region between the dendritic and stray grains in a laser-assisted 3D printed Ni-based superalloy. The dendritic region was found to be under tensile strain transversely to the primary dendrite arm directions. The dendrite edges, where high level of strains and geometrically necessary dislocations were detected, were discerned as low angle grain boundaries. Lastly, high angle grain boundaries were observed in the stray grain region, and the orientation of the strain tensor in this region varied dramatically at the micron scale, in contrastmore » with the more or less homogeneous distribution in the dendritic region.« less

  5. Hardness and microstructural inhomogeneity at the epitaxial interface of laser 3D-printed Ni-based superalloy

    SciTech Connect

    Qian, Dan; Zhang, Anfeng; Zhu, Jianxue; Li, Yao; Zhu, Wenxin; Qi, Baolu; Tamura, Nobumichi; Li, Dichen; Song, Zhongxiao; Chen, Kai

    2016-09-09

    Here 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. Lastly, the hardening mechanism of the claddin g 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.

  6. Hardness and microstructural inhomogeneity at the epitaxial interface of laser 3D-printed Ni-based superalloy

    DOE PAGES

    Qian, Dan; Zhang, Anfeng; Zhu, Jianxue; ...

    2016-09-09

    Here 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. Lastly, the hardening mechanism of the claddin g region, on the other hand, is shown to originatemore » not only from high dislocation density but also and more importantly from the fine γ/γ' microstructure.« less

  7. A synchrotron study of defect and strain inhomogeneity in laser-assisted three-dimensionally-printed Ni-based superalloy

    SciTech Connect

    Li, Yao; Qian, Dan; Xue, Jiawei; Wan, Jingchun; Zhang, Anfeng; Tamura, Nobumichi; Song, Zhongxiao; Chen, Kai

    2015-11-02

    Synchrotron X-ray microdiffraction was employed to investigate the inhomogeneous distribution of defect and residual strain in the transitional region between the dendritic and stray grains in a laser-assisted 3D printed Ni-based superalloy. The dendritic region was found to be under tensile strain transversely to the primary dendrite arm directions. The dendrite edges, where high level of strains and geometrically necessary dislocations were detected, were discerned as low angle grain boundaries. Lastly, high angle grain boundaries were observed in the stray grain region, and the orientation of the strain tensor in this region varied dramatically at the micron scale, in contrast with the more or less homogeneous distribution in the dendritic region.

  8. V-Notched Bar Creep Life Prediction: GH3536 Ni-Based Superalloy Under Multiaxial Stress State

    NASA Astrophysics Data System (ADS)

    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.

  9. The wetting characteristics and surface tension of some Ni-based alloys on yttria, hafnia, alumina, and zirconia substrates

    NASA Technical Reports Server (NTRS)

    Kanetkar, C. S.; Kacar, A. S.; Stefanescu, D. M.

    1988-01-01

    The surface tension and wetting characteristics of four commercial Ni-based alloys (UD718, Waspaloy, UD720, and UD520), pure Ni, and three special alloys (Ni-20 percent Cr, Ni-20 percent Cr-1 percent Al, and Ni-20 percent Cr-4 percent Al) on various ceramic substrates (including alumina, zirconia, hafnia, and yttria) were investigated using sessile drop experiments. Most of the systems studied exhibited a nonwetting behavior. Wetting improved with holding time at a given temperature to the point that some systems, such as Ni-20Cr on alumina, Ni-20Cr-4Al on alumina and on yttria, became marginally wetting. Wetting characteristics were apparently related to constitutional undercooling, which in turn could be affected by the metal dissolving some of the substrate during measurements.

  10. Formation of Ni-Base Self-Fluxing Alloy Layers by Diode Laser Cladding with Powder Feeder

    NASA Astrophysics Data System (ADS)

    Kusuhara, Takayoshi; Morimoto, Junji; Ozaki, Taisuke; Abe, Nobuyuki; Tsukamoto, Masahiro

    2010-10-01

    The diode laser is more compact and the electro-optical-efficiency is higher about one order of magnitude. This is an advantage in both the small-size manufacturing field and large-size construction out door field. Another advantage is the wavelength. Due to shorter wave length most of the metals absorb diode laser (808 nm) radiation more efficiently compared with CO2 laser (10600 nm) enabling together with high power the use of wide beam optics. The deposition efficiency and energy balance were investigated. At the powder feeder nozzle angle of 45°, the Ni-base self-fusing alloy layers of more than 650 μm in thickness were formed. The layers formed at laser power of 200 W and angle of 45deg; had a high hardness of HV1012.

  11. Corrosion behavior of Ni-base superalloys at 1373 K in simulated HTGR impure helium gas environment

    NASA Astrophysics Data System (ADS)

    Mutoh, Isao; Nakasone, Yuji; Hiraga, Keijiro; Tanabe, Tatsuhiko

    1993-12-01

    The present paper describes the corrosion behavior of recently developed Ni-base superalloys: an oxide dispersion strengthened (ODS) alloy, two kinds of Ni-Cr-W alloys and Hastelloy XR at 1373 K in a simulated HTGR impure helium gas. Corrosion tests were carried out using a transparent quartz retort at 1373 K for up to 3.6 Ms in circulating helium gas which contained a small amount of H 2, CH 4, CO, CO 2 and H 2O. The mass change versus exposure time relation revealed that the ODS alloy exhibited excellent oxidation resistance. One Ni-Cr-W alloy (113MA) and Hastelloy XR showed exfoliation of the oxide films after the tests. All the alloys were decarburized from the early exposure times. These results are discussed on the basis of phase stability diagrams for constituent elements in the alloys.

  12. Preparation and Micro Mechanical Properties of Nano-Al2O3 Particles Strengthened Ni-based Composite Coatings

    NASA Astrophysics Data System (ADS)

    Wang, Hongmei; Shi, Peijing; Yu, Helong; Xu, Binshi

    Ni-based composite solution containing nano-Al2O3 particles was prepared by high-energy mechanical and chemical processes. The microstructure and nano-particle content of nano-Al2O3/Ni composite coatings were determined by SEM, EDS and TEM. The micro mechanical properties were tested by nano-indentation technique, and the strengthening mechanism was analyzed. The results show that 85 percent of particles in the solution are dispersed in size of nano meter, nano-particles co-deposited in the coating increases by a factor of 53 percent and the structure of the composite coating is more compact and uniform than that of Ni coating. Nano-Al2O3/Ni coatings exhibit excellent micro mechanical properties, the nanohardness and Young's modulus are 7.04 GPa and 225 GPa respectively, which are attributed to finer crystals strengthening, dispersion strengthening and high- density dislocations strengthening.

  13. Application of Computational Thermodynamics to the Design of a Co-Ni-Based γ'-Strengthened Superalloy

    NASA Astrophysics Data System (ADS)

    Lass, Eric A.

    2017-03-01

    A currently available commercial Calphad thermodynamic database was utilized to investigate its applicability to alloy design in the new class of Co-Ni-based γ'-strengthened high-temperature alloys. A simple primary design criterion was chosen: maximize the γ' solvus temperature in the six-component Co-Ni-Al-Ti-W-Ta system while ensuring no formation of secondary, potentially deleterious phases. Secondary design considerations included the effects of alloying elements on equilibrium γ' volume fraction and on solidus and liquidus temperatures. The identified composition, Co-30Ni-9Al-3Ti-7W-2Ta-0.1B (expressed in mole percent), representing a conservative estimate of the maximum allowable concentrations of alloying additions Al, Ti, W, and Ta, was subsequently produced and characterized. The experimentally measured γ' solvus temperature of the new alloy was 1491 ± 3 K (1218 ± 3 °C), about 35 K (35 °C) above any previously reported two-phase γ-γ' Co-(Ni)-based alloy. No secondary phases were observed in the alloy after annealing at temperatures between 1173 K and 1473 K (900 °C and 1200 °C). Additional alloy compositions with experimentally measured γ' solvus temperatures in excess of 1533 K (1260 °C) were also identified employing the same basic approach. The efficacy of currently available thermodynamic databases in their application to Co-based γ'-strengthened superalloy development is discussed, including expanding design efforts to include additional alloying elements, as well as specific areas for improvement of future databases.

  14. Application of Computational Thermodynamics to the Design of a Co-Ni-Based γ'-Strengthened Superalloy

    NASA Astrophysics Data System (ADS)

    Lass, Eric A.

    2017-05-01

    A currently available commercial Calphad thermodynamic database was utilized to investigate its applicability to alloy design in the new class of Co-Ni-based γ'-strengthened high-temperature alloys. A simple primary design criterion was chosen: maximize the γ' solvus temperature in the six-component Co-Ni-Al-Ti-W-Ta system while ensuring no formation of secondary, potentially deleterious phases. Secondary design considerations included the effects of alloying elements on equilibrium γ' volume fraction and on solidus and liquidus temperatures. The identified composition, Co-30Ni-9Al-3Ti-7W-2Ta-0.1B (expressed in mole percent), representing a conservative estimate of the maximum allowable concentrations of alloying additions Al, Ti, W, and Ta, was subsequently produced and characterized. The experimentally measured γ' solvus temperature of the new alloy was 1491 ± 3 K (1218 ± 3 °C), about 35 K (35 °C) above any previously reported two-phase γ-γ' Co-(Ni)-based alloy. No secondary phases were observed in the alloy after annealing at temperatures between 1173 K and 1473 K (900 °C and 1200 °C). Additional alloy compositions with experimentally measured γ' solvus temperatures in excess of 1533 K (1260 °C) were also identified employing the same basic approach. The efficacy of currently available thermodynamic databases in their application to Co-based γ'-strengthened superalloy development is discussed, including expanding design efforts to include additional alloying elements, as well as specific areas for improvement of future databases.

  15. Regeneration of Sulfur Deactivated Ni-based Biomass Syngas Cleaning Catalysts

    SciTech Connect

    Li, Liyu; Howard, Christopher J.; King, David L.; Gerber, Mark A.; Dagle, Robert A.; Stevens, Don J.

    2010-09-14

    Nickel-based catalysts have been widely tested in decomposing tar and methane in hot biomass syngas cleanup researches. However these catalysts can be easily deactivated by the sulfur compounds in syngas due to the strong sulfur adsorption effect on the Ni surface. Here we report on a new regeneration process, which can effectively and efficiently regenerate the sulfur-poisoned Ni reforming catalysts. This process consists of four sequential treatments: 1) controlled oxidation at 750oC in 1% O2, 2) decomposition at 900oC in Ar, 3) reduction at 900oC in 2% H2, and 4) reaction at 900oC under reforming condition. The duration of this 4-step regeneration process is only about 8 hours, which is shorter than that of the conventional steaming regeneration treatment.

  16. Use of the Spin-Trapping method to establish the radical steps in the reactions of organic compounds of zinc, cadmium, and mercury with various peroxides

    SciTech Connect

    Dodonov, V.A.; Grishin, D.F.

    1985-06-01

    This paper uses the spin trapping method to investigate the homolytic reactions of group II organometallic compounds (OMC) with organic and heteroorganic peroxides. The radical reactions of the OMC with peroxides was investigated and the reactivity of the spin traps was examined with respect to compounds of zinc, cadmium, and mercury. Phenyl-tert-butylnitron (I), 2-methyl-2-nitrosopropane (II), and tri-bromonitrobenzene (III) were chosen as spin traps. The radicals formed are aable to initiate the polymerization of vinyl monomers.

  17. Organometallic Polymers.

    ERIC Educational Resources Information Center

    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)

  18. A Photoferroelectric Perovskite-Type Organometallic Halide with Exceptional Anisotropy of Bulk Photovoltaic Effects.

    PubMed

    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.

  19. Reactivity of seventeen- and nineteen-valence electron complexes in organometallic chemistry

    NASA Technical Reports Server (NTRS)

    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.

  20. p-type Mesoscopic nickel oxide/organometallic perovskite heterojunction solar cells.

    PubMed

    Wang, Kuo-Chin; Jeng, Jun-Yuan; Shen, Po-Shen; Chang, Yu-Cheng; Diau, Eric Wei-Guang; Tsai, Cheng-Hung; Chao, Tzu-Yang; Hsu, Hsu-Cheng; Lin, Pei-Ying; Chen, Peter; Guo, Tzung-Fang; Wen, Ten-Chin

    2014-04-23

    In this article, we present a new paradigm for organometallic hybrid perovskite solar cell using NiO inorganic metal oxide nanocrystalline as p-type electrode material and realized the first mesoscopic NiO/perovskite/[6,6]-phenyl C61-butyric acid methyl ester (PC61BM) heterojunction photovoltaic device. The photo-induced transient absorption spectroscopy results verified that the architecture is an effective p-type sensitized junction, which is the first inorganic p-type, metal oxide contact material for perovskite-based solar cell. Power conversion efficiency of 9.51% was achieved under AM 1.5 G illumination, which significantly surpassed the reported conventional p-type dye-sensitized solar cells. The replacement of the organic hole transport materials by a p-type metal oxide has the advantages to provide robust device architecture for further development of all-inorganic perovskite-based thin-film solar cells and tandem photovoltaics.

  1. Soluble Two-Dimensional Covalent Organometallic Polymers by (Arene)Ruthenium-Sulfur Chemistry.

    PubMed

    Coraux, Johann; Hourani, Wael; Müller, Valentin L; Lamare, Simon; Kamaruddin, Danial Aiman; Magaud, Laurence; Bendiab, Nedjma; Den Hertog, Martien; Leynaud, Olivier; Palmino, Frank; Salut, Roland; Chérioux, Frédéric

    2017-08-16

    A class of two-dimensional (2D) covalent organometallic polymers, with nanometer-scale crosslinking, was obtained by arene(ruthenium) sulfur chemistry. Their ambivalent nature, with positively charged crosslinks and lypophylic branches is the key to the often sought-for and usually hard-to-achieve solubility of 2D polymers in various kinds of solvents. Solubility is here controlled by the planarity of the polymer, which in turn controls Coulomb interactions between the polymer layers. High planarity is achieved for high symmetry crosslinks and short, rigid branches. Owing to their solubility, the polymers are easily processable, and can be handled as powder, deposited on surfaces by mere spin-coating, or suspended across membranes by drop-casting. The novel 2D materials are potential candidates as flexible membranes for catalysis, cancer therapy, and electronics. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Anisotropic Mo2-phthalocyanine sheet: a new member of the organometallic family.

    PubMed

    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.

  3. On-Surface Observation of the Formation of Organometallic Complex in a Supramolecular Network

    NASA Astrophysics Data System (ADS)

    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.

  4. Anodic Deposition of a Robust Iridium-Based Water-Oxidation Catalyst from Organometallic Precursors

    SciTech Connect

    Blakemore, James D; Schley, Nathan D; Olack, G.; Incarvito, Christopher D; Brudvig, Gary W; Crabtree, Robert H

    2011-01-01

    Artificial photosynthesis, modeled on natural light-driven oxidation of water in Photosystem II, holds promise as a sustainable source of reducing equivalents for producing fuels. Few robust water-oxidation catalysts capable of mediating this difficult four-electron, four-proton reaction have yet been described. We report a new method for generating an amorphous electrodeposited material, principally consisting of iridium and oxygen, which is a robust and long-lived catalyst for water oxidation, when driven electrochemically. The catalyst material is generated by a simple anodic deposition from Cp*Ir aqua or hydroxo complexes in aqueous solution. This work suggests that organometallic precursors may be useful in electrodeposition of inorganic heterogeneous catalysts.

  5. Reactivity of seventeen- and nineteen-valence electron complexes in organometallic chemistry

    NASA Technical Reports Server (NTRS)

    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.

  6. Microelectrode fabrication by laser direct curing of tiny nanoparticle self-generated from organometallic ink.

    PubMed

    Kang, Bongchul; Ko, Seunghwan; Kim, Jongsu; Yang, Minyang

    2011-01-31

    In this paper, we present a new laser direct patterning method that selectively cures nanoparticles self-generated from organometallic ink by proper thermal decomposition. This approach has several advantages in the curing rate, resolution and pattern quality compared with the conventional nanoparticle ink based direct laser curing method. It was found that a laser wavelength which is more weakly absorbed by the nanoparticles could produce a more stable and homogeneous curing condition. Finally, arbitrary shaped silver electrodes with narrow width and uniform profile could be achieved on a polymer substrate at a high curing rate of 25 mm/s. This process can be applied for flexible electronics fabrications on heat sensitive polymer substrates.

  7. Rational Design of Polynuclear Organometallic Assemblies from a Simple Heteromultifunctional Ligand.

    PubMed

    Zhang, Long; Lin, Yue-Jian; Li, Zhen-Hua; Jin, Guo-Xin

    2015-10-28

    In modern coordination chemistry, supramolecular coordination complexes take advantage of ligand design to control the shapes and sizes of such architectures. Here we describe how to utilize starting building blocks and a multifunctional ligand to rationally design and synthesize different types of discrete assemblies. Using a hydroxamate ligand featuring two pair of chelating sites together with half-sandwich iridium and rhodium fragments, we were able to construct a series multinuclear organometallic macrocycles and cages through stepwise coordination-driven self-assembly. Experimental observations, supported by computational work, show that selective coordination modes were ascribed to the significant electronic density differences of the two chelating sites, (O,O') and (N,N'). The results underline the advantages of the discrimination between soft and hard binding sites, and suggest that hydroxamic acids can be used as a versatile class of facile multifunctional scaffold for the construction of novel two-dimensional and three-dimensional architectures.

  8. Quasi-one-dimensional spin-orbit-coupled correlated insulator in a multinuclear coordinated organometallic crystal

    NASA Astrophysics Data System (ADS)

    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.

  9. Metal-organometallic polymers and frameworks derived from facially metalated arylcarboxylates

    NASA Astrophysics Data System (ADS)

    Kumalah Robinson, Sayon A.

    The interest in coordination polymers, also known as metal-organic frameworks, has risen drastically over the past 2 decades. In this time, the field has matured and given rise to a diverse range of crystalline structures possessing various functionalities. Coordination polymers are typically formed from the self assembly of metal ions which serve as nodes and organic ligands which act as bridges. By the careful selection of the organic ligand and the metal ion, the overall physical properties of the material may be tuned. In this work, the use of organometallic bridging ligands are explored using facially metalated aryl carboxylates ligands to synthesize metal-organometallic frameworks (MOMFs). Therefore, with the aim of synthesizing [CpM]+-functionalized (M = FeII, RuII; Cp = cyclopentadienyl) coordination polymers and metal organic frameworks, various [CpFe]+and [CpRu] + functionalized aryl carboxylates were synthesized and characterized. In particular, the [CpFe]+-functionalized benzoic, terephthalic and trimesic acids as well as the [CpRu]+-functionalized terephthalic acid were made. Using the [CpFe]+ complexes of the benzoic and terephthalic acid as bridging ligands, a number of 1D and 2D coordination polymers were synthesized. For instance, the reaction of [CpFe]+-functionalized benzoic acid with CdCl2 yielded the 1D chain of [Cd(benzoate)Cl 2]˙H2O whilst the reaction of [CpFe]+-functionalized terephthalic acid with Cu(NO3)2˙6H2O yielded a 2D square grid sheet. Using the [CpFe]+-functionalized terephthalic acid, a series of polymorphic, 3D metal-organometallic frameworks of the general formula [M3(terephthalate)4(mu-H2O)2(H 2O)2][NO3]2˙xsolvent (M = Co II, NiII ; solvent = EtOH, DMF, H2O) were synthesized and fully characterized. The polymorphic nature of these frameworks may be attributed to the different orientations that the [CpFe]+ moiety may adapt within the cavities in the 3D frameworks. The selectivity of the desolvated forms of the polymorphs for

  10. Low oxygen and carbon incorporation in AIGaAs using tritertiarybutylaluminum in organometallic vapor phase epitaxy

    NASA Astrophysics Data System (ADS)

    Wang, C. A.; Salimand, S.; Jensen, K. F.; Jones, A. C.

    1996-05-01

    High-quality AIGaAs epilayers have been grown by low pressure organometallic vapor phase epitaxy with a new aluminum precursor tritertiarybutylaluminum (TTBAl). Layers grown at 650°C have a featureless mirror surface morphology and strong room temperature photoluminescence. Carbon was not detectable in chemical analysis by secondary ion mass spectroscopy, nor in low temperature (4K) photoluminescence spectra. Oxygen concentration in Al0.25Ga0.75As is as low as ˜2-3 × 1017 cm-3. Nominally undoped AIGaAs layers exhibit n-type conductiv-ity with electron concentrations at ˜ 1-1.5 × 1016 cm-3. A high degree of compo-sitional uniformity over 5 cm diam substrates (0.268 ±0.001) was obtained. These results indicate the potential for TTBA1 as an aluminum precursor for low temperature growth of Al-containing III-V alloys.

  11. p-type Mesoscopic Nickel Oxide/Organometallic Perovskite Heterojunction Solar Cells

    NASA Astrophysics Data System (ADS)

    Wang, Kuo-Chin; Jeng, Jun-Yuan; Shen, Po-Shen; Chang, Yu-Cheng; Diau, Eric Wei-Guang; Tsai, Cheng-Hung; Chao, Tzu-Yang; Hsu, Hsu-Cheng; Lin, Pei-Ying; Chen, Peter; Guo, Tzung-Fang; Wen, Ten-Chin

    2014-04-01

    In this article, we present a new paradigm for organometallic hybrid perovskite solar cell using NiO inorganic metal oxide nanocrystalline as p-type electrode material and realized the first mesoscopic NiO/perovskite/[6,6]-phenyl C61-butyric acid methyl ester (PC61BM) heterojunction photovoltaic device. The photo-induced transient absorption spectroscopy results verified that the architecture is an effective p-type sensitized junction, which is the first inorganic p-type, metal oxide contact material for perovskite-based solar cell. Power conversion efficiency of 9.51% was achieved under AM 1.5 G illumination, which significantly surpassed the reported conventional p-type dye-sensitized solar cells. The replacement of the organic hole transport materials by a p-type metal oxide has the advantages to provide robust device architecture for further development of all-inorganic perovskite-based thin-film solar cells and tandem photovoltaics.

  12. Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes.

    PubMed

    Camasso, Nicole M; Sanford, Melanie S

    2015-03-13

    Homogeneous nickel catalysis is used for the synthesis of pharmaceuticals, natural products, and polymers. These reactions generally proceed via nickel intermediates in the Ni(0), Ni(I), Ni(II), and/or Ni(III) oxidation states. In contrast, Ni(IV) intermediates are rarely accessible. We report herein the design, synthesis, and characterization of a series of organometallic Ni(IV) complexes, accessed by the reaction of Ni(II) precursors with the widely used oxidant S-(trifluoromethyl)dibenzothiophenium triflate. These Ni(IV) complexes undergo highly selective carbon(sp(3))-oxygen, carbon(sp(3))-nitrogen, and carbon(sp(3))-sulfur coupling reactions with exogenous nucleophiles. The observed reactivity has the potential for direct applications in the development of nickel-catalyzed carbon-heteroatom coupling reactions.

  13. Radical SAM catalysis via an organometallic intermediate with an Fe-[5'-C]-deoxyadenosyl bond.

    PubMed

    Horitani, Masaki; Shisler, Krista; Broderick, William E; Hutcheson, Rachel U; Duschene, Kaitlin S; Marts, Amy R; Hoffman, Brian M; Broderick, Joan B

    2016-05-13

    Radical S-adenosylmethionine (SAM) enzymes use a [4Fe-4S] cluster to cleave SAM to initiate diverse radical reactions. These reactions are thought to involve the 5'-deoxyadenosyl radical intermediate, which has not yet been detected. We used rapid freeze-quenching to trap a catalytically competent intermediate in the reaction catalyzed by the radical SAM enzyme pyruvate formate-lyase activating enzyme. Characterization of the intermediate by electron paramagnetic resonance and (13)C, (57)Fe electron nuclear double-resonance spectroscopies reveals that it contains an organometallic center in which the 5' carbon of a SAM-derived deoxyadenosyl moiety forms a bond with the unique iron site of the [4Fe-4S] cluster. Discovery of this intermediate extends the list of enzymatic bioorganometallic centers to the radical SAM enzymes, the largest enzyme superfamily known, and reveals intriguing parallels to B12 radical enzymes.

  14. Preparation and characterization of barium hexaferrite powders produced by decomposition of organometallic complexes

    SciTech Connect

    Chandrasekhar, R.; Charles, S.W.; O'Grady, K. ); Moerup, S.; van Wonterghem, J. )

    1987-01-01

    Barium hexaferrite (BaFe{sub 12}O{sub 19}) particles have been prepared by the decomposition of an organometallic salt. The properties of the ferrite particles have been investigated by x-ray diffractometry, Moessbauer spectroscopy, scanning electron microscopy, and magnetic measurements. The size of the particles produced lie between 0.1 and 0.5 {mu}m. To form the hexaferrite the decomposition product must be heated to > 620{degree}C. Typical values of the saturation magnetization, coercivity, and remanence ratio of the hexaferrite particles are 333 kA{center dot}m{sup {minus}1} (63 emu/g{sup {minus}1}), 320 kA{center dot}m{sup {minus}1} (4 kOe), and 0.49, respectively.

  15. Computational Estimate of the Photophysical Capabilities of Four Series of Organometallic Iron(II) Complexes.

    PubMed

    Dixon, Isabelle M; Boissard, Gauthier; Whyte, Hannah; Alary, Fabienne; Heully, Jean-Louis

    2016-06-06

    In this study, we examine a large range of organometallic iron(II) complexes with the aim of computationally identifying the most promising ones in terms of photophysical properties. These complexes combine polypyridine, bis(phosphine), and carbon-bound ligands. Density functional theory has allowed us to establish a comparative Jablonski diagram displaying the lowest singlet, triplet, and quintet states. All of the proposed FeN5C or FeN3P2C complexes unfavorably possess a lowest triplet state of metal-centered (MC) nature. Among the FeN4C2 and FeN2P2C2 series, the carbene complexes display the least favorable excited-state distribution, also having a low-lying (3)MC state. Validating our design strategy, we are now able to propose seven iron(II) complexes displaying a lowest excited state of triplet metal-to-ligand charge-transfer nature.

  16. Synthesis of organometallic complexes containing Group 13 elements and transition metals

    SciTech Connect

    Kong, G.

    1993-01-01

    New organometallic complexes containing Group 13 elements and transition metals were synthesized characterized by X-ray diffraction methods. (C[sub 5]H[sub 5])[sub 2]W[l brace]In(CH[sub 3])[sub 2][r brace][sub 2], (C[sub 5]H[sub 5])[sub 2]Mo[l brace]In(CH[sub 3])[sub 2][r brace][sub 2], and (C[sub 5]H[sub 5])[sub 2]W(I)[l brace]In(CH[sub 3])[sub 2][r brace] were synthesized by alkane elimination reactions between trimethylindium and metal hydride complexes (C[sub 5]H[sub 5])[sub 2]MH[sub 2] (M = W, Mo). [K]-[In[l brace]Fe[sub 2] (CO[sub 8])[r brace][sub 2

  17. Technomimetic molecules: synthesis of ruthenium(II) 1,2,3,4,5-penta(p-bromophenyl)cyclopentadienyl hydrotris(indazolyl)borate, an organometallic molecular turnstile.

    PubMed

    Carella, Alexandre; Jaud, Jöel; Rapenne, Gwénaël; Launay, Jean-Pierre

    2003-10-07

    A short route to prepare a ruthenium complex with a pentaphenyl substituted cyclopentadienyl and a hydrotris(indazolyl)borate ligand is described: this complex can be seen as an organometallic molecular turnstile.

  18. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    SciTech Connect

    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.

  19. Multi-targeted organometallic ruthenium(II)-arene anticancer complexes bearing inhibitors of poly(ADP-ribose) polymerase-1: A strategy to improve cytotoxicity.

    PubMed

    Wang, Zhigang; Qian, Hui; Yiu, Shek-Man; Sun, Jianwei; Zhu, Guangyu

    2014-02-01

    Small-molecule inhibitors of poly(ADP-ribose) polymerase-1 (PARP-1) have currently drawn much attention as promising chemotherapeutic drug candidates, and there is a need to develop more potent PARP inhibitors with improved bioavailability. Here we report a strategy to improve the cytotoxicity of PARP inhibitors by conjugation with organometallic ruthenium(II)-arene compounds. We also report a systematic study to reveal the mechanism of action of these ruthenium-PARP inhibitor conjugates. The complexes have been synthesized and characterized spectroscopically. The improved antiproliferative activity from the as-prepared complexes in four human cancer cell lines has indicated their potential for further development as antitumor drugs. Cellular uptake study reveals that the most active complex 3 easily entered into cells. Target validation assays show that the complexes inhibited PARP-1 slightly better than the original PARP inhibitors, that complex 3 strongly bound to DNA and inhibited transcription, and that this complex arrested the cell cycle at the G0/G1 stage. This type of information could shed light on the design of the next generation of more active ruthenium-PARP inhibitor conjugates.

  20. Ruthenium(II) and osmium(II) 1,2,3-triazolylidene organometallics: a preliminary investigation into the biological activity of 'click' carbene complexes.

    PubMed

    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).

  1. Toward new organometallic architectures: synthesis of carbene-centered rhodium and palladium bisphosphine complexes. stability and reactivity of [PC(BIm)PRh(L)][PF6] pincers.

    PubMed

    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.

  2. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    SciTech Connect

    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.

    2016-06-13

    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. Furthermore, 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.

  3. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    DOE PAGES

    Getsoian, Andrew "Bean"; Das, Ujjal; Camacho-Bunquin, Jeffrey; ...

    2016-06-13

    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 tomore » 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. Furthermore, 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.« less

  4. Recent progress in GaInAsSb thermophotovoltaics grown by organometallic vapor phase epitaxy

    SciTech Connect

    Wang, C.A.; Choi, H.K.; Oakley, D.C.; Charache, G.W.

    1998-06-01

    Studies on the materials development of Ga{sub 1{minus}x}In{sub x}As{sub y}Sb{sub 1{minus}y} alloys for thermophotovoltaic (TPV) devices are reviewed. Ga{sub 1{minus}x}In{sub x}As{sub y}Sb{sub 1{minus}y} epilayers were grown lattice matched to GaSb substrates by organometallic vapor phase epitaxy (OMVPE) using all organometallic precursors including triethylgallium, trimethylindium, tertiarybutylarsine, and trimethylantimony with diethyltellurium and dimethylzinc as the n- and p-type dopants, respectively. The overall material quality of these alloys depends on growth temperature, In content, V/III ratio, substrate misorientation, and to a lesser extent, growth rate. A mirror-like surface morphology and room temperature photoluminescence (PL) are obtained for GaInAsSb layers with peak emission in the wavelength range between 2 and 2.5 {micro}m. The crystal quality improves for growth temperature decreasing from 575 to 525 C, and with decreasing In content, as based on epilayer surface morphology and low temperature PL spectra. A trend of smaller full width at half-maximum for low temperature PL spectra is observed as the growth rate is increased from 1.5 to 2.5 and 5 {micro}m/h. In general, GaInAsSb layers grown on (100) GaSb substrates with a 6{degree} toward (111)B misorientation exhibited overall better material quality than layers grown on the more standard substrate (100)2{degree} toward (110). Consistent growth of high performance lattice-matched GaInAsSb TPV devices is also demonstrated.

  5. NMR studies in chemistry. I. Organometallic tin and geramanium compounds. II. The sorbitol pathway in intact lenses

    SciTech Connect

    Williams, W.F.

    1985-01-01

    Nuclear magnetic resonance spectroscopy has been utilized in the study of two very different chemical problems. The bonding and structure of various cyclopropyl derivatives of tin and germanium has been investigated by means of Sn-119, Ge-73, C-13, and H-1 NMR spectroscopy. Intact rabbit lenses have also been studied using NMR spectroscopy with regard to diabetic cataract formation. C-13 and P-31 NMR spectroscopies have been utilized in the study of the sorbitol pathway and aldose reductase inhibition.

  6. Studies on the reactivity of organometallic Ru-, Rh- and Os-pta complexes with DNA model compounds.

    PubMed

    Dorcier, Antoine; Hartinger, Christian G; Scopelliti, Rosario; Fish, Richard H; Keppler, Bernhard K; Dyson, Paul J

    2008-01-01

    The reactions of arene-metal complexes (arene=p-cymene, benzene or pentamethylcyclopentadienyl, metal=Ru, Rh or Os), including 1,3,5-triaza-7-phosphatricyclo-[3.3.1.1]decanephosphine (pta) and chloro co-ligands, with 9-methylguanine, adenine, and a series of nucleosides were studied in water to ascertain the binding modes. The products were characterized by NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Tandem mass spectrometry was found to provide excellent information on preferential binding sites. In general, the N7 position on guanine (the most basic site) was found to be the preferred donor atom for coordination to the metal complexes. The X-ray structures of the precursor complexes, [(eta5-C10H15)RhCl(pta-Me)2]Cl2, [(eta6-C10H14)OsCl(pta)2]Cl, and [(eta6-C6H6)OsCl2(CH3CN)], are also reported.

  7. Photonics of a conjugated organometallic Pt-Ir polymer and its model compounds exhibiting hybrid CT excited states.

    PubMed

    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.

  8. Electron-Transfer Reactions of Organometallic and Coordination Compounds in the Absence of Solvent: Experimental Results and Theoretical Approaches

    DTIC Science & Technology

    1988-07-07

    OI C FILE COF AD-A 197 086 ). ... ENTA TION PAGE AD A 197 086 b. RESTRICTIVE MARKINGS L~ a. SECURITY CLASSIFICATION AUTH 3. DISTRIBUTION/ AV...and theoretically estimated factors are compared to experiment for a typical metallocene, ferrocene . (’ 20. DISTRIBUItuN/AVAILABILITY OF ABSTRACT 21...is examined, and theoretically estimated factors are ,’or compared to experiment for a typical metallocene, ferrocene . I L) I t *~6% ~ * ’." .-- 4

  9. Crystal and molecular structures of selected organic and organometallic compounds and an algorithm for empirical absorption correction

    SciTech Connect

    Karcher, B.

    1981-10-01

    Cr(CO)/sub 5/(SCMe/sub 2/) crystallizes in the monoclinic space group P2/sub 1//a with a = 10.468(8), b = 11.879(5), c = 9.575(6) A, and ..beta.. = 108.14(9)/sup 0/, with an octahedral coordination around the chromium atom. PSN/sub 3/C/sub 6/H/sub 12/ crystallizes in the monoclinic space group P2/sub 1//n with a = 10.896(1), b = 11.443(1), c = 7.288(1) A, and ..beta.. = 104.45(1)/sup 0/. Each of the five-membered rings in this structure contains a carbon atom which is puckered toward the sulfur and out of the nearly planar arrays of the remaining ring atoms. (RhO/sub 4/N/sub 4/C/sub 48/H/sub 56/)/sup +/(BC/sub 24/H/sub 20/)/sup -/.1.5NC/sub 2/H/sub 3/ crystallizes in the triclinic space group P1 with a = 17.355(8), b = 21.135(10), c = 10.757(5) A, ..cap alpha.. = 101.29(5), ..beta.. = 98.36(5), and ..gamma.. = 113.92(4)/sup 0/. Each Rh cation complex is a monomer. MoP/sub 2/O/sub 10/C/sub 16/H/sub 22/ crystallizes in the monoclinic space group P2/sub 1//c with a = 12.220(3), b = 9.963(2), c = 20.150(6) A, and ..beta.. = 103.01(3)/sup 0/. The molybdenum atom occupies the axial position of the six-membered ring of each of the two phosphorinane ligands. An empirical absorption correction program was written.

  10. Unravelling novel synergies between organometallic and biological partners: a quantum mechanics/molecular mechanics study of an artificial metalloenzyme.

    PubMed

    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.

  11. Functionalization of a ruthenium-diacetylide organometallic complex as a next-generation push-pull chromophore.

    PubMed

    De Sousa, Samuel; Ducasse, Laurent; Kauffmann, Brice; Toupance, Thierry; Olivier, Céline

    2014-06-02

    The design and preparation of an asymmetric ruthenium-diacetylide organometallic complex was successfully achieved to provide an original donor-π-[M]-π-acceptor architecture, in which [M] corresponds to the [Ru(dppe)2] (dppe: bisdiphenylphosphinoethane) metal fragment. The charge-transfer processes occurring upon photoexcitation of the push-pull metal-dialkynyl σ complex were investigated by combining experimental and theoretical data. The novel push-pull complex, appropriately end capped with an anchoring carboxylic acid function, was further adsorbed onto a semiconducting metal oxide porous thin film to serve as a photosensitizer in hybrid solar cells. The resulting photoactive material, when embedded in dye-sensitized solar cell devices, showed a good spectral response with a broad incident photon-to-current conversion efficiency profile and a power conversion efficiency that reached 7.3 %. Thus, this material paves the way to a new generation of organometallic chromophores for photovoltaic applications.

  12. Stepwise construction of discrete parallelogram- and prism-shaped organometallic architectures based on half-sandwich rhodium fragments.

    PubMed

    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.

  13. Unravelling novel synergies between organometallic and biological partners: a quantum mechanics/molecular mechanics study of an artificial metalloenzyme

    PubMed Central

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

    2014-01-01

    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. PMID:24829279

  14. Preparation of Surface Organometallic Catalysts by Gas-Phase Ligand Stripping and Reactive Landing of Mass-Selected Ions

    SciTech Connect

    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.

  15. Organometallic nickel(III) complexes relevant to cross-coupling and carbon-heteroatom bond formation reactions.

    PubMed

    Zheng, Bo; Tang, Fengzhi; Luo, Jia; Schultz, Jason W; Rath, Nigam P; Mirica, Liviu M

    2014-04-30

    Nickel complexes have been widely employed as catalysts in C-C and C-heteroatom bond formation reactions. In addition to Ni(0) and Ni(II) intermediates, several Ni-catalyzed reactions are proposed to also involve odd-electron Ni(I) and Ni(III) oxidation states. We report herein the isolation, structural and spectroscopic characterization, and organometallic reactivity of Ni(III) complexes containing aryl and alkyl ligands. These Ni(III) species undergo transmetalation and/or reductive elimination reactions to form new C-C or C-heteroatom bonds and are also competent catalysts for Kumada and Negishi cross-coupling reactions. Overall, these results provide strong evidence for the direct involvement of organometallic Ni(III) species in cross-coupling reactions and oxidatively induced C-heteroatom bond formation reactions.

  16. Search for the ground-state electronic configurations of correlated organometallic metallocenes from constraint density functional theory

    NASA Astrophysics Data System (ADS)

    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.

  17. 'Clickable' ZnO nanocrystals: the superiority of a novel organometallic approach over the inorganic sol-gel procedure.

    PubMed

    Grala, Agnieszka; Wolska-Pietkiewicz, Małgorzata; Danowski, Wojciech; Wróbel, Zbigniew; Grzonka, Justyna; Lewiński, Janusz

    2016-05-31

    We demonstrate for the first time a highly efficient Cu(i)-catalyzed alkyne-azide cycloaddition reaction on the surface of ZnO nanocrystals with retention of their photoluminescence properties. Our comparative studies highlight the superiority of a novel self-supporting organometallic method for the preparation of brightly luminescent and well-passivated ZnO nanocrystals over the traditional sol-gel procedure.

  18. Effect of Cyclic Oxidation Exposure on Tensile Properties of a Pt-Aluminide Bond-Coated Ni-Base Superalloy

    NASA Astrophysics Data System (ADS)

    Zafir Alam, Md.; Hazari, N.; Varma, Vijay K.; Das, Dipak K.

    2011-12-01

    The tensile behavior of a directionally solidified (DS) Ni-base superalloy, namely, CM-247LC, was evaluated in the presence of a Pt-aluminide bond coat. The effect of the thermal cycling exposure of the coated alloy at 1373 K (1100 °C) on its tensile properties was examined. The tensile properties were evaluated at a temperature of 1143 K (870 °C). The presence of the bond coating caused an approximately 8 pct drop in the strength of the alloy in the as-coated condition. However, the coating did not appreciably affect the tensile ductility of the substrate alloy. The bond coat prevented oxidation-related surface damage to the superalloy during thermal cycling exposure in air at 1373 K (1100 °C). Such cyclic oxidation exposure (up to 750 hours) did not cause any further reduction in yield strength (YS) of the coated alloy. There was a marginal decrease in the ultimate tensile strength (UTS) with increased exposure duration. Because of the oxidation protection provided by the bond coat, the drastic loss in ductility of the alloy, which would have happened in the absence of the coating, was prevented.

  19. Synthesis and cyclic oxidation behavior of a (Ni, Pt) Al coating on a desulfurized Ni-base superalloy

    SciTech Connect

    Zhang, Y.; Lee, W.Y.; Haynes, J.A.; Wright, I.G.; Pint, B.A.; Cooley, K.M.; Liaw, P.K.

    1999-10-01

    The influences of sulfur impurities and Pt incorporation on the scale adhesion behavior of aluminide coatings were studied and compared. Low-sulfur NiAl coatings were prepared on a desulfurized, yttrium-free, single-crystal Ni-based superalloy by a modified version of a conventional aluminizing procedure based on chemical vapor deposition. The sulfur level in the resulting NiAl coatings was measured to be less than {approximately}0.5 ppmw by glow-discharge mass spectroscopy. Platinum-modified aluminide coatings were synthesized by first electroplating a thin layer of Pt({approximately}7 {micro}m) on the superalloy, followed by the same low-sulfur aluminizing procedure. The measured sulfur content in the (Ni,Pt)Al coating was substantially higher than that of the low-sulfur NiAl coating due to contamination during the Pt electroplating process. A very adherent {alpha}-Al{sub 2}O{sub 3} scale formed on the grain surfaces of the low-sulfur NiAl coating during cyclic oxidation testing at 1,150 C, but scale spallation eventually occurred over many of the NiAl grain boundaries. In contrast, despite the higher level of sulfur in the (NI,Pt)Al coating, a very adherent scale was formed over both the coating grain surfaces and grain boundaries during thermal cycling. These results suggest that Pt additions can mitigate the detrimental influence of sulfur on scale adhesion.

  20. Influences of synthesis methods and modifier addition on the properties of Ni-based catalysts supported on reticulated ceramic foams

    NASA Astrophysics Data System (ADS)

    Nikolić, Vesna; Kamberović, Željko; Anđić, Zoran; Korać, Marija; Sokić, Miroslav; Maksimović, Vesna

    2014-08-01

    A method of synthesizing Ni-based catalysts supported on α-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 reduction process was nearly complete at 533 K in the sample that contained 0.1wt% Pd. A lower reduction temperature was utilized, and the calcination step was avoided, which may enhance the economical and technological aspects of the developed catalyst production method.

  1. Predicting minimum Al concentrations for protective scale fromation on Ni-base alloys. I - Isothermal oxidation. II - Cyclic oxidation

    NASA Technical Reports Server (NTRS)

    Nesbitt, James A.

    1989-01-01

    Criteria proposed to predict the minimum bulk Al concentration for the formation of protective Al2O3 scales on Ni-based alloys during isothermal oxidation (two criteria proposed by Wagner, 1952 and 1959) and cyclic oxidation (the criteria proposed by Wahl, 1983, and Whittle, 1972/Wahl, 1983) were applied to Ni-Al and Ni-Cr-Al(Zr) alloys, respectively. It is shown that the first Wagner (1952) criterion underpredicted, by a factor of 3, the experimentally observed minimum Al concentration for the formation of an external Al2O3 scale on Ni-Al alloys at 1200 C; the second Wagner criterion predicted a transition from internal oxidation to continuous Al2O3 formation in good agreement with experimentally observed concentrations. It was also found that the two criteria for an Al2O3 scale formation during cyclic oxidation of Ni-Cr-Al(Zr) alloys were inadequate to predict the minimum Al concentration necessary for repeated formation of an Al2O3 scale, regardless of the adherence of the scale.

  2. Thin Co/Ni-based bottom pinned spin-transfer torque magnetic random access memory stacks with high annealing tolerance

    NASA Astrophysics Data System (ADS)

    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. Synthesis and Oxidation Behavior of Platinum-Enriched γ+γ' Bond Coatings on Ni-Based Superalloys

    SciTech Connect

    Zhang, Ying; Ballard, D A; Stacy, J P; Pint, Bruce A; Haynes, James A

    2006-01-01

    Simple Pt-enriched {gamma}+{gamma}{prime} coatings were synthesized on Rene 142 and Rene N5 Ni-based superalloys by electroplating a thin layer of Pt followed by a diffusion treatment at 1150-1175 C. The Al content in the resulting {gamma}+{gamma}{prime} coating was in the range of 16-19 at.% on superalloys with 13-14 at.% Al. After oxidation testing, alumina scale adherence to these {gamma}+{gamma}{prime} coatings was not as uniform as to the {beta}-(Ni,Pt)Al coatings on the same superalloy substrates. To better understand the effect of Al, Pt and Hf concentrations on coating oxidation resistance, a number of Ni-Pt-Al cast alloys with {gamma}+{gamma}{prime} or {beta} phase were cyclically oxidized at 1100 C. The Hf-containing {gamma}+{gamma}{prime} alloys with 22 at.% Al and 10-30 at.% Pt exhibited similar oxidation resistance to the {beta} alloys with 50 at.% Al. An initial effort was made to increase the Al content in the Pt-enriched {gamma}+{gamma}{prime} coatings by introducing a short-term aluminizing process via chemical vapor deposition or pack cementation. However, too much Al was deposited, leading to the formation of {beta} or martensitic phase on the coating surface.

  4. Deactivation Mechanisms of Ni-Based Tar Reforming Catalysts As Monitored by X-ray Absorption Spectroscopy

    SciTech Connect

    Yung, Matthew M.; Kuhn, John N.

    2010-12-06

    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.

  5. Tailoring the physical properties of Ni-based single-phase equiatomic alloys by modifying the chemical complexity

    SciTech Connect

    Jin, Ke; Sales, Brian C.; Stocks, George Malcolm; Samolyuk, German D.; Daene, Markus; Weber, William J.; Zhang, Yanwen; Bei, Hongbin

    2016-02-01

    We discovered that equiatomic alloys (e.g. high entropy alloys) have recently attracted considerable interest due to their exceptional properties, which might be closely related to their extreme disorder induced by the chemical complexity. To understand the effects of chemical complexity on their fundamental physical properties, a family of (eight) Ni-based, face-center-cubic (FCC), equiatomic alloys, extending from elemental Ni to quinary high entropy alloys, has been synthesized, and their electrical, thermal, and magnetic properties are systematically investigated in the range of 4–300 K by combining experiments with ab initio Korring-Kohn-Rostoker coherent-potential-approximation (KKR-CPA) calculations. The scattering of electrons is significantly increased due to the chemical (especially magnetic) disorder. It has weak correlation with the number of elements but strongly depends on the type of elements. Thermal conductivities of the alloys are largely lower than pure metals, primarily because the high electrical resistivity suppresses the electronic thermal conductivity. Moreover, the temperature dependence of the electrical and thermal transport properties is further discussed, and the magnetization of five alloys containing three or more elements is measured in magnetic fields up to 4 T.

  6. Tailoring the physical properties of Ni-based single-phase equiatomic alloys by modifying the chemical complexity

    DOE PAGES

    Jin, Ke; Sales, Brian C.; Stocks, George Malcolm; ...

    2016-02-01

    We discovered that equiatomic alloys (e.g. high entropy alloys) have recently attracted considerable interest due to their exceptional properties, which might be closely related to their extreme disorder induced by the chemical complexity. To understand the effects of chemical complexity on their fundamental physical properties, a family of (eight) Ni-based, face-center-cubic (FCC), equiatomic alloys, extending from elemental Ni to quinary high entropy alloys, has been synthesized, and their electrical, thermal, and magnetic properties are systematically investigated in the range of 4–300 K by combining experiments with ab initio Korring-Kohn-Rostoker coherent-potential-approximation (KKR-CPA) calculations. The scattering of electrons is significantly increased duemore » to the chemical (especially magnetic) disorder. It has weak correlation with the number of elements but strongly depends on the type of elements. Thermal conductivities of the alloys are largely lower than pure metals, primarily because the high electrical resistivity suppresses the electronic thermal conductivity. Moreover, the temperature dependence of the electrical and thermal transport properties is further discussed, and the magnetization of five alloys containing three or more elements is measured in magnetic fields up to 4 T.« less

  7. Detached Melt Nucleation during Diffusion Brazing of a Technical Ni-based Superalloy: A Phase-Field Study

    NASA Astrophysics Data System (ADS)

    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.

  8. Deactivation mechanisms of Ni-based tar reforming catalysts as monitored by X-ray absorption spectroscopy.

    PubMed

    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.

  9. Effect of La2O3 on High-Temperature Oxidation Resistance of Electrospark Deposited Ni-BASED Coatings

    NASA Astrophysics Data System (ADS)

    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.

  10. The Influence of Dwell Time on Low Cycle Fatigue Behavior of Ni-base Superalloy IC10

    NASA Astrophysics Data System (ADS)

    Wang, Anqiang; Liu, Lu; Wen, Zhixun; Li, Zhenwei; Yue, Zhufeng

    2017-09-01

    Low cycle fatigue and creep-fatigue experiments of IC10 Ni-base superalloy plate specimens with multiple holes were performed below 1,000 °C. The average fatigue life is 105.4 cycles, while the creep-fatigue life is 103.4 cycles, which shows that the life of creep-fatigue is reduced 1-2 times compared with low cycle fatigue life. After tests, the detailed fracture and microscopic structure evolution were observed by scanning electron microscopy (SEM); meanwhile, the constitutive model based on crystal plasticity theory was established and the fracture mechanism was analyzed. Three conclusions have been obtained: First, the load during dwell time leads to the damage accumulation caused by deformation and the interaction of fatigue and creep shortens the service life of materials seriously. Second, in order to maintain the macroscopic deformation, a new slip plane starts to makes the dislocation slide in reverse direction, which leads to fatigue damage and initial cracks. Third, the inner free surface creates opportunities for escape of the dislocation line, which is caused by the cavity. What's more, the cure dislocation generated by cyclic loading contributes to the formation and growth of cavities.

  11. Corrosion Resistance of Ni-Based WC/Co Coatings Deposited by Spray and Fuse Process Varying the Oxygen Flow

    NASA Astrophysics Data System (ADS)

    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.

  12. Corrosion Resistance of Ni-Based WC/Co Coatings Deposited by Spray and Fuse Process Varying the Oxygen Flow

    NASA Astrophysics Data System (ADS)

    Jiménez, H.; Olaya, J. J.; Alfonso, J. E.; Mtshali, C. B.; Pineda-Vargas, C. A.

    2017-10-01

    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.

  13. Initial assessment of Ni-base alloy performance in 0.1 MPa and supercritical CO2

    DOE PAGES

    Pint, B. A.; Keiser, J. R.

    2015-09-25

    There is considerable interest in increasing the working temperature of both open and closed supercritical CO2 (sCO2) cycles to ≥700 °C. At these temperatures, it is unlikely that any Fe-base alloys have suitable strength and therefore the focus is on Ni-base alloys for this application. To begin addressing the lack of compatibility data under these conditions, initial work exposed a wide range of candidate alloys in 500-h exposures at 20 MPa (200 bar) CO2 at 650 -750 °C in high purity CO2. In general, the reaction products were thin and protective in these exposures. A smaller group of alloy couponsmore » focusing on chromia- and alumina-forming alloys was exposed for 500h in 0.1 MPa (1bar) air, CO2, CO2+O2 and CO2+H2O for comparison. Thus, the thin surface oxides formed were very similar to those formed at high pressure and no clear detrimental effect of CO2 oxidation or O2 or H2O impurities could be observed in these exposures.« less

  14. Direct methane solid oxide fuel cells based on catalytic partial oxidation enabling complete coking tolerance of Ni-based anodes

    NASA Astrophysics Data System (ADS)

    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.

  15. Effects of thermal aging on microstructures of low alloy steel-Ni base alloy dissimilar metal weld interfaces

    NASA Astrophysics Data System (ADS)

    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.

  16. A Platinum-Enriched gamma+gamma' Two-Phase Bond Coat on Ni-Base Superalloys

    SciTech Connect

    Zhang, Ying; Pint, Bruce A; Haynes, James A; Wright, Ian G

    2005-01-01

    Pt-enriched {gamma} + {gamma}{prime} two-phase coating was applied to directionally-solidified Ni-based superalloy Ren{acute e} 142 substrates with three different Hf levels (0.02, 0.76, and 1.37 wt.%). The coating was prepared by electroplating a thin layer of Pt on the superalloy followed by a diffusion treatment. The as-deposited coating exhibited a {gamma} + {gamma}{prime} two-phase microstructure with a major composition of Ni-16Al-18Pt-7Cr-9Co (in at.%) along with some incorporation of refractory elements from the substrates. Cyclic oxidation testing at 1100 C in air indicated improved oxidation resistance of the Ren{acute e} 142 alloys with the Pt-enriched {gamma} + {gamma}{prime} coatings. In addition, the oxidation resistance of both uncoated and coated alloys was proportional to the Hf content in the substrate. Compared with the single-phase {beta}-(Ni,Pt)Al coating, slightly higher mass gains and localized spallation were observed on the {gamma} + {gamma}{prime} two-phase coating, which might be due to the segregation of refractory elements and high sulfur levels in these superalloy substrates.

  17. Real-time microstructure imaging by Laue microdiffraction: A sample application in laser 3D printed Ni-based superalloys

    NASA Astrophysics Data System (ADS)

    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).

  18. Tailoring the physical properties of Ni-based single-phase equiatomic alloys by modifying the chemical complexity

    PubMed Central

    Jin, K.; Sales, B. C.; Stocks, G. M.; Samolyuk, G. D.; Daene, M.; Weber, W. J.; Zhang, Y.; Bei, H.

    2016-01-01

    Equiatomic alloys (e.g. high entropy alloys) have recently attracted considerable interest due to their exceptional properties, which might be closely related to their extreme disorder induced by the chemical complexity. In order to understand the effects of chemical complexity on their fundamental physical properties, a family of (eight) Ni-based, face-center-cubic (FCC), equiatomic alloys, extending from elemental Ni to quinary high entropy alloys, has been synthesized, and their electrical, thermal, and magnetic properties are systematically investigated in the range of 4–300 K by combining experiments with ab initio Korring-Kohn-Rostoker coherent-potential-approximation (KKR-CPA) calculations. The scattering of electrons is significantly increased due to the chemical (especially magnetic) disorder. It has weak correlation with the number of elements but strongly depends on the type of elements. Thermal conductivities of the alloys are largely lower than pure metals, primarily because the high electrical resistivity suppresses the electronic thermal conductivity. The temperature dependence of the electrical and thermal transport properties is further discussed, and the magnetization of five alloys containing three or more elements is measured in magnetic fields up to 4 T. PMID:26832223

  19. Weld Bead Geometry of Ni-Based Alloy Deposited by PTA Process for Pipe Conduction of Shale Gas

    NASA Astrophysics Data System (ADS)

    Echavarria-Figueroa, C.; García-Vázquez, F.; Ruiz-Mondragón, J.; Hernández-García, H. M.; González-González, D.; Vargas, A.

    The transportation of shale gas has the problem that the piping used for the extraction does not resist the erosion generated by the amount of solids causing cracks over the surface and it is necessary to extend the life of the pipelines. Plasma transferred arc (PTA) welded coatings are used to improve the surface properties of mechanical parts. Therefore, in this paper is studied the use of Ni-based filler metal as weld bead deposits on A36 steel substrates by PTA. In order to determine the suitable conditions to ensure coating quality on the substrate a design of experiments (DOE) was determined. Welding current, feed rate, and travel speed were used as input parameters and the dilution percentage as the response variable. The composition and properties of hardfacing or overlay deposited are strongly influenced by the dilution obtained. Control of dilution is important, where typically low dilution is desirable. When the dilution is low, the final deposit composition will be closer to that of the filler metal, and the wear and corrosion resistance of the hardfacing will also be maintained. To evaluate the features on the weld beads/substrate interface a microstructural characterization was performed by using scanning electron microscopy and to evaluate the mechanical properties was carried out hardness test.

  20. Real-time microstructure imaging by Laue microdiffraction: A sample application in laser 3D printed Ni-based superalloys

    DOE PAGES

    Zhou, Guangni; Zhu, Wenxin; Shen, Hao; ...

    2016-06-15

    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 realmore » 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).« less