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Sample records for intermetallic compound formation

  1. Formation of Intermetallic Compounds During Explosive Welding

    NASA Astrophysics Data System (ADS)

    Greenberg, Bella A.; Ivanov, Mikhail A.; Pushkin, Mark S.; Inozemtsev, Alexei V.; Patselov, Alexander M.; Tankeyev, Anatoliy P.; Kuzmin, Sergey V.; Lysak, Vladimir I.

    2016-11-01

    Transition states between traditional, i.e., plain and wavy, shapes of the interface during explosive welding were studied. A sequence of the transition states was found for the studied copper-titanium and copper-tantalum joints. Some transition states are common for the joints under study, while others are only typical of the copper-titanium joints, due to sufficiently high solubility of original elements. A transition state has been found, during which cusps, even though they are solid phase, look like splashes on the water. The key role of these splashes is that they evidence the lower boundary of the `weldability window.' The study found certain self-organization processes of the cusps that cause them to turn into a quasi-wavy shape of the interface, and then, as the welding mode is intensified, into a wavy shape. The role of intermetallic compounds was analyzed, due to which a wave only consists of cusps in case mutual solubility of original metals is sufficiently high.

  2. Intermetallic Compounds

    NASA Astrophysics Data System (ADS)

    Takagiwa, Y.; Matsuura, Y.; Kimura, K.

    2014-06-01

    We have focused on the binary narrow-bandgap intermetallic compounds FeGa3 and RuGa3 as thermoelectric materials. Their crystal structure is FeGa3-type (tetragonal, P42/ mnm) with 16 atoms per unit cell. Despite their simple crystal structure, their room temperature thermal conductivity is in the range 4-5-W-m-1-K-1. Both compounds have narrow-bandgaps of approximately 0.3-eV near the Fermi level. Because their Seebeck coefficients are quite large negative values in the range 350-<-| S 373K|-<-550- μV-K-1 for undoped samples, it should be possible to obtain highly efficient thermoelectric materials both by adjusting the carrier concentration and by reducing the thermal conductivity. Here, we report the effects of doping on the thermoelectric properties of FeGa3 and RuGa3 as n and p-type materials. The dimensionless figure of merit, ZT, was significantly improved by substitution of Sn for Ga in FeGa3 (electron-doping) and by substitution of Zn for Ga in RuGa3 (hole-doping), mainly as a result of optimization of the electronic part, S 2 σ.

  3. Intermetallic compound formation at Cu-Al wire bond interface

    NASA Astrophysics Data System (ADS)

    Bae, In-Tae; Young Jung, Dae; Chen, William T.; Du, Yong

    2012-12-01

    Intermetallic compound (IMC) formation and evolution at Cu-Al wire bond interface were studied using focused ion beam /scanning electron microscopy, transmission electron microscopy (TEM)/energy dispersive x-ray spectroscopy (EDS), nano beam electron diffraction (NBED) and structure factor (SF) calculation. It was found that discrete IMC patches were formed at the Cu/Al interface in as-packaged state and they grew toward Al pad after high temperature storage (HTS) environment at 150 °C. TEM/EDS and NBED results combined with SF calculation revealed the evidence of metastable θ'-CuAl2 IMC phase (tetragonal, space group: I4¯m2, a = 0.404 nm, c = 0.580 nm) formed at Cu/Al interfaces in both of the as-packaged and the post-HTS samples. Two feasible mechanisms for the formation of the metastable θ'-CuAl2 phase are discussed based on (1) non-equilibrium cooling of wire bond that is attributed to highly short bonding process time and (2) the epitaxial relationships between Cu and θ'-CuAl2, which can minimize lattice mismatch for θ'-CuAl2 to grow on Cu.

  4. Formation of intermetallic compound coating on magnesium AZ91 cast alloy

    NASA Astrophysics Data System (ADS)

    Zhu, Tianping; Gao, Wei

    2009-08-01

    This study describes an intermetallic compound coating formed on AZ91 Mg cast alloy. The Al sputtered on AZ91 cast alloy reacted with substrate during a short period of heat treatment at 435°C, resulting in the formation of a continuous intermetallic compound layer. The short period treatment has the advantage of minimizing the negative effect on the microstructure of substrate and the mechanical properties, comparing with the reported diffusion coatings. DSC measurement and examination on the cross-section of Al sputtered samples show that local melting occurred along the Al/substrate interface at the temperature range between 430~435°C. The formation mechanism of intermetallic compound coating is proposed in terms of the local melting at Al/substrate interface. The salt water immersion test showed significant improvement in corrosion resistance of the intermetallic compound coated AZ91 cast alloy compared with the as-cast alloys.

  5. Evaluation of Gibbs free energies of formation of Ce-Cd intermetallic compounds using electrochemical techniques

    NASA Astrophysics Data System (ADS)

    Shibata, Hiroki; Hayashi, Hirokazu; Akabori, Mitsuo; Arai, Yasuo; Kurata, Masaki

    2014-08-01

    Gibbs free energies of formation of six Ce-Cd intermetallic compounds, CeCd, CeCd2, CeCd3, CeCd58/13, CeCd6 and CeCd11, were evaluated systematically using electrochemical techniques in the temperature range of 673-923 K in the LiCl-KCl-CeCl3-CdCl2 molten salt bath. The linear dependence of the Gibbs free energies of formation on temperature yields to the enthalpies and entropies of formation of these intermetallic compounds. By extrapolating the Gibbs free energy of Ce-Cd intermetallic compounds to the Cd distillation temperature, it was clear that the Gibbs free energy of Ce-Cd intermetallic compounds decreases gradually from CeCd6 to CeCd2 and attains minimum value at CeCd2. This suggests on the Cd distillation from the U-Pu-Ce-Cd alloy that the dissolution of U or Pu into CeCd2 should be mostly taken into consideration.

  6. Metastable phase formation in Be-Nb intermetallic compounds

    SciTech Connect

    Brimhall, J.L.; Charlot, L.A.; Bruemmer, S.M.

    1990-11-01

    Amorphous structures or metastable crystalline phases are produced in sputter-deposited Beryllium-Niobium (Be-Nb) alloys (5-15 at. % Nb) depending on the substrate temperature. The metastable phases transform to the stable Be{sub 12}Nb, Be{sub 17}Nb{sub 2}Nb phases on annealing at temperatures >800{degree}C. No Be{sub 5}Nb phase was found and the Be{sub 17}Nb{sub 2} phase is stable to low temperature. The Be{sub 12}Nb phase appeared to have a stoichiometric range of about 5.5 to 7.7 at. % Nb. The formation of the metastable phases is consistent with current models and theories. 17 refs., 1 fig., 2 tabs.

  7. Kinetics of intermetallic compound formation in thermally evaporated Ag-In bilayers

    NASA Astrophysics Data System (ADS)

    Rossi, P. J.; Zotov, N.; Mittemeijer, E. J.

    2016-10-01

    The kinetics of intermetallic compound (IMC) formation in thermally evaporated Ag-In bilayers, with In on top of Ag, was investigated using X-ray diffractometry, applied to the surfaces of the bilayer specimens, as well as scanning electron microscopy, applied to cross-sections of the bilayer specimens, prepared by a focused ion beam instrument. IMC formation was followed at room temperature as well as at elevated temperatures of 50 ° C , 60 ° C , and 70 ° C . Two distinct growth regimes were observed coinciding with the availability of pure In. The AgIn2 IMC nucleated initially, followed by nucleation of the Ag2In IMC. The growth of AgIn2 was found to be controlled by both diffusional processes as well as interfacial reactions. The growth of the Ag2In IMC is dominantly diffusion-controlled. An interdiffusion coefficient of D = 1.1 ± 3.9 . 10 - 4 cm 2 s - 1 exp ( - 60.5 ± 9.2 kJ mol - 1 R - 1 T - 1 ) was obtained for the Ag2In IMC. The observations were discussed in terms of the interplay of thermodynamic and kinetic constraints.

  8. MECHANICAL BEHAVIOR OF INTERMETALLIC COMPOUNDS.

    DTIC Science & Technology

    AGING(MATERIALS), AGING(MATERIALS), INTERMETALLIC COMPOUNDS, VANADIUM ALLOYS, COBALT ALLOYS, NICKEL ALLOYS, MECHANICAL PROPERTIES, TEMPERATURE, TIME ... CRYSTAL STRUCTURE, MICROSTRUCTURE, HARDNESS, TRANSFORMATIONS, ELECTRICAL RESISTANCE, MEASUREMENT, MICROSCOPY, ALLOYS, METALLOGRAPHY, X RAY DIFFRACTION.

  9. Effects of filling material and laser power on the formation of intermetallic compounds during laser-assisted friction stir butt welding of steel and aluminum alloys

    NASA Astrophysics Data System (ADS)

    Fei, Xinjiang; Jin, Xiangzhong; Peng, Nanxiang; Ye, Ying; Wu, Sigen; Dai, Houfu

    2016-11-01

    In this paper, two kinds of materials, Ni and Zn, are selected as filling material during laser-assisted friction stir butt welding of Q235 steel and 6061-T6 aluminum alloy, and their influences on the formation of intermetallic compounds on the steel/aluminum interface of the joints were first studied. SEM was used to analyze the profile of the intermetallic compound layer and the fractography of tensile fracture surfaces. In addition, EDS was applied to investigate the types of the intermetallic compounds. The results indicate that a thin iron-abundant intermetallic compound layer forms and ductile fracture mode occurs when Ni is added, but a thick aluminum-abundant intermetallic compound layer generates and brittle fracture mode occurs when Zn is added. So the tensile strength of the welds with Ni as filling material is greater than that with Zn as filling material. Besides, the effect of laser power on the formation of intermetallic compound layer when Ni is added was investigated. The preheated temperature field produced by laser beam in the cross section of workpiece was calculated, and the tensile strength of the joints at different laser powers was tested. Results show that only when suitable laser power is adopted, can suitable preheating temperature of the steel reach, then can thin intermetallic compound layer form and high tensile strength of the joints reach. Either excessive or insufficient laser power will reduce the tensile strength of the joints.

  10. Formation of GaPd2 and GaPd intermetallic compounds on GaN(0001)

    NASA Astrophysics Data System (ADS)

    Grodzicki, M.; Mazur, P.; Pers, J.; Brona, J.; Zuber, S.; Ciszewski, A.

    2015-09-01

    Palladium was deposited gradually under ultrahigh vacuum onto a well-defined surface of (0001)-oriented n-type GaN, at room temperature. Each deposition step was followed by annealing. Physicochemical properties of the Pd adlayers were in situ investigated prior to and after annealing by the X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, low-energy electron diffraction, scanning tunneling microscopy and atomic force microscopy techniques. Annealing resulted in the formation of GaPd2 and GaPd intermetallic compounds at 550 °C and at 800 °C. Even for thicker layers, the compounds were strongly dispersed, forming 3D nanostructures. The substrate uncovered by the compounds revealed Ga-rich GaN(0001)-(1 × 1) surface. Formation of Ga-Pd-N bonds or Pd nitrides was not detected at the surface. The Ga-Pd intermetallic compound surface engineered on the GaN(0001) substrate can be used as the strongly dispersed catalyst or a model catalyst.

  11. Some statistics on intermetallic compounds.

    PubMed

    Dshemuchadse, Julia; Steurer, Walter

    2015-02-02

    It is still largely unknown why intermetallic phases show such a large variety of crystal structures, with unit cell sizes varying between 1 and more than 20 000 atoms. The goal of our study was, therefore, to get a general overview of the symmetries, unit cell sizes, stoichiometries, most frequent structure types, and their stability fields based on the Mendeleev numbers as ordering parameters. A total of 20829 structures crystallizing in 2166 structure types have been studied for this purpose. Thereby, the focus was on a subset of 6441 binary intermetallic compounds, which crystallize in 943 structure types.

  12. Enthalpies of formation of Cd–Pr intermetallic compounds and thermodynamic assessment of the Cd–Pr system

    PubMed Central

    Reichmann, Thomas L.; Richter, Klaus W.; Delsante, Simona; Borzone, Gabriella; Ipser, Herbert

    2014-01-01

    In the present study standard enthalpies of formation were measured by reaction and solution calorimetry at stoichiometric compositions of Cd2Pr, Cd3Pr, Cd58Pr13 and Cd6Pr. The corresponding values were determined to be −46.0, −38.8, −35.2 and −24.7 kJ/mol(at), respectively. These data together with thermodynamic data and phase diagram information from literature served as input data for a CALPHAD-type optimization of the Cd–Pr phase diagram. The complete composition range could be described precisely with the present models, both with respect to phase equilibria as well as to thermodynamic input data. The thermodynamic parameters of all intermetallic compounds were modelled following Neumann–Kopp rule. Temperature dependent contributions to the individual Gibbs energies were used for all compounds. Extended solid solubilities are well described for the low- and high-temperature modifications of Pr and also for the intermetallic compound CdPr. A quite good agreement with all viable data available from literature was found and is presented. PMID:25540475

  13. The Intermetallic Compound Formation for the Wire Bond Between an Al Pad and Ag-xPd Alloy Wire

    NASA Astrophysics Data System (ADS)

    Huang, Wei-Hsiang; Lin, Kwang-Lung; Lin, Yu-Wei; Cheng, Yun-Kai

    2016-12-01

    Silver-palladium alloy wire has been shown as an economical and reliable substitute for gold wire in various applications in the electronic packaging industry. The success of wire bonding relies on the formation of an interfacial intermetallic compound (IMC). This study is aimed to investigate the formation behavior of IMCs between an Al pad and Ag-Pd alloy wire with various Pd concentrations of 1.0-6.0% for the as-bonded commercial Ag/Al joint. The interfacial IMCs were investigated with scanning electron microscopy and energy-dispersive x-ray spectroscopy. The IMCs formed are separate (Ag, Pd)2Al and (Ag, Pd)3Al2 for a Ag6Pd wire bond, while (Ag, Pd)2Al and (Ag, Pd)3Al2 are mixed for the other Ag(1-4.5)Pd alloy wire bonds. The thickness of the total IMC layer varies from 0.65 μm for Ag1Pd to 0.91 μm for Ag6Pd, yet a minimum of 0.44 μm exists for Ag3.5Pd. The compound formation behavior was found to correspond with the Ag-Al phase diagram. After pressure cooker tests, a less stable IMC (Ag, Pd)3Al formed at the AgxPd/Al interface.

  14. Effect of Sn Grain Orientation on Formation of Cu6Sn5 Intermetallic Compound Under Current Stressing

    NASA Astrophysics Data System (ADS)

    Chen, Ming-Yao; Lin, Han-wen; Chen, Chih

    2016-12-01

    Solder joints with Cu/Sn-Ag/Cu structure and bump height of 15 μm have been used to investigate the electromigration phenomenon at different temperatures and current densities. Moreover, the grain orientation was analyzed using electron backscatter diffraction. It was found that the anisotropic properties of tin affected the formation rate of Cu-Sn intermetallic compounds (IMCs), and that the angle between the electron flow direction and tin grain orientation played an important role in the formation of Cu6Sn5 IMC. With changes in angle, the diffusion rate of copper atoms in tin also varied. When the c-axis of tin was parallel to the electron flux, copper atoms diffused rapidly, resulting in fast formation of Cu-Sn IMCs. On the other hand, if the angle between the c-axis of the grain and the electron flow direction was large, the tin grains were more resistant to Cu diffusion during current stressing, leading to a very slow IMC formation rate.

  15. Influence of Ti and La Additions on the Formation of Intermetallic Compounds in the Al-Zn-Si Bath

    NASA Astrophysics Data System (ADS)

    Xu, Jin; Gu, Qin-Fen; Li, Qian; Lu, Hu-Sheng

    2016-12-01

    The effect of Ti and La additions on the formation of intermetallic compounds (IMCs) in the galvalume (55Al-Zn-1.6Si wt pct) bath was investigated experimentally and further studied with first-principles calculation. The studied baths contain: 1 wt pct Fe, with Ti content ranging from 0.05 to 0.15 wt pct and La content ranging from 0.05 to 0.30 wt pct. Combination of the experimental results with the thermodynamic analysis shows that the solubility of Fe in the alloy bath decreases with an increase of Ti content, which results in the formation of mass dross. Compared with the Ti-containing alloy, La promotes the formation of τ 5 phase (Fe2Al8Si). When both Ti and La are added, Fe4Al13, τ 5, τ 6 (β-Al4.5FeSi), TiAl3, and Ti2Al20La phases were observed. Since these IMCs would consume more Si in the bath, the decrease of Si content with Ti and La additions is more significant than that of the bath without these additions. Furthermore, the formation mechanism of Ti/TiAl3/Ti2La20La core-shell structure in the coating bath is proposed. This study has implications for strategic design of industry hot-dip production with exceptional mechanical properties of Al alloy coating.

  16. Effect of Sn Grain Orientation on Formation of Cu6Sn5 Intermetallic Compound Under Current Stressing

    NASA Astrophysics Data System (ADS)

    Chen, Ming-Yao; Lin, Han-wen; Chen, Chih

    2017-04-01

    Solder joints with Cu/Sn-Ag/Cu structure and bump height of 15 μm have been used to investigate the electromigration phenomenon at different temperatures and current densities. Moreover, the grain orientation was analyzed using electron backscatter diffraction. It was found that the anisotropic properties of tin affected the formation rate of Cu-Sn intermetallic compounds (IMCs), and that the angle between the electron flow direction and tin grain orientation played an important role in the formation of Cu6Sn5 IMC. With changes in angle, the diffusion rate of copper atoms in tin also varied. When the c-axis of tin was parallel to the electron flux, copper atoms diffused rapidly, resulting in fast formation of Cu-Sn IMCs. On the other hand, if the angle between the c-axis of the grain and the electron flow direction was large, the tin grains were more resistant to Cu diffusion during current stressing, leading to a very slow IMC formation rate.

  17. Ultrarapid formation of homogeneous Cu6Sn5 and Cu3Sn intermetallic compound joints at room temperature using ultrasonic waves.

    PubMed

    Li, Zhuolin; Li, Mingyu; Xiao, Yong; Wang, Chunqing

    2014-05-01

    Homogeneous intermetallic compound joints are demanded by the semiconductor industry because of their high melting point. In the present work, ultrasonic vibration was applied to Cu/Sn foil/Cu interconnection system at room temperature to form homogeneous Cu6Sn5 and Cu3Sn joints. Compared with other studies based on transient-liquid-phase soldering, the processing time of our method was dramatically reduced from several hours to several seconds. This ultrarapid intermetallic phase formation process resulted from accelerated interdiffusion kinetics, which can be attributed to the sonochemical effects of acoustic cavitation at the interface between the liquid Sn and the solid Cu during the ultrasonic bonding process.

  18. Electrocatalytic Formation and Inactivation of Intermetallic Compounds in Electrorefining of Silicon

    NASA Astrophysics Data System (ADS)

    Olsen, Espen; Rolseth, Sverre; Thonstad, Jomar

    2010-08-01

    Silicon for solar cell purposes is today produced by an energy intensive process exhibiting high irreversible thermodynamic energy losses. The purity of the product; 99,9999999 pct (9N), far exceeds what is generally accepted to be the requirements for photovoltaic purposes (4-6N). According to thermodynamics, all elements except boron may be removed from silicon by three layer electrochemical refining above the melting point of Si. Boron, on the other hand, shows higher affinity to specific transition metals compared to silicon. This may be exploited by applying two principles in parallel; electrochemical refining and electrocatalyzed reaction-precipitation of transition metal borides as heavy, stable particles. In this study we report on the formation of such compounds at the cathode-electrolyte interface during electrochemical refining. The trends and mechanisms observed in the laboratory scale investigation indicate that high purity silicon may be produced in industrial scale reactors at low cost- and energy intensity.

  19. New twisted intermetallic compound superconductor: A concept

    NASA Technical Reports Server (NTRS)

    Coles, W. D.; Brown, G. V.; Laurence, J. C.

    1972-01-01

    Method for processing Nb3Sn and other intermetallic compound superconductors produces a twisted, stabilized wire or tube which can be used to wind electromagnetics, armatures, rotors, and field windings for motors and generators as well as other magnetic devices.

  20. First-principles studies of Ni-Ta intermetallic compounds

    SciTech Connect

    Zhou Yi; Wen Bin; Ma Yunqing; Melnik, Roderick; Liu Xingjun

    2012-03-15

    The structural properties, heats of formation, elastic properties, and electronic structures of Ni-Ta intermetallic compounds are investigated in detail based on density functional theory. Our results indicate that all Ni-Ta intermetallic compounds calculated here are mechanically stable except for P21/m-Ni{sub 3}Ta and hc-NiTa{sub 2}. Furthermore, we found that Pmmn-Ni{sub 3}Ta is the ground state stable phase of Ni{sub 3}Ta polymorphs. The polycrystalline elastic modulus has been deduced by using the Voigt-Reuss-Hill approximation. All Ni-Ta intermetallic compounds in our study, except for NiTa, are ductile materials by corresponding G/K values and poisson's ratio. The calculated heats of formation demonstrated that Ni{sub 2}Ta are thermodynamically unstable. Our results also indicated that all Ni-Ta intermetallic compounds analyzed here are conductors. The density of state demonstrated the structure stability increases with the Ta concentration. - Graphical abstract: Mechanical properties and formation heats of Ni-Ta intermetallic compounds are discussed in detail in this paper. Highlights: Black-Right-Pointing-Pointer Ni-Ta intermetallic compounds are investigated by first principle calculations. Black-Right-Pointing-Pointer P21/m-Ni{sub 3}Ta and hc-NiTa{sub 2} are mechanically unstable phases. Black-Right-Pointing-Pointer Pmmn-Ni{sub 3}Ta is ground stable phase of Ni{sub 3}Ta polymorphs. Black-Right-Pointing-Pointer All Ni-Ta intermetallic compounds are conducting materials.

  1. Crystal structure analysis of intermetallic compounds

    NASA Technical Reports Server (NTRS)

    Conner, R. A., Jr.; Downey, J. W.; Dwight, A. E.

    1968-01-01

    Study concerns crystal structures and lattice parameters for a number of new intermetallic compounds. Crystal structure data have been collected on equiatomic compounds, formed between an element of the Sc, Ti, V, or Cr group and an element of the Co or Ni group. The data, obtained by conventional methods, are presented in an easily usable tabular form.

  2. Chemical effect on diffusion in intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Chen, Yi-Ting

    With the trend of big data and the Internet of things, we live in a world full of personal electronic devices and small electronic devices. In order to make the devices more powerful, advanced electronic packaging such as wafer level packaging or 3D IC packaging play an important role. Furthermore, ?-bumps, which connect silicon dies together with dimension less than 10 ?m, are crucial parts in advanced packaging. Owing to the dimension of ?-bumps, they transform into intermetallic compound from tin based solder after the liquid state bonding process. Moreover, many new reliability issues will occur in electronic packaging when the bonding materials change; in this case, we no longer have tin based solder joint, instead, we have intermetallic compound ?-bumps. Most of the potential reliability issues in intermetallic compounds are caused by the chemical reactions driven by atomic diffusion in the material; thus, to know the diffusivities of atoms inside a material is significant and can help us to further analyze the reliability issues. However, we are lacking these kinds of data in intermetallic compound because there are some problems if used traditional Darken's analysis. Therefore, we considered Wagner diffusivity in our system to solve the problems and applied the concept of chemical effect on diffusion by taking the advantage that large amount of energy will release when compounds formed. Moreover, by inventing the holes markers made by Focus ion beam (FIB), we can conduct the diffusion experiment and obtain the tracer diffusivities of atoms inside the intermetallic compound. We applied the technique on Ni3Sn4 and Cu3Sn, which are two of the most common materials in electronic packaging, and the tracer diffusivities are measured under several different temperatures; moreover, microstructure of the intermetallic compounds are investigated to ensure the diffusion environment. Additionally, the detail diffusion mechanism was also discussed in aspect of diffusion

  3. More statistics on intermetallic compounds - ternary phases.

    PubMed

    Dshemuchadse, Julia; Steurer, Walter

    2015-05-01

    How many different intermetallic compounds are known so far, and in how many different structure types do they crystallize? What are their chemical compositions, the most abundant ones and the rarest ones? These are some of the questions we are trying to find answers for in our statistical analysis of the structures of the 20,829 intermetallic phases included in the database Pearson's Crystal Data, with the goal of gaining insight into some of their ordering principles. In the present paper, we focus on the subset of 13,026 ternary intermetallics, which crystallize in 1391 different structure types; remarkably, 667 of them have just one representative. What makes these 667 structures so unique that they are not adopted by any other of the known intermetallic compounds? Notably, ternary compounds are known in only 5109 of the 85,320 theoretically possible ternary intermetallic systems so far. In order to get an overview of their chemical compositions we use structure maps with Mendeleev numbers as ordering parameters.

  4. Oxygen stabilized zirconium vanadium intermetallic compound

    DOEpatents

    Mendelsohn, Marshall H.; Gruen, Dieter M.

    1982-01-01

    An oxygen stabilized intermetallic compound having the formula Zr.sub.x OV.sub.y where x=0.7 to 2.0 and y=0.18 to 0.33. The compound is capable of reversibly sorbing hydrogen at temperatures from -196.degree. C. to 450.degree. C. at pressures down to 10.sup.-6 Torr. The compound is also capable of selectively sorbing hydrogen from gaseous mixtures in the presence of CO and CO.sub.2.

  5. Surface structures of In-Pd intermetallic compounds. I. Experimental study of In thin films on Pd(111) and alloy formation

    SciTech Connect

    McGuirk, G. M.; Ledieu, J.; Gaudry, É.; Weerd, M.-C. de; Fournée, V.

    2014-08-28

    A combination of experimental methods was used to study the structure of In thin films deposited on the Pd(111) surface and the alloying behavior. X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED), and scanning tunneling microscopy results indicate that surface alloying takes place at room temperature. Below 2 monolayer equivalents (MLEs), the LEED patterns show the formation of three rotational domains of InPd(110) of poor structural quality on top of the Pd(111) substrate. Both core-levels and valence band XPS spectra show that the surface alloy does not yet exhibit the electronic structure characteristic of the 1:1 intermetallic compound under these conditions. Annealing the 1 MLE thin film up to 690 K yields to a transition from a multilayer InPd near-surface intermetallic phase to a monolayer-like surface alloy exhibiting a well ordered (√(3)×√(3)) R30{sup ∘} superstructure and an estimated composition close to In{sub 2}Pd{sub 3}. Annealing above 690 K leads to further In depletion and a (1 × 1) pattern is recovered. The (√(3)×√(3)) R30{sup ∘} superstructure is not observed for thicker films. Successive annealing of the 2 MLE thin film leads the progressive disappearance of the InPd diffraction spots till a sharp (1 × 1) pattern is recovered above 690 K. In the high coverage regime (from 4 to 35 MLE), the formation of three rotational domains of a bcc-In{sub 7}Pd{sub 3} compound with (110) orientation is observed. This In-rich phase probably grows on top of interfacial InPd(110) domains and is metastable. It transforms into a pure InPd(110) near-surface intermetallic phase in a temperature range between 500 and 600 K depending on the initial coverage. At this stage, the surface alloy exhibits core-level chemical shifts and valence band (VB) spectra identical to those of the 1:1 InPd intermetallic compound and resembling Cu-like density of states. Annealing at higher temperatures yields to a decrease of the In

  6. Influence of nanoparticle addition on the formation and growth of intermetallic compounds (IMCs) in Cu/Sn-Ag-Cu/Cu solder joint during different thermal conditions.

    PubMed

    Ting Tan, Ai; Wen Tan, Ai; Yusof, Farazila

    2015-06-01

    Nanocomposite lead-free solders are gaining prominence as replacements for conventional lead-free solders such as Sn-Ag-Cu solder in the electronic packaging industry. They are fabricated by adding nanoparticles such as metallic and ceramic particles into conventional lead-free solder. It is reported that the addition of such nanoparticles could strengthen the solder matrix, refine the intermetallic compounds (IMCs) formed and suppress the growth of IMCs when the joint is subjected to different thermal conditions such as thermal aging and thermal cycling. In this paper, we first review the fundamental studies on the formation and growth of IMCs in lead-free solder joints. Subsequently, we discuss the effect of the addition of nanoparticles on IMC formation and their growth under several thermal conditions. Finally, an outlook on the future growth of research in the fabrication of nanocomposite solder is provided.

  7. Influence of nanoparticle addition on the formation and growth of intermetallic compounds (IMCs) in Cu/Sn–Ag–Cu/Cu solder joint during different thermal conditions

    PubMed Central

    Ting Tan, Ai; Wen Tan, Ai; Yusof, Farazila

    2015-01-01

    Nanocomposite lead-free solders are gaining prominence as replacements for conventional lead-free solders such as Sn–Ag–Cu solder in the electronic packaging industry. They are fabricated by adding nanoparticles such as metallic and ceramic particles into conventional lead-free solder. It is reported that the addition of such nanoparticles could strengthen the solder matrix, refine the intermetallic compounds (IMCs) formed and suppress the growth of IMCs when the joint is subjected to different thermal conditions such as thermal aging and thermal cycling. In this paper, we first review the fundamental studies on the formation and growth of IMCs in lead-free solder joints. Subsequently, we discuss the effect of the addition of nanoparticles on IMC formation and their growth under several thermal conditions. Finally, an outlook on the future growth of research in the fabrication of nanocomposite solder is provided. PMID:27877786

  8. Heats of formation in transition intermetallic alloys

    SciTech Connect

    Pasturel, A.; Colinet, C.; Hicter, P.

    1984-07-01

    The heats of formation in intermetallic alloys are calculated within a tight-binding scheme for the d band. The difference in bandwidth between the metals and the difference between their energy levels are two dominant effects in determination of the formation energy. The influence of charge transfer on alloy formation is studied.

  9. Forging of FeAl intermetallic compounds

    SciTech Connect

    Flores, O.; Juarez, J.; Campillo, B.; Martinez, L.; Schneibel, J.H.

    1994-09-01

    Much activity has been concentrated on the development of intermetallic compounds with the aim of improving tensile ductility, fracture toughness and high notch sensitivity in order to develop an attractive combination of properties for high and low temperature applications. This paper reports experience in processing and forging of FeAl intermetallic of B2 type. During the experiments two different temperatures were employed, and the specimens were forged after annealing in air, 10{sup {minus}2} torr vacuum and argon. From the results it was learned that annealing FeAl in argon atmosphere prior to forging resulted in better deformation behavior than for the other two environments. For the higher forging temperature used in the experiments (700C), the as-cast microstructure becomes partially recrystallized.

  10. Intermetallic compounds in heterogeneous catalysis-a quickly developing field.

    PubMed

    Armbrüster, Marc; Schlögl, Robert; Grin, Yuri

    2014-06-01

    The application of intermetallic compounds for understanding in heterogeneous catalysis developed in an excellent way during the last decade. This review provides an overview of concepts and developments revealing the potential of intermetallic compounds in fundamental as well as applied catalysis research. Intermetallic compounds may be considered as platform materials to address current and future catalytic challenges, e.g. in respect to the energy transition.

  11. Intermetallic compounds in heterogeneous catalysis—a quickly developing field

    PubMed Central

    Armbrüster, Marc; Schlögl, Robert; Grin, Yuri

    2014-01-01

    The application of intermetallic compounds for understanding in heterogeneous catalysis developed in an excellent way during the last decade. This review provides an overview of concepts and developments revealing the potential of intermetallic compounds in fundamental as well as applied catalysis research. Intermetallic compounds may be considered as platform materials to address current and future catalytic challenges, e.g. in respect to the energy transition. PMID:27877674

  12. SYNTHESIS AND CHARACTERIZATION OF NEW INTERMETALLIC COMPOUNDS

    SciTech Connect

    Professor Monica Sorescu

    2003-05-07

    This six-month work is focused mainly on the properties of novel magnetic intermetallics. In the first project, we synthesized several 2:17 intermetallic compounds, namely Nd{sub 2}Fe{sub 15}Si{sub 2}, Nd{sub 2}Fe{sub 15}Al{sub 2}2, Nd{sub 2}Fe{sub 15}SiAl and Nd{sub 2}Fe{sub 15}SiMn, as well as several 1:12 intermetallic compounds, such as NdFe{sub 10}Si{sub 2}, NdFe{sub 10}Al{sub 2}, NdFe{sub 10}SiAl and NdFe{sub 10}MnAl. In the second project, seven compositions of Nd{sub x}Fe{sub 100-x-y}B{sub y} ribbons were prepared by a melt spinning method with Nd and B content increasing from 7.3 and 3.6 to 11 and 6, respectively. The alloys were annealed under optimized conditions to obtain a composite material consisting of the hard magnetic Nd{sub 2}Fe{sub 14}B and soft magnetic {alpha}-Fe phases, typical of a spring magnet structure. In the third project, intermetallic compounds of the type Zr{sub 1}Cr{sub 1}Fe{sub 1}T{sub 0.8} with T=Al, Co and Fe were subjected to hydrogenation. In the fourth project, we performed three crucial experiments. In the first experiment, we subjected a mixture of Fe{sub 3}O{sub 4} and Fe(80-20 wt%) to mechanochemical activation by high-energy ball milling, for time periods ranging from 0.5 to 14 hours. In the second experiment, we ball-milled Fe{sub 3}O{sub 4}:Co{sup 2+} (x=0.1) for time intervals between 2.5 and 17.5 hours. Finally, we exposed a mixture of Fe{sub 3}O{sub 4} and Co(80-20 wt%) to mechanochemical activation for time periods ranging from 0.5 to 10 hours. In all cases, the structural and magnetic properties of the systems involved were elucidated by X-ray diffraction (XRD), Moessbauer spectroscopy and hysteresis loop measurements. The four projects resulted in four papers, which are currently being considered for publication in Intermetallics, IEEE Transactions on Magnetics, Journal of Materials Science Letters and Journal of Materials Science. The contributions reveal for the first time in literature the effect of

  13. Sonochemical formation of intermetallic coatings

    SciTech Connect

    Sweet, J.D.; Casadonte, D.J. Jr.

    1994-11-01

    An energy-dispersive X-ray (EDX) study of the agglomerates produced during the sonication of a series of mixed-metal powders in decane indicates that metal particles are both fused by the action of ultrasound and develop coatings which are intermetallic in nature. The principal mechanism of these effects is believed to be interparticle collision caused by the rapid movement of particles of less than 50 {mu}m diameter which are propelled by shockwaves generated at cavitation sites. By examination of mixed-metal systems including Ni/Co, Al/Ni, Al/Co, Ni/Mg, and Cu/Mo with substantially different tribological characteristics, it has been determined that the coatings are generated by both adhesive wear and direct impact. The fusion of Cu and Mo is particularly intriguing, as these two metals are immiscible below 1000{degrees}C. This indicates the enormous impact temperatures produced in sonically induced collisions. The mechanisms of intermetallic coatings produced via ultrasound are discussed. 26 refs., 4 figs.

  14. Service limitations for oxidation resistant intermetallic compounds

    SciTech Connect

    Smialek, J.L.; Nesbitt, J.A.; Brindley, W.J.; Brady, M.P.; Doychak, J.; Dickerson, R.M.; Hull, D.R.

    1995-07-01

    Oxidation resistant intermetallic compounds based on NiAl, TiAl, and MoSi{sub 2} are of interest for high temperature applications. Each system exhibits different life-limiting degradation modes due to oxidation. {beta}-NiAl forms protective {alpha}-Al{sub 2}O scales. Breakdown follows well-established diffusion controlled processes resulting in survival for thousands of hours. The effect of thermal cycling and spalling is well established. Ti{sub 3}Al and TiAl compounds form less protective mixed TiO{sub 2} and Al{sub 2}O{sub 3} scales. However at realistic use temperatures (600--800 C), scale growth rates are acceptably low. The critical factor is embrittlement due to interstitial oxygen diffusion over a matter of hours. Solutions based on alloy development and coatings have not been satisfactory. MoSi{sub 2} materials exhibit very low oxidation rates at very high temperatures. However, low temperature (500 C) pest oxidation can be a catastrophic transient effect. Material integrity is a key factor. Fracture occurs because of accelerated growth of non-protective mixed MoO{sub 2}-SiO{sub 2} scales in pores and microcracks.

  15. FORMATION OF INTERMETALLIC COMPOUND DISPERSIONS

    DOEpatents

    Bryner, J.S.

    1959-12-01

    BS>A method is presented for preparing dispersions containing thorium bismuthide in equiaxed form and having an average particle size of about 30 microns. Thorium particles having one dimension not greater than 0.015 in. are immersed in liquid bismuth at a temperature between 500 and 600 deg C, the quantity of thorium being in excess of its solubility in the bismuth.

  16. Enhancement on wettability and intermetallic compound formation with an addition of Al on Sn-0.7Cu lead-free solder fabricated via powder metallurgy method

    NASA Astrophysics Data System (ADS)

    Adli, Nisrin; Razak, Nurul Razliana Abdul; Saud, Norainiza

    2016-07-01

    Due to the toxicity of lead (Pb), the exploration of another possibility for lead-free solder is necessary. Nowadays, SnCu alloys are being established as one of the lead-free solder alternatives. In this study, Sn-0.7Cu lead-free solder with an addition of 1wt% and 5wt% Al were investigated by using powder metallurgy method. The effect of Al addition on the wettability and intermetallic compound thickness (IMC) of Sn-0.7Cu-Al lead-free solder were appraised. Results showed that Al having a high potential to enhance Sn-0.7Cu lead-free solder due to its good wetting and reduction of IMC thickness. The contact angle and IMC of the Sn-0.7Cu-Al lead-free solder were decreased by 14.32% and 40% as the Al content increased from 1 wt% to 5 wt%.

  17. Explosive reaction pressing of intermetallic compounds from stoichiometric powder mixtures

    SciTech Connect

    Kochsiek, D.; Pruemmer, R.; Brunold, A.

    1995-09-01

    Intermetallic NiAl, TiAl, and TiAl{sub 3} were synthesized by shock compression experiments from stoichiometric powder mixtures of nickel and aluminium as well as of titanium and aluminium. Good consolidation and complete intermetallic reaction were achieved by the direct method of explosive compaction. For each powder mixture, a certain individual threshold pressure has to be exceeded in order to initiate intermetallic reaction. The reacting compounds melted completely with subsequent rapid solidification during the passage of the shock wave. The new material shows high hardness. Pores are formed by gaseous reaction products in the NiAl and TiAl{sub 3} compacts. The TiAl structure is fully-dense and dendritic.

  18. Magnetization of RFe3 intermetallic compounds: Molecular field theory analysis

    NASA Astrophysics Data System (ADS)

    Herbst, J. F.; Croat, J. J.

    1982-06-01

    We report magnetization measurements of all RFe3 intermetallic compounds known to form (R = Y, Sm, Gd, Tb, Dy, Ho, Er, Tm). A two-sublattice molecular field model is employed to analyze the data except in the case of YFe3, for which one magnetic sublattice is assumed. In general, the model adequately describes the temperature dependence of the magnetization. For SmFe3 our results suggest that the samarium and iron moments are ferromagnetically coupled.

  19. Oxygen-stabilized zirconium-vanadium intermetallic compound

    DOEpatents

    Mendelsohn, M.H.; Gruen, D.M.

    1981-10-06

    An oxygen stabilized intermetallic compound having the formula Zr/sub x/OV/sub y/ where x = 0.7 to 2.0 and y = 0.18 to 0.33 is described. The compound is capable of reversibly sorbing hydrogen at temperatures from - 196/sup 0/C to 450/sup 0/C at pressures down to 10/sup -6/ Torr. The compound is also capable of selectively sorbing hydrogen from gaseous mixtures in the presence of CO and CO/sub 2/.

  20. Point Defects Quenched in Nickel Aluminide and Related Intermetallic Compounds

    NASA Astrophysics Data System (ADS)

    Fan, Jiawen

    Point defects in the highly ordered B2 compounds NiAl, CoAl and FeAl were studied using the perturbed gammagamma angular correlations (PAC) technique. Quadrupole interactions detected at dilute ^{111}In probes on Al sites in NiAl and CoAl were identified with complexes containing one or two vacancies in the first atomic shell. Measurements on rapidly quenched NiAl and CoAl exhibited increases in site fractions of vacancy-probe complexes caused by formation of thermal defects. Site fractions were analyzed using the law of mass action to obtain absolute vacancy concentrations. PAC is shown to be a powerful new technique for the quantitative study of equilibrium defects in solids. For NiAl, the vacancy concentration quenched-in from a given temperature was found to be independent of composition over the range 50.4 -53.5 at.% Ni, identifying the Schottky defect (vacancy pair) as the dominant equilibrium defect, and ruling out the so-called triple defect. Formation energies and entropies of Schottky pairs were determined to be 2.66(8) and 3.48(12) eV, and 12(1) and 17(2) k_{rm B}, respectively, for NiAl and CoAl. The entropies suggest huge vacancy concentrations, 13%, at the melting temperatures of NiAl and CoAl. Migration energies of Ni and Co vacancies were found to be 1.8(2) and 2.5(2) eV, respectively. FeAl exhibited complex behavior. A low-temperature regime was detected in NiAl and CoAl within which vacancies are mobile but do not anneal out, so that the vacancy concentration remains constant. In NiAl, this "bottleneck" regime extends from 350 to 700 ^circC. Vacancies were found to be bound to the In probes with an energy very close to 0.20 eV in NiAl and CoAl. An explanation of the bottleneck is proposed in terms of saturation of all lattice sinks. This annealing bottleneck should exist in a wide range of intermetallic compounds when there is a sufficiently high vacancy concentration.

  1. High Temperature Advanced Structural Composites. Book 1: Executive Summary and Intermetallic Compounds

    DTIC Science & Technology

    1993-04-02

    reprints of papers on Intermetallic Compounds. Volume two contains reprints of papers on Ceramic Matrix Composites, Fiber Processi and Properties and...SUMMARY OF TABLE OF CONTENTS BOOK 1: EXECUTIVE SUMMARY INTERMETALLIC COMPOUNDS BOOK 2: CERAMIC MATRIX COMPOSITES FIBER PROCESSING AND PROPERTIES INTERFACES...COMPOUNDS .................................. 1 1. Processing ...................... ................... 1 2. Mechanical Properties

  2. Unexpected Xe anions in XeLin intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Liu, Zhen; Botana, Jorge; Miao, Maosheng; Yan, Dadong

    2017-01-01

    The reactivity of Xe is important in both fundamental chemistry and geological science. The discovery of the reductive reactivity of Xe extended the doctrinal boundary of chemistry for which a completed shell is inert to reaction. The oxidation of Xe by various elements has been explored. On the other hand, the opposite chemical inclination, i.e., gaining electrons and forming anions, has not been thoroughly studied for Xe or other noble-gas elements. In this work, we demonstrate, using first-principles calculations and an efficient structure prediction method, that Xe can form stable \\text{XeLi}n (n=1\\text{--}5) compounds under high pressure. These compounds are intermetallic and Xe are negatively charged. The stability of these compounds indicates that atoms or ions with completely filled shell may still gain electrons in chemical reactions.

  3. Structural and Electronic Investigations of Complex Intermetallic Compounds

    SciTech Connect

    Ko, Hyunjin

    2008-01-01

    In solid state chemistry, numerous investigations have been attempted to address the relationships between chemical structure and physical properties. Such questions include: (1) How can we understand the driving forces of the atomic arrangements in complex solids that exhibit interesting chemical and physical properties? (2) How do different elements distribute themselves in a solid-state structure? (3) Can we develop a chemical understanding to predict the effects of valence electron concentration on the structures and magnetic ordering of systems by both experimental and theoretical means? Although these issues are relevant to various compound classes, intermetallic compounds are especially interesting and well suited for a joint experimental and theoretical effort. For intermetallic compounds, the questions listed above are difficult to answer since many of the constituent atoms simply do not crystallize in the same manner as in their separate, elemental structures. Also, theoretical studies suggest that the energy differences between various structural alternatives are small. For example, Al and Ga both belong in the same group on the Periodic Table of Elements and share many similar chemical properties. Al crystallizes in the fcc lattice with 4 atoms per unit cell and Ga crystallizes in an orthorhombic unit cell lattice with 8 atoms per unit cell, which are both fairly simple structures (Figure 1). However, when combined with Mn, which itself has a very complex cubic crystal structure with 58 atoms per unit cell, the resulting intermetallic compounds crystallize in a completely different fashion. At the 1:1 stoichiometry, MnAl forms a very simple tetragonal lattice with two atoms per primitive unit cell, while MnGa crystallizes in a complicated rhombohedral unit cell with 26 atoms within the primitive unit cell. The mechanisms influencing the arrangements of atoms in numerous crystal structures have been studied theoretically by calculating electronic

  4. Development of New Cryocooler Regenerator Materials-Ductile Intermetallic Compounds

    SciTech Connect

    K.A. Gschneidner; A.O. Pecharsky; V.K. Pecharsky

    2004-09-30

    The volumetric heat capacities of a number of binary and ternary Er- and Tm-based intermetallic compounds, which exhibited substantial ductilities, were measured from {approx}3 to {approx}350 K. They have the RM stoichiometry (where R = Er or Tm, and M is a main group or transition metal) and crystallize in the CsCl-type structure. The heat capacities of the Tm-based compounds are in general larger than the corresponding Er-based materials. Many of them have heat capacities which are significantly larger than those of the low temperature (<15 K) prototype cryocooler regenerator materials HoCu{sub 2}, Er{sub 3}Ni and ErNi. Utilization of the new materials as regenerators in the various cryocoolers should improve the performance of these refrigeration units for cooling below 15 K.

  5. Superplasticity and solid state bonding of the TiAl intermetallic compound with micro- and submicrocrystalline structure

    SciTech Connect

    Lutfullin, R.Ya.; Imayev, R.M.; Kaibyshev, O.A.; Hismatullin, F.N.; Imayev, V.M.

    1995-11-01

    The use of superplastic phenomenon makes it possible to reduce considerably the temperature of solid state bonding of the TiAl intermetallic compound as compared with conventional diffusion bonding. At decreasing the superplastic deformation temperature due to the reduction of the grain size an adequate decrease of the temperature threshold of solid state weldability of the TiAl intermetallic compound was observed. In the TiAl intermetallic compound with submicrocrystalline grain size the formation of a sound solid state joint occurs in the process of deformation at the temperature t = 850 C and strain {var_epsilon} = 10%. Since the temperature-strain-rate conditions of solid state bonding and those of superplasticity coincide, it is assumed that the mechanism controlling the bonding process is grain boundary sliding, the main deformation mechanism of superplasticity.

  6. Intermetallic Phase Formation in Explosively Welded Al/Cu Bimetals

    NASA Astrophysics Data System (ADS)

    Amani, H.; Soltanieh, M.

    2016-08-01

    Diffusion couples of aluminum and copper were fabricated by explosive welding process. The interface evolution caused by annealing at different temperatures and time durations was investigated by means of optical microscopy, scanning electron microscopy equipped with energy dispersive spectroscopy, and x-ray diffraction. Annealing in the temperature range of 573 K to 773 K (300 °C to 500 °C) up to 408 hours showed that four types of intermetallic layers have been formed at the interface, namely Al2Cu, AlCu, Al3Cu4, and Al4Cu9. Moreover, it was observed that iron trace in aluminum caused the formation of Fe-bearing intermetallics in Al, which is near the interface of the Al-Cu intermetallic layers. Finally, the activation energies for the growth of Al2Cu, AlCu + Al3Cu4, Al4Cu9, and the total intermetallic layer were calculated to be about 83.3, 112.8, 121.6, and 109.4 kJ/mol, respectively. Considering common welding methods ( i.e., explosive welding, cold rolling, and friction welding), although there is a great difference in welding mechanism, it is found that the total activation energy is approximately the same.

  7. CO2 laser welding of titanium aluminide intermetallic compound

    NASA Astrophysics Data System (ADS)

    Kuwahara, Gaku; Yamaguchi, Shigeru; Nanri, Kenzo; Ootani, Masanori; Seto, Sachio; Arai, Mikiya; Fujioka, Tomoo

    2000-02-01

    Titanium aluminide intermetallic compound is studied to find out good welding conditions using CO2 laser irradiation. In the experiment, we used the casting titanium aluminide containing iron, vanadium and boron with a thickness of 2 mm. We carried out bead-on-plate laser welding at various initial temperatures of specimens varied from room temperature to 873 [K] in inert gas environment filled with argon. We measured fused depth, bead width and Vickers hardness. As a result of experiments, welding speeds that allow full bead-on- plate welding to be possible were strongly by dependent on the initial temperature, 3000 [mm/min], initial temperature 873 [K], 2600 [mm/mm], initial temperature 673 [K], and 2000 [mm/min] with 300 [K]. Transverse crack-free welding was achieved, when initial temperature was at 873 [K].

  8. Alumina as diffusion barrier to intermetallic formation in thermal interface materials made from indium and copper

    NASA Astrophysics Data System (ADS)

    Saleh, Ibrahim Khalifa

    Indium and copper react at wide range of temperatures to form intermetallic compounds that have different physical, mechanical and thermal properties. Liquid Phase Sintered indium-copper composite long-term performance as thermal interface material is adversely affected by the evolution of the intermetallic. In this study, i) the effect of intermetallic formation and growth on the performance of Liquid Phase Sintered copper-indium composite, ii) the effect of alumina as diffusion barrier between indium and copper, (iii) thermal stability and wettability between indium and alumina, iv) the indium and quartz wettability, v) indium and tungsten oxide wettability have been studied. Deleterious effect of the intermetallic formation and growth on the thermal and mechanical properties has been observed. 5nm of alumina deposited by Atomic Layer Deposition on flat copper surface has been optimized to prevent diffusion process between indium and copper at 120°C. 15nm of alumina prevented the reaction at 230°C. Instability of indium thin film thermally deposited on sapphire substrate was observed. Also, decrease in the sintering density of indium-alumina composite with increasing temperature was observed. The dewetting contact angle between liquid indium and sapphire was ˜127°. The wetting experiments between indium and different oxides showed that indium wets tungsten oxide and quartz..

  9. Ultra-high vacuum compatible preparation chain for intermetallic compounds.

    PubMed

    Bauer, A; Benka, G; Regnat, A; Franz, C; Pfleiderer, C

    2016-11-01

    We report the development of a versatile material preparation chain for intermetallic compounds, which focuses on the realization of a high-purity growth environment. The preparation chain comprises an argon glovebox, an inductively heated horizontal cold boat furnace, an arc melting furnace, an inductively heated rod casting furnace, an optically heated floating-zone furnace, a resistively heated annealing furnace, and an inductively heated annealing furnace. The cold boat furnace and the arc melting furnace may be loaded from the glovebox by means of a load-lock permitting to synthesize compounds starting with air-sensitive elements while handling the constituents exclusively in an inert gas atmosphere. All furnaces are all-metal sealed, bakeable, and may be pumped to ultra-high vacuum. We find that the latter represents an important prerequisite for handling compounds with high vapor pressure under high-purity argon atmosphere. We illustrate the operational aspects of the preparation chain in terms of the single-crystal growth of the heavy-fermion compound CeNi2Ge2.

  10. Intermetallic compounds as negative electrodes of Ni/MH batteries

    NASA Astrophysics Data System (ADS)

    Cuevas, F.; Joubert, J.-M.; Latroche, M.; Percheron-Guégan, A.

    2001-04-01

    This review is devoted to the main families of thermodynamically stable intermetallic compounds (AB5-, AB2- and AB-type alloys) that have been researched in the last thirty years as materials for negative electrodes in nickel-metal hydride batteries. The crystal structure of these compounds and their hydrides is widely described. Their solid-gas hydrogenation properties and, particularly, the related desorption isotherm curves are examined as a useful criterion for the selection of suitable battery materials. The electrochemical performances obtained with these alloys are reported and the given solutions to common problems such as corrosion, passivation, decrepitation and short cycle life are discussed. Only AB5-based compounds have achieved, up to now, enough development for being widely present on the market, and exhibit improved battery performances in comparison with the polluting Ni/Cd batteries. The high capacity of AB2-based compounds and the remarkable electrochemical activity of some AB-based alloys make, however, further research on all the reviewed families still valuable.

  11. Ultra-high vacuum compatible preparation chain for intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Bauer, A.; Benka, G.; Regnat, A.; Franz, C.; Pfleiderer, C.

    2016-11-01

    We report the development of a versatile material preparation chain for intermetallic compounds, which focuses on the realization of a high-purity growth environment. The preparation chain comprises an argon glovebox, an inductively heated horizontal cold boat furnace, an arc melting furnace, an inductively heated rod casting furnace, an optically heated floating-zone furnace, a resistively heated annealing furnace, and an inductively heated annealing furnace. The cold boat furnace and the arc melting furnace may be loaded from the glovebox by means of a load-lock permitting to synthesize compounds starting with air-sensitive elements while handling the constituents exclusively in an inert gas atmosphere. All furnaces are all-metal sealed, bakeable, and may be pumped to ultra-high vacuum. We find that the latter represents an important prerequisite for handling compounds with high vapor pressure under high-purity argon atmosphere. We illustrate the operational aspects of the preparation chain in terms of the single-crystal growth of the heavy-fermion compound CeNi2Ge2.

  12. Micromechanisms of intergranular brittle ftacture in intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Vitek, V.

    1991-06-01

    Grain boundaries in intermetallic compounds such as Ni3A1 are inherently brittle. The reason is usually sought in grain boundary cohesion but in metals even brittle fracture is accompanied by some local plasticity and thus not only cohesion but also dislocation mobility in the boundary region need to be studied. We first discuss here the role of an irreversible shear deformation at the crack tip during microcrack propagation assuming that these two processes are concomitant. It is shown that a pre-existing crack cannot propagate in a brittle manner once the dislocation emission occurs. However, if a microcrack nucleates during loading it can propagate concurrently with the development of the irreversible shear deformation at the crack tip. The latter is then the major energy dissipating process. In the second part of this paper we present results of atomistic studies of grain boundaries in Ni3A1 and CU3Au which suggest that substantial structural differences exist between strongly and weakly ordered L12 alloys. We discuss then the consequence of these differences for intergranular brittleness in the framework of the above model for microcrack propagation. On this basis we propose an explanation for the intrinsic intergranular brittleness in some L12 alloys and relate it directly to the strength of ordering. Les joints de grains dans les composés intermétalliques de type Ni3AI sont de nature fragile. L'origine de cette fragilité est habituellement dans la cohésion des joints de grains. Dans les métaux, cependant, même la rupture fragile est accompagnée d'une certaine déformation plastique locale, de telle sorte que non seulement la cohésion mais aussi la mobilité des dislocations près des joints doit être étudiée. Nous discutons d'abord le rôle d'une déformation en cisaillement irréversible en tête de fissure pendant la propagation de cette fissure, en supposant que les deux processus sont concomitants. Nous montrons qu'une fissure préexistante ne

  13. Hydrogen occupancy in the RNi{sub 4}Mg (R=Y, La, Ce, and Nd) intermetallic compounds and hydrides

    SciTech Connect

    Hahn-Herrera, Otto; Orgaz, Emilio; Aburto, Andrea

    2009-10-15

    We have investigated the effect of hydrogen on the electronic strtucture of the RNi{sub 4}Mg (R=Y, La, Ce, Pr, and Nd) intermetallics. By means of a two-step approach, the projected plane-wave and linearized plane-waves methods, we studied the hydrogen-insertion energetics on the intermetallic matrix and the H-vacancy formation in the hydride compound. We found that particular interstitial sites in the intermetallics are suitable to allocate hydrogen and form a solid solution. The effect of these interstitials on the electronic structure is discussed. In the other hand, the hydrogen-occupied sites in the hydride are found to be energetically equivalent.

  14. Application of random walk concept to the cyclic diffusion mechanisms for self-diffusion in intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Tiwari, G. P.; Mehrotra, R. S.; Iijima, Y.

    2014-02-01

    Huntington-Elcock-McCombie (HEM) mechanism involving six consecutive and correlated jumps, a triple-defect mechanism (TDM) involving three correlated jumps and an anti-structure bridge (ASB) mechanism invoking the migration of an anti-structure atom are the three mechanisms currently in vogue to explain the self- and solute diffusion in intermetallic compounds. Among them, HEM and TDM are cyclic in nature. The HEM and TDM constitute the theme of the present article. The concept of random walk is applied to them and appropriate expressions for the diffusion coefficient are derived. These equations are then employed to estimate activation energies for self-diffusion via HEM and TDM processes and compared with the available experimental data on activation energy for self-diffusion in intermetallic compounds. The resulting activation energies do not favour HEM and TDM for the self-diffusion in intermetallic compounds. A comparison of the sum of experimentally determined activation energies for vacancy formation and migration with the activation energies for self-diffusion determined from radioactive tracer method favours the conventional monovacancy-mediated process for self-diffusion in intermetallic compounds.

  15. High hardness in the biocompatible intermetallic compound β-Ti3Au

    PubMed Central

    Svanidze, Eteri; Besara, Tiglet; Ozaydin, M. Fevsi; Tiwary, Chandra Sekhar; Wang, Jiakui K.; Radhakrishnan, Sruthi; Mani, Sendurai; Xin, Yan; Han, Ke; Liang, Hong; Siegrist, Theo; Ajayan, Pulickel M.; Morosan, E.

    2016-01-01

    The search for new hard materials is often challenging, but strongly motivated by the vast application potential such materials hold. Ti3Au exhibits high hardness values (about four times those of pure Ti and most steel alloys), reduced coefficient of friction and wear rates, and biocompatibility, all of which are optimal traits for orthopedic, dental, and prosthetic applications. In addition, the ability of this compound to adhere to ceramic parts can reduce both the weight and the cost of medical components. The fourfold increase in the hardness of Ti3Au compared to other Ti–Au alloys and compounds can be attributed to the elevated valence electron density, the reduced bond length, and the pseudogap formation. Understanding the origin of hardness in this intermetallic compound provides an avenue toward designing superior biocompatible, hard materials. PMID:27453942

  16. High hardness in the biocompatible intermetallic compound β-Ti3Au.

    PubMed

    Svanidze, Eteri; Besara, Tiglet; Ozaydin, M Fevsi; Tiwary, Chandra Sekhar; Wang, Jiakui K; Radhakrishnan, Sruthi; Mani, Sendurai; Xin, Yan; Han, Ke; Liang, Hong; Siegrist, Theo; Ajayan, Pulickel M; Morosan, E

    2016-07-01

    The search for new hard materials is often challenging, but strongly motivated by the vast application potential such materials hold. Ti3Au exhibits high hardness values (about four times those of pure Ti and most steel alloys), reduced coefficient of friction and wear rates, and biocompatibility, all of which are optimal traits for orthopedic, dental, and prosthetic applications. In addition, the ability of this compound to adhere to ceramic parts can reduce both the weight and the cost of medical components. The fourfold increase in the hardness of Ti3Au compared to other Ti-Au alloys and compounds can be attributed to the elevated valence electron density, the reduced bond length, and the pseudogap formation. Understanding the origin of hardness in this intermetallic compound provides an avenue toward designing superior biocompatible, hard materials.

  17. New Interest in Intermetallic Compound ZnSb

    NASA Astrophysics Data System (ADS)

    Fedorov, M. I.; Prokof'eva, L. V.; Pshenay-Severin, D. A.; Shabaldin, A. A.; Konstantinov, P. P.

    2014-06-01

    The intermetallic compound ZnSb has been known since the 1830s. It has semiconductor properties, but its mechanical, thermal, and chemical properties are very close to those of a metallic alloy. When thermoelectrics based on (BiSb)2(TeSe)3 solid solutions were created, interest in ZnSb subsided. However, the current situation is different, as tellurium has become expensive and rare. Moreover, its compounds are too toxic, and it is too difficult to produce such materials and devices from these solid solutions. Recently, n-type material based on Mg2(SnSi) solid solution was proposed in the Laboratory of Physics for Thermoelements of the Ioffe Physical-Technical Institute. This material together with ZnSb may form a promising couple for creating various thermoelectric modules. In this paper, various properties (Hall and Seebeck coefficients, electrical and thermal conductivities) are reported in the temperature range from 80 K to 797 K. Different acceptor impurities have been tested. The Hall concentration at room temperature varied from 1.5 × 1018 cm-3 to 2.7 × 1019 cm-3. Some features have been discovered in the behavior of the thermoelectric parameters of double-doped ZnSb samples at temperatures above 500 K. Their nature points to a temperature-dependent increase of the Hall concentration. The existence of two temperature ranges with additional doping is revealed by Hall coefficient and electrical conductivity measurements in the range from 80 K to 797 K. The experimental data are discussed based on a model of the energy spectrum with impurity and native defect states localized in the energy gap. It is shown that the dimensionless thermoelectric figure of merit of ZnSb: Cd, Ag, Sn is not less than 1.0 at 600 K.

  18. Environmental Effects in Niobium Base Alloys and Other Selected Intermetallic Compounds

    DTIC Science & Technology

    1988-12-15

    Niobium aluminides and silicides as well as other intermetallic corn unds have potential for use in advanced gas turbines where increased operating...diffusion aluminide coatings on Ni-base alloys(10), Fe- silicides (l 1), and Ni- ’ silicides (12) indicate similar behavior to that in Figure 8. Typical... Niobium W MAR- 2 7 1983 Base Alloys and Other Selected Intermetallic Compounds &Simukx Defense Advanced Research Projects Agency . DARPA Order No. 6155

  19. Twinning Mechanisms in Complex High Tm Intermetallic Compounds

    DTIC Science & Technology

    2007-11-02

    Darolia, J.J. Lewandowski, C.T. Liu, P.L. Martin, D.B. Miracle and M.V. Nathal, Editors, TMS, Warrendale, PA (1993), pp 637-646. 12. "Deformation...of the 1995 Hume -Rothery Award Symposium, TMS, Warrendale, PA. 18. "Ductility and Toughness Considerations in Intermetallics", Y. Kimura and D.P...Pope, in Structural Intermetallics 1997, M. V. Nathal, R. Darolia, C. T. Liu, P. L. Martin, D. B. Miracle , R. Wagner, and M. Yamaguchi, Editors, TMS

  20. Structural size effects of intermetallic compounds on the mechanical properties of Mo-Si-B alloy: An experimental investigation

    NASA Astrophysics Data System (ADS)

    Byun, Jong Min; Bang, Su-Ryong; Park, Chun Woong; Suk, Myung-Jin; Kim, Young Do

    2016-01-01

    In general, size, shape and dispersion of phases in alloys significantly affect mechanical properties. In this study, the mechanical properties of Mo-Si-B alloys were experimentally investigated with regards to the refinement of intermetallic compound. To confirm the size effect of the intermetallic compound phases on mechanical properties, two differently sized intermetallic compound powders consisting Mo5SiB2 and Mo3Si were fabricated by mechano-chemical process and high-energy ball milling. A modified powder metallurgy method was used with core-shell intermetallic powders where the intermetallic compound particles were the core and nano-sized Mo particles which formed by the hydrogen reduction of Mo oxide were the shells, leading to the microstructures with uniformly distributed intermetallic compound phases within a continuous α-Mo matrix phase. Vickers hardness and fracture toughness were measured to examine the mechanical properties of sintered bodies. Vickers hardness was 472 Hv for the fine intermetallic compound powder and 415 Hv for the coarse intermetallic compound powder. The fracture toughness was 12.4 MPa·√m for the fine IMC powders and 13.5 MPa·√m for the coarse intermetallic compound powder.

  1. On pseudoelasticity in single crystals of the intermetallic compound Fe{sub 3}Al

    SciTech Connect

    Brinck, A.; Engelke, C.; Neuhaeuser, H.

    1997-09-01

    Only few notes can be found in literature which report on pseudoelastic effects in Fe{sub 3}Al intermetallic compounds. Reversible deformation on {l_brace}110{r_brace} and {l_brace}112{r_brace} planes was observed in shear and compression experiments by Guedou and Rieu and explained by microtwinning, while Kubin et al. showed by in-situ TEM observations that the motion of the front partial of a superdislocation appeared to cause the slip reversal on {l_brace}110{r_brace} planes. The authors have recently observed such a similar effect during in-situ slip line formation studies of Fe{sub 3}Al crystals with a special crystal orientation deformed in compression at and above room temperature. In the following these observations are described and the possible reasons are discussed in connection with the data from literature.

  2. X-Ray Diffraction of Intermetallic Compounds: A Physical Chemistry Laboratory Experiment

    ERIC Educational Resources Information Center

    Varberg, Thomas D.; Skakuj, Kacper

    2015-01-01

    Here we describe an experiment for the undergraduate physical chemistry laboratory in which students synthesize the intermetallic compounds AlNi and AlNi3 and study them by X-ray diffractometry. The compounds are synthesized in a simple one-step reaction occurring in the solid state. Powder X-ray diffractograms are recorded for the two compounds…

  3. Charge transfer on the metallic atom-pair bond, and the crystal structures adopted by intermetallic compounds.

    PubMed

    Rajasekharan, T; Seshubai, V

    2012-01-01

    It has been argued in our recent papers that the heat of formation of intermetallic compounds is mostly concentrated in the nearest neighbor unlike atom-pair bonds, and that the positive term in Miedema's equation is associated with charge transfer on the bond to maintain electroneutrality. In this paper, taking examples of some well populated crystal-structure types such as MgCu(2), AsNa(3), AuCu(3), MoSi(2) and SiCr(3) types, the effect of such charge transfer on the crystal structures adopted by intermetallic compounds is examined. It is shown that the correlation between the observed size changes of atoms on alloying and their electronegativity differences is supportive of the idea of charge transfer between atoms. It is argued that the electronegativity and valence differences need to be of the required magnitude and direction to alter, through charge transfer, the elemental radius ratios R(A)/R(B) to the internal radius ratios r(A)/r(B) allowed by the structure types. Since the size change of atoms on alloying is highly correlated to how different R(A)/R(B) is from the ideal radius ratio for a structure type, the lattice parameters of intermetallic compounds can be predicted with excellent accuracy knowing R(A)/R(B). A practical application of the approach developed in our recent papers to superalloy design is presented.

  4. Resonant ultrasound spectroscopy: Elastic properties of some intermetallic compounds

    SciTech Connect

    Chu, F.; Thoma, D.J.; He, Y.; Maloy, S.A.; Mitchell, T.E.

    1996-09-01

    A novel nondestructive evaluation method, resonant ultrasound spectroscopy (RUS), is reviewed with an emphasis upon defining the elastic properties of intermetallic phases. The applications and advantages of RUS as compared to other conventional elastic constant measurement methods are explained. RUS has been employed to measure the elastic properties of single crystal and/or polycrystalline intermetallics, such as Laves phases (C15 HfV{sub 2} and NbCr{sub 2}), Nb-modified titanium aluminides, and transition metal disilicides (C11{sub b} MoSi{sub 2}, C40 NbSi{sub 2} and TaSi{sub 2}). For Laves phases, the elastic properties of HfV{sub 2}-based C15 phases show various anomalies and those of C15 NbCr{sub 2} do not. For Nb-modified titanium aluminides, the elastic properties of O-phase alloys are investigated as a function of alloying content. For transition metal disilicides, single crystal elastic constants of MoSi{sub 2}, NbSi{sub 2}, and TaSi{sub 2} are obtained and compared. Based on the experimentally determined elastic properties, the characteristics of interatomic bonding in these materials are examined and the possible impact of the elastic properties on mechanical behavior is discussed.

  5. Hydrides of intermetallic compounds and alloys: their properties and application in atomic technology

    SciTech Connect

    Perevezentsev, A. N.; Andreev, B. M.; Kapyshev, V. K.; Rivkis, L. A.; Malek, M. P.; Bystritskii, V. M.; Stolupin, V. A.

    1988-11-01

    The Soviet and foreign literature is reviewed and an attempt is made to systematize the large amount of information on the fundamental properties of most of the well-known hydride-forming intermetallic compounds and their practical use for the extraction, cleaning, and storage of hydrogen and the separation of its isotopes.

  6. RESEARCH ON THE DEPOSITION OF MAGNETIC INTERMETALLIC COMPOUNDS IN THIN FILMS.

    DTIC Science & Technology

    A process for the vacuum deposition of thin films of intermetallic compounds of cobalt and yttrium, samarium, or neodymium, was developed. The...of the evaporation rates. Thin films of the desired stoichiometric compositions, Co5R, were produced in an extensive series of sequential experiments

  7. On the site preferences of ternary additions to triple defect B2 intermetallic compounds

    SciTech Connect

    Pike, L.M.; Chen, S.L.; Chang, Y.A.

    1995-12-31

    Knowledge of the site preference of ternary solute additions is essential to developing an understanding of how these solutes affect the properties of B2 intermetallic compounds. A quasichemical model will be presented which is able to predict the site preferences of dilute solute additions to triple defect B2 compounds. The only parameters required are enthalpies of formation at the stoichiometric composition. General equations are developed which can be used to determine site occupations and defect concentrations for dilute as well as non-dilute solute additions. These equations use atom pair bond enthalpies as the parameters. It is found that the site preferences of dilute additions are not always in agreement with predictions based on the solubility lobes in ternary Gibbs isotherms, Predictions for dilute additions to NiAl and FeAl are compared to experimental results found in the literature. Satisfactory correlation is found between the model and the experimental results. In addition, the predictions from the model on vacancy concentrations in Fe doped NiAl are compared to recent experimental results by the authors.

  8. Synthesis, Characterization and Properties of Nanoparticles of Intermetallic Compounds

    SciTech Connect

    DiSalvo, Francis J.

    2015-03-12

    The research program from 2010 to the end of the grant focused on understanding the factors important to the synthesis of single phase intermetallic nano-particles (NPs), their size, crystalline order, surface properties and electrochemical activity. The synthetic method developed is a co-reduction of mixtures of single metal precursors by strong, soluble reducing agents in a non-protic solvent, tetrahydrofuran (THF). With some exceptions, the particles obtained by room temperature reduction are random alloys that need to be annealed at modest temperatures (200 to 600 °C) in order to develop an ordered structure. To avoid significant particle size growth and agglomeration, the particles must be protected by surface coatings. We developed a novel method of coating the metal nanoparticles with KCl, a by-product of the reduction reaction if the proper reducing agents are employed. In that case, a composite product containing individual metal nanoparticles in a KCl matrix is obtained. The composite can be heated to at least 600 °C without significant agglomeration or growth in particle size. Washing the annealed product in the presence of catalyst supports in ethylene glycol removes the KCl and deposits the particles on the support. Six publications present the method and its application to producing and studying new catalyst/support combinations for fuel cell applications. Three publications concern the use of related methods to explore new lithium-sulfur battery concepts.

  9. TiNiSn: A gateway to the (1,1,1) intermetallic compounds

    SciTech Connect

    Cook, B.A.; Harringa, J.L.; Tan, Z.S.; Jesser, W.A.

    1996-06-01

    Recent awareness of the transport properties of Skutterudite pnictides has stimulated an interest in numerous other intermetallic compounds having a gap in the density of states at the Fermi level including the MNiSn compounds where M = (Ti, Zr, Hf). These intermetallic half-Heusler compounds are characterized by high Seebeck coefficients ({minus}150 to {minus}300 {micro}V/deg.) and reasonable carrier mobilities (30 to 50 cm{sup 2}/V-s) at room temperature which make them attractive candidates for intermediate temperature thermoelectric applications. Samples of TiNiSn were prepared by arc melting and homogenized by heat treatment. The temperature dependence of the electrical resistivity, Seebeck coefficient, and thermal diffusivity of these samples was characterized between 22 C and 900 C. The electrical resistivity and thermopower both decrease with temperature although the resistivity decreases at a faster rate. Electrical power factors in excess of 25 {micro}W/cm-C{sup 2} were observed in nearly single phase alloys within a 300 to 600 C temperature range. A brief survey of other selected ternary intermetallic compounds is also presented.

  10. Increasing strength and conductivity of Cu alloy through abnormal plastic deformation of an intermetallic compound.

    PubMed

    Han, Seung Zeon; Lim, Sung Hwan; Kim, Sangshik; Lee, Jehyun; Goto, Masahiro; Kim, Hyung Giun; Han, Byungchan; Kim, Kwang Ho

    2016-08-04

    The precipitation strengthening of Cu alloys inevitably accompanies lowering of their electric conductivity and ductility. We produced bulk Cu alloys arrayed with nanofibers of stiff intermetallic compound through a precipitation mechanism using conventional casting and heat treatment processes. We then successfully elongated these arrays of nanofibers in the bulk Cu alloys to 400% of original length without breakage at room temperature using conventional rolling process. By inducing such an one-directional array of nanofibers of intermetallic compound from the uniform distribution of fine precipitates in the bulk Cu alloys, the trade-off between strength and conductivity and between strength and ductility could be significantly reduced. We observed a simultaneous increase in electrical conductivity by 1.3 times and also tensile strength by 1.3 times in this Cu alloy bulk compared to the conventional Cu alloys.

  11. Increasing strength and conductivity of Cu alloy through abnormal plastic deformation of an intermetallic compound

    NASA Astrophysics Data System (ADS)

    Han, Seung Zeon; Lim, Sung Hwan; Kim, Sangshik; Lee, Jehyun; Goto, Masahiro; Kim, Hyung Giun; Han, Byungchan; Kim, Kwang Ho

    2016-08-01

    The precipitation strengthening of Cu alloys inevitably accompanies lowering of their electric conductivity and ductility. We produced bulk Cu alloys arrayed with nanofibers of stiff intermetallic compound through a precipitation mechanism using conventional casting and heat treatment processes. We then successfully elongated these arrays of nanofibers in the bulk Cu alloys to 400% of original length without breakage at room temperature using conventional rolling process. By inducing such an one-directional array of nanofibers of intermetallic compound from the uniform distribution of fine precipitates in the bulk Cu alloys, the trade-off between strength and conductivity and between strength and ductility could be significantly reduced. We observed a simultaneous increase in electrical conductivity by 1.3 times and also tensile strength by 1.3 times in this Cu alloy bulk compared to the conventional Cu alloys.

  12. Increasing strength and conductivity of Cu alloy through abnormal plastic deformation of an intermetallic compound

    PubMed Central

    Han, Seung Zeon; Lim, Sung Hwan; Kim, Sangshik; Lee, Jehyun; Goto, Masahiro; Kim, Hyung Giun; Han, Byungchan; Kim, Kwang Ho

    2016-01-01

    The precipitation strengthening of Cu alloys inevitably accompanies lowering of their electric conductivity and ductility. We produced bulk Cu alloys arrayed with nanofibers of stiff intermetallic compound through a precipitation mechanism using conventional casting and heat treatment processes. We then successfully elongated these arrays of nanofibers in the bulk Cu alloys to 400% of original length without breakage at room temperature using conventional rolling process. By inducing such an one-directional array of nanofibers of intermetallic compound from the uniform distribution of fine precipitates in the bulk Cu alloys, the trade-off between strength and conductivity and between strength and ductility could be significantly reduced. We observed a simultaneous increase in electrical conductivity by 1.3 times and also tensile strength by 1.3 times in this Cu alloy bulk compared to the conventional Cu alloys. PMID:27488621

  13. On the origin of magnetic a.c. susceptibility non-SRT anomalies in intermetallic compounds

    SciTech Connect

    Bartolome, J.; Garcia, L.M.; Lazaro, F.J.; Grincourt, Y.; Fuente, L.G. de la; Francisco, C. de; Munoz, J.M.; Fruchart, D.

    1994-03-01

    The anomaly detected in the magnetic a.c. susceptibility of many intermetallic compounds between 100 and 300 K, and in particular in Nd{sub 2}Fe{sub 14}B at 220 K, has been induced in a controlled manner by thermal annealing. The anomaly has been interpreted in terms of thermal activated processes of defects imposing their dynamical behavior on the domain walls coupled to them, thus solving the controversy on its origin.

  14. Magnetic properties of a new intermetallic compound Ho2Ni2Pb

    NASA Astrophysics Data System (ADS)

    Muñoz-Sandoval, E.; Chinchure, A. D.; Hendrikx, R. W. A.; Mydosh, J. A.

    2001-10-01

    Single-phase, textured samples of a new orthorhombic intermetallic compound Ho2Ni2Pb have been fabricated (space group Cmmm). Here the bulk magnetic properties are presented as determined via magnetization, susceptibility, heat capacity and resistivity measurements. The results exhibit two distinct magnetic transitions and large metamagnetic effects. Such behaviour is related to the unusual rare-earth symmetry of the highly anisotropic crystal structure.

  15. Domain Structure of R2Fe17 Intermetallic Compounds with Planar-Type Anisotropy

    NASA Astrophysics Data System (ADS)

    Pastushenkov, Yu. G.; Skokov, K. P.; Lyakhova, M. B.; Antonova, E. S.

    2017-01-01

    Magnetic domain structure is studied in single crystals of R2Fe17 (R = Tb, Dy, Ho, Er) intermetallic compounds in a wide range of temperatures (10 - 300 K) and magnetic fields (μ0 H = 0 - 0.1 T). It is shown that single crystal specimens of hexagonal magnetics with planar-type anisotropy acquire domain structures containing not only 180-degree domain boundaries but also 60- and 120-degree ones.

  16. Electronic and high pressure elastic properties of RECd and REHg (RE=Sc, La and Yb) intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Devi, Hansa; Pagare, Gitanjali; Chouhan, Sunil S.; Sanyal, Sankar P.

    2015-01-01

    Structural, electronic, elastic and mechanical properties of Cd and Hg based rare earth intermetallics (RECd and REHg; RE=Sc, La and Yb) have been investigated using the full-potential linearized augmented plane-wave (FP-LAPW) method within the density-functional theory (DFT). The ground state properties such as lattice constant (a0), bulk modulus (B) and its pressure derivative (B‧) have been obtained using optimization method and are found in good agreement with the available experimental results. The calculated enthalpy of formation shows that LaHg has the strongest alloying ability and structural stability. The electronic band structures and density of states reveal the metallic character of these compounds. The structural stability mechanism is also explained through the electronic structures of these compounds. The chemical bonding between rare earth atoms and Cd, Hg is interpreted by the charge density plots along (1 1 0) direction. The elastic constants are predicted from which all the related mechanical properties like Poisson's ratio (σ), Young's modulus (E), shear modulus (GH) and anisotropy factor (A) are calculated. The ductility/brittleness of these intermetallics is predicted. Chen's method has been used to predict the Vicker's hardness of RECd and REHg compounds. The pressure variation of the elastic constants is also reported in their B2 phase.

  17. Long-Term Behavior of the Tritides Formed by Nickel-Based Intermetallic Compounds

    SciTech Connect

    Bowman, Jr., R. C.; Steinmeyer, R. H.; Matson, L. K.; Attalla, A.; Craft, B. D.

    1985-04-01

    Some properties of the tritide phases formed by the intermetallic compounds Mg2Ni, ZrNi, and LaNi5 have been studied. Whereas ZrNiT3 will retain its stoichiometry indefinitely when sufficient gaseous tritium is available, the stoichiometries of Mg2NiT4 and LaNi5T6.9 decrease with time. Although all three intermetallic tritides can retain large quantities of the helium-3 tritium decay daughter product in the solid phase, irreversible release of helium begins after several hundred days for ZrNiTx and Mg2NiTx. However, LaNi5Tx retains all of the helium generated in the solid for at least 2400 days. NMR measurements for ZrNiTx and Mg2NiTx imply that helium is retained in microscopic bubbles as previously observed in several binary metal tritides.

  18. Na-Au intermetallic compounds formed under high pressure at room temperature

    NASA Astrophysics Data System (ADS)

    Takemura, K.; Fujihisa, H.

    2011-07-01

    High-pressure powder x-ray diffraction experiments have revealed that sodium and gold react at room temperature and form Na-Au intermetallic compounds under high pressure. We have identified four intermetallic phases up to 60 GPa. The first phase (phase I) is the known Na2Au with the tetragonal CuAl2-type structure. It changed to the second phase (phase II) at ˜0.8 GPa, which has the composition Na3Au with the trigonal Cu3As-type or hexagonal Cu3P-type structure. Phase II further transformed to phase III at 3.6 GPa. Phase III has the same composition, Na3Au, with the cubic BiF3-type structure. Finally, phase III changed to phase IV at ˜54 GPa. Phase IV gives broad diffraction peaks, indicating large structural disorder.

  19. Neutron Scattering Study of TbPtin Intermetallic Compound

    SciTech Connect

    Garlea, Vasile O; Morosan, E.; Bud'ko, S. L.; Zarestky, Jerel L; Canfield, P. C.; Stassis, C.

    2005-01-01

    Neutron diffraction techniques have been used to study the magnetic properties of a TbPtIn single-crystal as a function of temperature and magnetic field. In the absence of an externally applied magnetic field, the compound orders, below approximately 47 K, in an antiferromagnetic structure with propagation vector k=(1/2,0,1/2); the magnetic moments were found to be parallel to the [1 {ovr 2} 0] direction. Measurements at 4.2 K, with a magnetic field applied along the [1 {ovr 2} 0] direction, revealed metamagnetic transitions at approximately 20 kG and 40 kG.

  20. Low temperature properties of some Er-rich intermetallic compounds

    SciTech Connect

    K.A. Gshneidner,jr; A.O. Pecharsky; L.Hale; V.K. Pecharsky

    2004-09-30

    The low temperature volumetric heat capacity ({approx}3.5 to 350 K) and magnetic susceptibility ({approx}4 to 320 K) of Er{sub 3}Rh, Er{sub 3}Ir, Er{sub 3}Pt, Er{sub 2}Al, and Er{sub 2}Sn have been measured. All of the compounds order antiferromagnetically (or ferrimagnetically), and most exhibit more than one magnetic ordering transition. The volumetric heat capacities in general are smaller than those of the prototype magnetic regenerator materials, except for Er{sub 3}Ir in the 12 to 14 K temperature range.

  1. The atomic structure of low-index surfaces of the intermetallic compound InPd.

    PubMed

    McGuirk, G M; Ledieu, J; Gaudry, É; de Weerd, M-C; Hahne, M; Gille, P; Ivarsson, D C A; Armbrüster, M; Ardini, J; Held, G; Maccherozzi, F; Bayer, A; Lowe, M; Pussi, K; Diehl, R D; Fournée, V

    2015-08-21

    The intermetallic compound InPd (CsCl type of crystal structure with a broad compositional range) is considered as a candidate catalyst for the steam reforming of methanol. Single crystals of this phase have been grown to study the structure of its three low-index surfaces under ultra-high vacuum conditions, using low energy electron diffraction (LEED), X-ray photoemission spectroscopy (XPS), and scanning tunneling microscopy (STM). During surface preparation, preferential sputtering leads to a depletion of In within the top few layers for all three surfaces. The near-surface regions remain slightly Pd-rich until annealing to ∼580 K. A transition occurs between 580 and 660 K where In segregates towards the surface and the near-surface regions become slightly In-rich above ∼660 K. This transition is accompanied by a sharpening of LEED patterns and formation of flat step-terrace morphology, as observed by STM. Several superstructures have been identified for the different surfaces associated with this process. Annealing to higher temperatures (≥750 K) leads to faceting via thermal etching as shown for the (110) surface, with a bulk In composition close to the In-rich limit of the existence domain of the cubic phase. The Pd-rich InPd(111) is found to be consistent with a Pd-terminated bulk truncation model as shown by dynamical LEED analysis while, after annealing at higher temperature, the In-rich InPd(111) is consistent with an In-terminated bulk truncation, in agreement with density functional theory (DFT) calculations of the relative surface energies. More complex surface structures are observed for the (100) surface. Additionally, individual grains of a polycrystalline sample are characterized by micro-spot XPS and LEED as well as low-energy electron microscopy. Results from both individual grains and "global" measurements are interpreted based on comparison to our single crystals findings, DFT calculations and previous literature.

  2. The atomic structure of low-index surfaces of the intermetallic compound InPd

    SciTech Connect

    McGuirk, G. M.; Ledieu, J.; Gaudry, É.; Weerd, M.-C.; Fournée, V. de; Hahne, M.; Gille, P.; Ivarsson, D. C. A.; Armbrüster, M.; Ardini, J.; Held, G.; Maccherozzi, F.; Bayer, A.; Lowe, M.; Pussi, K.; Diehl, R. D.

    2015-08-21

    The intermetallic compound InPd (CsCl type of crystal structure with a broad compositional range) is considered as a candidate catalyst for the steam reforming of methanol. Single crystals of this phase have been grown to study the structure of its three low-index surfaces under ultra-high vacuum conditions, using low energy electron diffraction (LEED), X-ray photoemission spectroscopy (XPS), and scanning tunneling microscopy (STM). During surface preparation, preferential sputtering leads to a depletion of In within the top few layers for all three surfaces. The near-surface regions remain slightly Pd-rich until annealing to ∼580 K. A transition occurs between 580 and 660 K where In segregates towards the surface and the near-surface regions become slightly In-rich above ∼660 K. This transition is accompanied by a sharpening of LEED patterns and formation of flat step-terrace morphology, as observed by STM. Several superstructures have been identified for the different surfaces associated with this process. Annealing to higher temperatures (≥750 K) leads to faceting via thermal etching as shown for the (110) surface, with a bulk In composition close to the In-rich limit of the existence domain of the cubic phase. The Pd-rich InPd(111) is found to be consistent with a Pd-terminated bulk truncation model as shown by dynamical LEED analysis while, after annealing at higher temperature, the In-rich InPd(111) is consistent with an In-terminated bulk truncation, in agreement with density functional theory (DFT) calculations of the relative surface energies. More complex surface structures are observed for the (100) surface. Additionally, individual grains of a polycrystalline sample are characterized by micro-spot XPS and LEED as well as low-energy electron microscopy. Results from both individual grains and “global” measurements are interpreted based on comparison to our single crystals findings, DFT calculations and previous literature.

  3. Development of Cu alloy anode and separator coated with Al-Ni intermetallic compound

    SciTech Connect

    Toyokura, K.; Hoshino, K.; Yamamoto, M.

    1996-12-31

    Anode made of Cu alloy and separator coated with Al-Ni intermetallic compound have been developed for VCFC. Anode of Ni alloy is usually used. However, the alternative of cost lower than Ni alloy anode should be needed, because Ni is expensive. Cu is attractive as an anode material for VCFC because it is inexpensive and electrochemically noble. However, the creep resistance of Cu is not sufficient, compared with Ni alloy. In this study, strengthening due to oxide-dispersed microstructure has been developed in Cu-Ni-Al alloy with the two-step sintering process. A wet-seal technique has been widely applied for gas-sealing and supporting of electrolyte in MCFC. Since the wet-seal area is exposed to a severe corrosive environment, corrosion resistance of material for wet sealing is related with the cell performance. Al-Ni plating with post-heat treating for stainless steel has been investigated. Stainless steel substrate was plated with Al after being coated with Ni, then heat-treated at 750 {degrees}C for 1 hour in Ar gas atmosphere. Due to the treatment, Al-Ni intermetallic compound ( mainly Al3Ni2 ) layer is formed on stainless steel surface. The long-term immersion test was carried out till 14,500 hours in 62 mol% Li{sub 2}CO{sub 3}-38 mol% K{sub 2}CO{sub 3} at 650 {degrees}C under air-30%CO{sub 2} atmosphere, for the purpose of evaluating the corrosion resistance and thermal stability of Al-Ni intermetallic compound layer in actual generating with VCFC.

  4. A review on the synthesis, crystal growth, structure and physical properties of rare earth based quaternary intermetallic compounds

    SciTech Connect

    Mumbaraddi, Dundappa; Sarkar, Sumanta; Peter, Sebastian C.

    2016-04-15

    This review highlights the synthesis and crystal growth of quaternary intermetallic compounds based on rare earth metals. In the first part of this review, we highlight briefly about intermetallics and their versatile properties in comparison to the constituent elements. In the next part, we have discussed about various synthesis techniques with more focus on the metal flux technique towards the well shaped crystal growth of novel compounds. In the subsequent parts, several disordered quaternary compounds have been reviewed and then outlined most known ordered quaternary compounds with their complex structure. A special attention has been given to the ordered compounds with structural description and relation to the parent binary and ternary compounds. The importance of electronic and structural feature is highlighted as the key roles in designing these materials for emerging applications. - Graphical abstract: Rare earth based quaternary intermetallic compounds crystallize in complex novel crystal structures. The diversity in the crystal structure may induce unique properties and can be considered them as future materials. - Highlights: • Crystal growth and crystal structure of quaternary rare earth based intermetallics. • Structural complexity of quaternary compounds in comparison to the parent compounds. • Novel quaternary compounds display unique crystal structure.

  5. Point defects quenched in NiAl and related intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Fan, Jiawen

    1991-08-01

    Point defects in the highly ordered B2 compounds NiAl, CoAl and FeAl were studied using the perturbed gamma-gamma angular correlations (PAC) technique. Quadrupole interactions detected at dilute In-111 probes on Al sites in NiAl and CoAl were identified with complexes containing one or two vacancies in the first atomic shell. Measurements on rapidly quenched NiAl and CoAl exhibited increases in site fractions of vacancy-probe complexes caused by formation of thermal defects. Site fractions were analyzed using the law of mass action to obtain absolute vacancy concentrations. PAC is shown to be a powerful new technique for the quantitative study of equilibrium defects in solids. For NiAl, the vacancy concentration quenched-in from a given temperature was found to be independent of composition over the range 50.4 to 53.5 at. pct. Ni, identifying the Schottky defect (vacancy pair) as the dominant equilibrium defect, and ruling out the so-called triple defect. Formation energies and entropies of Schottky pairs were determined to be 2.66(8) and 3.48(12) eV, and 12(1) and 17(2) k sub B, respectively, for NiAl and CoAl. The entropies suggest huge vacancy concentrations, 13 pct. at the melting temperatures of NiAl and CoAl. Migration energies of Ni and Co vacancies were found to be 1.8(2) and 2.5(2) eV, respectively. FeAl exhibited complex behavior. A low temperature regime was detected in NiAl and CoAl within which vacancies are mobile but do not anneal out, so that the vacancy concentration remains constant. In NiAl, this 'bottleneck' regime extends from 350 to 700 C. Vacancies were found to be bound to the In probes with an energy very close to 0.20 eV in NiAl and CoAl. An explanation of the bottleneck is proposed in terms of saturation of all lattice sinks. This annealing bottleneck should exist in a wide range of intermetallic compounds when there is a sufficiently high vacancy concentration.

  6. Extreme Poisson's ratios and their electronic origin in B2 CsCl-type AB intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Wang, X. F.; Jones, Travis E.; Li, W.; Zhou, Y. C.

    2012-04-01

    Negative Poisson's ratios have been observed in a variety of metals and alloys. However, the electronic origin of this effect remains unclear, as is evident by our limited knowledge about intermetallics showing this behavior. In an effort to clarify the electronic origin of a negative Poisson's ratio, we have performed a systematic and comprehensive study of extreme (both positive and negative) Poisson's ratios behavior in the B2 CsCl-type AB intermetallic family (including 14 common intermetallics and 128 rare-earth-metal transition or main-group-metal intermetallics) by way of density functional theory calculations. We found a pronounced correlation between the extreme Poisson's ratios and the elastic anisotropy, with approximately 70% of the B2 intermetallics showing intrinsic auxetic behavior. We went on to examine the topology and geometry of the electron charge density and found that the extreme Poisson's ratios are attributable to the directionality of the bonds of the material. Auxetic materials were found to have nondirectional bonds, and nonauxetic compounds had directional bonds. Our findings provide an essential electronic perspective to forecast the auxetic behavior, and suggest a new application for intermetallic compounds.

  7. In search of the elusive amalgam SrHg8: a mercury-rich intermetallic compound with augmented pentagonal prisms.

    PubMed

    Tkachuk, Andriy V; Mar, Arthur

    2010-08-14

    In confirmation of its predicted existence in the Sr-Hg phase diagram, the mercury-rich intermetallic compound SrHg(8) has been prepared by reaction of the elements at 200 degrees C. Single-crystal X-ray diffraction analysis revealed that it adopts a new structure type (Pearson symbol oP72, space group Pnma, a = 13.328(1) A, b = 4.9128(5) A, c = 26.446(3) A). The Sr atoms are centred within two types of 18-vertex Hg polyhedra formed by augmenting pentagonal prisms with octagonal waists. The condensation of these Sr@Hg(18) clusters is associated with the formation of a complex anionic Hg-Hg bonding network, as supported by electronic structure calculations which reveal strong mixing of Hg 6s and 6p states in highly delocalized bands superimposed with a narrower 5d band below the Fermi level.

  8. Intermetallic Formation at Interface of Al/Cu Clad Fabricated by Hydrostatic Extrusion and Its Properties.

    PubMed

    Lee, Jongbeom; Jeong, Haguk

    2015-11-01

    Al/Cu clad composed of Al core and Cu sheath has been produced by hydrostatic extrusion at 523 K, at an extrusion rate of 27. The prepared specimen was post-annealed at temperatures of 673 K and 773 K for various time durations, and the effect of annealing conditions have been analyzed. The hardness at the interface between Al and Cu matrix of the Al/Cu bimetal clad increases because of annealing. Results indicate that the hardness is more sensitive to annealing temperature than the annealing time. Three kinds of intermetallic compounds (IMC), namely, CuAl, Cu3Al2, and CuAl2, are formed at the Al-Cu interface, upon annealing at 673 K. On the other hand, four kinds of IMCs, namely, Cu4Al3, CuAl, Cu3Al2, CuAl2, are formed at the annealing temperature of 773 K. The growth of each IMC follows the parabolic law as a function of annealing times at certain annealing temperature. The growth rate of each IMC is limited to its interdiffusion rate constant. The IMC Cu4Al3 appears upon annealing at 773 K, and not during annealing at 673 K, because of the higher value of activation energy associated with its formation, when compared to other IMCs.

  9. Intermetallic nanoparticles

    DOEpatents

    Singh, Dileep; Yusufoglu, Yusuf; Timofeeva, Elena; Routbort, Jules

    2015-07-14

    A process for preparing intermetallic nanoparticles of two or more metals is provided. In particular, the process includes the steps: a) dispersing nanoparticles of a first metal in a solvent to prepare a first metal solution, b) forming a reaction mixture with the first metal solution and a reducing agent, c) heating the reaction mixture to a reaction temperature; and d) adding a second metal solution containing a salt of a second metal to the reaction mixture. During this process, intermetallic nanoparticles, which contain a compound with the first and second metals are formed. The intermetallic nanoparticles with uniform size and a narrow size distribution is also provided. An electrochemical device such as a battery with the intermetallic nanoparticles is also provided.

  10. Intermetallic nanoparticles

    DOEpatents

    Singh, Dileep; Yusufoglu, Yusuf; Timofeeva, Elena; Routbort, Jules L.

    2017-01-03

    A process for preparing intermetallic nanoparticles of two or more metals is provided. In particular, the process includes the steps: a) dispersing nanoparticles of a first metal in a solvent to prepare a first metal solution, b) forming a reaction mixture with the first metal solution and a reducing agent, c) heating the reaction mixture to a reaction temperature; and d) adding a second metal solution containing a salt of a second metal to the reaction mixture. During this process, intermetallic nanoparticles, which contain a compound with the first and second metals are formed. The intermetallic nanoparticles with uniform size and a narrow size distribution is also provided. An electrochemical device such as a battery with the intermetallic nanoparticles is also provided.

  11. Intermetallic nanoparticles

    SciTech Connect

    Singh, Dileep; Yusufoglu, Yusuf; Timofeeva, Elena; Routbort, Jules L.

    2015-11-20

    A process for preparing intermetallic nanoparticles of two or more metals is provided. In particular, the process includes the steps: a) dispersing nanoparticles of a first metal in a solvent to prepare a first metal solution, b) forming a reaction mixture with the first metal solution and a reducing agent, c) heating the reaction mixture to a reaction temperature; and d) adding a second metal solution containing a salt of a second metal to the reaction mixture. During this process, intermetallic nanoparticles, which contain a compound with the first and second metals are formed. The intermetallic nanoparticles with uniform size and a narrow size distribution is also provided. An electrochemical device such as a battery with the intermetallic nanoparticles is also provided.

  12. Characterization of second-phase plates in a Gd5Ge3 intermetallic compound

    SciTech Connect

    Cao, Qing; Chumbley, Leonard S.

    2013-05-16

    Rare-earth compounds based on the stoichiometry R5(SixGe1-x)4 (R = rare-earth elements) exhibit many unusual features, including possessing R5(SixGe1-x)3 thin plates which always precipitate from the matrix despite efforts to suppress their formation. In an effort to better understand the unique relationship between these two intermetallic alloy systems, the bulk microstructure of the compound Gd5Ge3 was examined using scanning (SEM) and transmission electron microscopy (TEM) and optical microscopy. Surprisingly, SEM examination revealed a series of thin plates present in the Gd5Ge3 matrix similar to what is seen in Gd5Ge4. TEM observation revealed that a role reversal had occurred, with the thin plates possessing the orthorhombic structure and composition of Gd5Ge4. The orientation relationship between Gd5Ge4 thin plates and the Gd5Ge3 matrix was determined to be Graphic the same relationship reported for Gd5Ge3 plates precipitating from a Gd5Ge4 matrix. However, by exchanging the respective roles of the phases as regards matrix vs. precipitate, the total number of precipitation variants seen can be increased from two to six. The persistence with which these two intermetallic systems co-exist is truly unique. However, understanding exactly the kinetic and thermodynamic conditions that lead to their unique relationship is hampered by the high formation temperatures at which the observed reaction occurs.

  13. Effect of intermetallic compounds on the thermal conductivity of Ti-Cu composites

    SciTech Connect

    Jagannadham, K.

    2016-03-15

    Ti films were deposited by magnetron sputtering on polycrystalline Cu substrates. The samples were annealed at different temperatures and characterized by x-ray diffraction for phase identification, scanning electron microscopy, and energy dispersive spectrometry for microstructure and composition and transient thermoreflectance for thermal conductivity and interface thermal conductance. The results showed that the diffused layer of Ti in Cu contained intermetallic compounds and solid solution of Ti in Cu. The thermal conductivity of the diffused layer is reduced, and the thickness increased for higher annealing temperature. The interface thermal conductance also decreased for higher temperature of annealing. A stable Cu{sub 4}Ti phase was formed after annealing at 725 °C with thermal conductivity of 10 W m{sup −1} K{sup −1}. The interface thermal conductance between the intermetallic compound and the solid solution of Ti in Cu also was reduced to 30 MW m{sup −2} K{sup −1}. The effective thermal resistance of the diffused layer and the interface was found to increase for higher annealing temperature.

  14. Surface structures of In-Pd intermetallic compounds. II. A theoretical study

    SciTech Connect

    Gaudry, É.; McGuirk, G. M.; Ledieu, J.; Fournée, V.

    2014-08-28

    The (110) surface of the InPd intermetallic compound and the In–Pd surface alloy properties are investigated in the framework of the density functional theory, within the projector augmented plane-wave method. Surface segregation is calculated to be energetically unfavorable at stoichiometric InPd(110) surfaces, while indium antisites are shown to segregate to the surface in off-stoichiometric InPd(110) systems. Concerning surface alloys obtained by burying In-doped Pd layers in Pd(111), we demonstrated that the most stable ones are those presenting atomic indium concentrations below 50 at. % (11 at. %, 25 at. %, 33 at. %). According to our calculations, the In-doped Pd layers with concentration above or equal to 50% lead to In-doped Pd multilayers, each presenting an atomic indium concentration below 50 at. %. Alloying and segregation effects in InPd intermetallic compound and In–Pd surface alloys clearly agree with the larger bonding strength of In–Pd (−0.44 eV) compared to In–In (−0.29 eV) and Pd–Pd (−0.31 eV)

  15. Exploring the Structural Complexity of Intermetallic Compounds by an Adaptive Genetic Algorithm

    NASA Astrophysics Data System (ADS)

    Zhao, X.; Nguyen, M. C.; Zhang, W. Y.; Wang, C. Z.; Kramer, M. J.; Sellmyer, D. J.; Li, X. Z.; Zhang, F.; Ke, L. Q.; Antropov, V. P.; Ho, K. M.

    2014-01-01

    Solving the crystal structures of novel phases with nanoscale dimensions resulting from rapid quenching is difficult due to disorder and competing polymorphic phases. Advances in computer speed and algorithm sophistication have now made it feasible to predict the crystal structure of an unknown phase without any assumptions on the Bravais lattice type, atom basis, or unit cell dimensions, providing a novel approach to aid experiments in exploring complex materials with nanoscale grains. This approach is demonstrated by solving a long-standing puzzle in the complex crystal structures of the orthorhombic, rhombohedral, and hexagonal polymorphs close to the Zr2Co11 intermetallic compound. From our calculations, we identified the hard magnetic phase and the origin of high coercivity in this compound, thus guiding further development of these materials for use as high performance permanent magnets without rare-earth elements.

  16. Exploring phase stability, electronic and mechanical properties of Ce–Pb intermetallic compounds using first-principles calculations

    SciTech Connect

    Tao, Xiaoma; Wang, Ziru; Lan, Chunxiang; Xu, Guanglong; Ouyang, Yifang; Du, Yong

    2016-05-15

    The phase stability, electronic and mechanical properties of Ce–Pb intermetallics have been investigated by using first-principles calculations. Five stable and four metastable phases of Ce–Pb intermetallics were verified. Among them, CePb{sub 2} has been confirmed as HfGa{sub 2}-type structure. For Ce{sub 5}Pb{sub 3}, the high pressure phase transformation from D8{sub m} to D8{sub 8} with trivalent Ce has been predicted to occur at P=1.2 GPa and a high temperature phase transformation has been predicted from D8{sub m} to D8{sub 8} with tetravalent Ce at 531.5 K. The calculated lattice constants of the five stable phases are in good agreement with experimental values. The electronic density of states, charge density and electron localization function of Ce{sub 3}Pb have been calculated, which indicated that the Ce and Pb show ionic behavior. The polycrystalline bulk modulus, shear modulus, Young's modulus, and Poisson's ratio are also estimated from the calculated single crystalline elastic constants. All of the calculated elastic constants satisfy mechanical stability criteria. The microhardness and mechanical anisotropy are predicted. The anisotropic nature of the Ce–Pb intermetallic compounds are demonstrated by the three-dimensional orientation dependent surfaces of Young's moduli and linear compressibility are also demonstrated. The longitudinal, transverse and average sound velocities and the Debye temperatures are also obtained in this work. The Ce{sub 3}Pb has the largest Debye temperature of 192.6 K, which means the Ce{sub 3}Pb has a highest melting point and high thermal conductivity than other compounds. - Graphical abstract: The convex hull plots of the enthalpies of formation for Ce–Pb binary systems calculated at 0 K. - Highlights: • The five stable and four metastable phases in the Ce–Pb binary system were predicted. • The crystal structure of CePb{sub 2} has been confirmed as HfGa{sub 2}-type.

  17. Dispersion of electronic bands in intermetallic compound LiBe and related properties

    NASA Astrophysics Data System (ADS)

    Reshak, A. H.

    2015-10-01

    Based on the all-electron full-potential linearized augmented plane wave within density functional theory calculations dispersion of the electronic band structure, total and the angular momentum resolved projected density of states, the shape of Fermi surface, the electronic charge density distribution and the optical response of the intermetallic LiBe compound are performed. Seeking the influence of the different exchange correlations on the ground state properties of the intermetallic LiBe, calculations are performed within four types of exchange correlations, namely the local density approximation, general gradient approximation, Engel-Vosko generalized gradient approximation and the modified Becke-Johnson potential. It has been found that replacing the exchange correlations exhibit insignificant influence on the bands dispersion, density of states and hence the optical properties. The obtained results suggest that there exists a strong hybridization between the states resulting in covalent bonds. The Fermi surface is formed by two bands and the center of the Fermi surface is formed by holes. The electronic charge density distribution confirms that the charge is attracted toward Be atoms and the calculated bond lengths are in good accordance with the available experimental data. To get deep insight into the electronic structure, the optical properties are investigated and analyzed in accordance with the calculated band structure and the density of states.

  18. A review on the synthesis, crystal growth, structure and physical properties of rare earth based quaternary intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Mumbaraddi, Dundappa; Sarkar, Sumanta; Peter, Sebastian C.

    2016-04-01

    This review highlights the synthesis and crystal growth of quaternary intermetallic compounds based on rare earth metals. In the first part of this review, we highlight briefly about intermetallics and their versatile properties in comparison to the constituent elements. In the next part, we have discussed about various synthesis techniques with more focus on the metal flux technique towards the well shaped crystal growth of novel compounds. In the subsequent parts, several disordered quaternary compounds have been reviewed and then outlined most known ordered quaternary compounds with their complex structure. A special attention has been given to the ordered compounds with structural description and relation to the parent binary and ternary compounds. The importance of electronic and structural feature is highlighted as the key roles in designing these materials for emerging applications.

  19. Effect of Intermetallic Compound Phases on the Mechanical Properties of the Dissimilar Al/Cu Friction Stir Welded Joints

    NASA Astrophysics Data System (ADS)

    Khodir, S. A.; Ahmed, M. M. Z.; Ahmed, Essam; Mohamed, Shaymaa M. R.; Abdel-Aleem, H.

    2016-11-01

    Types and distribution of intermetallic compound phases and their effects on the mechanical properties of dissimilar Al/Cu friction stir welded joints were investigated. Three different rotation speeds of 1000, 1200 and 1400 rpm were used with two welding speeds of 20 and 50 mm/min. The results show that the microstructures inside the stir zone were greatly affected by the rotation speed. Complex layered structures that containing intermetallic compound phases such as CuAl2, Al4Cu9 were formed in the stir zone. Their amount found to be increased with increasing rotation speed. However, the increasing of the rotation speed slightly lowered the hardness of the stir zone. Many sharp hardness peaks in the stir zones were found as a result of the intermetallic compounds formed, and the highest peaks of 420 Hv were observed at a rotation speed of 1400 rpm. The joints ultimate tensile strength reached a maximum value of 105 MPa at the rotation speed of 1200 rpm and travel speed of 20 mm/min with the joint efficiency ranged between 88 and 96% of the aluminum base metal. At the travel speed of 50 mm/min, the maximum value of the ultimate tensile strength was 96 MPa at rotation speed of 1400 rpm with the joint efficiency ranged between 79 and 90%. The fracture surfaces of tensile test specimens showed no evidence for the effect of the brittle intermetallic compounds in the stir zones on the tensile strength of the joints.

  20. Gas atomization synthesis of refractory or intermetallic compounds and supersaturated solid solutions

    DOEpatents

    Anderson, Iver E.; Lograsso, Barbara K.; Ellis, Timothy W.

    1994-01-01

    A metallic melt is atomized using a high pressure atomizing gas wherein the temperature of the melt and the composition of the atomizing gas are selected such that the gas and melt react in the atomization spray zone to form a refractory or intermetallic compound in the as-atomized powder particles. A metallic melt is also atomized using a high pressure atomizing gas mixture gas wherein the temperature of the melt and the ratio of a reactive gas to a carrier gas are selected to form powder particles comprising a supersaturated solid solution of the atomic species of the reactive gas in the particles. The powder particles are then heat treated to precipitate dispersoids in-situ therein to form a dispersion strengthened material.

  1. Gas atomization synthesis of refractory or intermetallic compounds and supersaturated solid solutions

    DOEpatents

    Anderson, I.E.; Lograsso, B.K.; Ellis, T.W.

    1994-11-29

    A metallic melt is atomized using a high pressure atomizing gas wherein the temperature of the melt and the composition of the atomizing gas are selected such that the gas and melt react in the atomization spray zone to form a refractory or intermetallic compound in the as-atomized powder particles. A metallic melt is also atomized using a high pressure atomizing gas mixture gas wherein the temperature of the melt and the ratio of a reactive gas to a carrier gas are selected to form powder particles comprising a supersaturated solid solution of the atomic species of the reactive gas in the particles. The powder particles are then heat treated to precipitate dispersoids in-situ therein to form a dispersion strengthened material. 9 figures.

  2. Magnetostriction and magnetism of rare earth intermetallic compounds: First principle study

    SciTech Connect

    Gavrilenko, V. I.; Wu, R. Q.

    2001-06-01

    Magnetism and magnetostriction of rare earth intermetallic compounds, GdCo{sub 2}, GdFe{sub 2}, NdCo{sub 2}, SmCo{sub 2}, and ErCo{sub 2}, have been studied by using the first principles full-potential linearized augmented plane-wave method with the generalized gradient approximation. The calculated magnetostriction coefficients agree well with experiment. The itinerant electrons of transition metal elements are found to play a significant role in magnetoelastic coupling. The strong anisotropy of magnetostriction in GdCo{sub 2} is explained. Contributions due to spatial anisotropic charge distribution of the incomplete 4f shells are calculated and discussed. {copyright} 2001 American Institute of Physics.

  3. Intermetallic compounds, copper and palladium alloys in Au-Pd ore of the Skaergaard pluton, Greenland

    NASA Astrophysics Data System (ADS)

    Rudashevsky, N. S.; Rudashevsky, V. N.; Nielsen, T. F. D.

    2015-12-01

    Copper-palladium intermetallic compounds and alloys (2314 grains) from the Au-Pd ore of the Skaergaard layered gabbroic pluton have been studied. Skaergaardite PdCu, nielsenite PdCu3, (Cu,Pd)β, (Cu,Pd)α, (Pd,Cu,Au,Pt) alloys, and native palladium have been identified as a result of 1680 microprobe analyses. The average compositions and various chemical varieties of these minerals are characterized, as well as vertical and lateral zoning in distribution of noble metals. The primary Pd-Cu alloys were formed within a wide temperature interval broadly synchronously with cooling and crystallization of host gabbro and in close association with separation of Fe-Cu sulfide liquid. In the course of crystallization of residual gabbroic melt enriched in iron, noble and heavy metals and saturated with the supercritical aqueous fluid, PGE and Au are selectively concentrated in the Fe-Cu sulfide phase as Pd-Cu and Cu-Au alloys.

  4. Multiconfigurational nature of 5f orbitals in uranium and plutonium and their intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Booth, Corwin

    2013-03-01

    The structural, electronic, and magnetic properties of U and Pu elements and intermetallics remain poorly understood despite decades of effort, and currently represent an important scientific frontier toward understanding matter. The last decade has seen great progress both due to the discovery of superconductivity in PuCoGa5 and advances in theory that finally can explain fundamental ground state properties in elemental plutonium, such as the phonon dispersion curve, the non-magnetic ground state, and the volume difference between the α and δ phases. A new feature of the recent calculations is the presence not only of intermediate valence of the Pu 5f electrons, but of multiconfigurational ground states, where the different properties of the α and δ phases are primarily governed by the different relative weights of the 5f4, 5f5, and 5f6 electronic configurations. The usual method for measuring multiconfigurational states in the lanthanides is to measure the lanthanide LIII-edge x-ray absorption near-edge structure (XANES), a method that is severely limited for the actinides because the spectroscopic features are not well enough separated. Advances in resonant x-ray emission spectroscopy (RXES) have now allowed for spectra with sufficient resolution to resolve individual resonances associated with the various actinide valence states. Utilizing a new spectrometer at the Stanford Synchrotron Radiation Lightsource (SSRL), RXES data have been collected that show, for the first time, spectroscopic signatures of each of these configurations and their relative changes in various uranium and plutonium intermetallic compounds. In combination with conventional XANES spectra on related compounds, these data indicate such states may be ubiquitous in uranium and plutonium intermetallics, providing a new framework toward understanding properties ranging from heavy fermion behavior, superconductivity, and intermediate valence to mechanical and fundamental bonding behavior in

  5. Fundamental study about CO2 laser welding of titanium aluminide intermetallic compound

    NASA Astrophysics Data System (ADS)

    Kuwahara, Gaku; Yamaguchi, Shigeru; Nanri, Kenzo; Ootani, Masanori; Tetsuka, Masato; Seto, Sachio; Arai, Mikiya; Fujioka, Tomoo

    2000-11-01

    Titanium aluminide intermetallic compound is attracting attentions as heat-resistant and high-specific strength material in the next generation, especially, it is promising material in the field of aerospace components. Conventional machining process including welding, however, can be hardly applied due to its very low ductility. The objective of this study, as a first stage, is to find out paying attention to crack and hardness the fundamental good conditions of the bead-on-plate welding of TiAl intermetallic compound using CO2 laser irradiation. In the experiment, we used the casting gamma titanium aluminide contained iron, vanadium and boron with a thickness of 2mm. We carried out bead-on-plate laser welding in the titanium aluminide material in inert gas environment filled with argon. We measured fused depth, Vickers hardness, transverse crack numbers and so on as major parameters of welding speed from 1000 to 4600 mm/min and initial temperature of specimen from R.T. to 873 K with a beam spot size of 0.5 mm and an output power of 1.5 kW. In addition, the specimens were analyzed by Electron Probe X-ray Micro Analyzer, Energy Dispersive X-ray Spectroscopy and X-ray Diffractometry. As a result of experiments, transverse crack-free welding was achieved, when initial temperature was at 873 K. In every condition, the value of Vickers hardness of fused zone increased compared with base. We think the reason of it is an increase of (alpha) 2(Ti3Al) phase, which is caused by rapid cooling, taking in Oxygen, fine structure and so on.

  6. Formation of optical properties of intermetallic nanoclusters formed by sequential ion implantation

    SciTech Connect

    Zuhr, R.A.; Magruder, R.H. III; Anderson, T.S.

    1997-09-01

    Recent demonstrations that large third order nonlinear responses can be achieved in metal nanocluster glass composites are of significant interest because of their potential for use in all optical switching networks. These composite materials exhibit picosecond switching and relaxation times, thermal and chemical stability, high laser damage thresholds, and low two photon absorption. Ion implantation has been shown to be a useful fabrication method to form these nanoclusters in silica because of its ability to produce thin films in waveguide configurations containing a high volume fraction (> 1%) of metal colloids with well defined vertical and horizontal dimensional control. Using sequential ion implantation of more than one element the authors can modify the composition and microstructure of the composites by forming intermetallic metal colloids. In this work the authors report on the improved optical response of metallic nanocluster composites formed by sequential implantation of Cd and Ag and Sb and Ag. Characterization of the samples by transmission electron microscopy (TEM) reveals that approximately spherical metallic colloids are formed for all implanted species during the implantation process. Selected area diffraction patterns indicate that the colloids formed are intermetallic in composition. Linear optical absorption measurements made at room temperature in air from 900 to 200 nm show significant changes in both the magnitude and wavelength of the surface plasmon resonance. The formation of intermetallic nanoclusters results in changes in both the linear and nonlinear optical properties of the composite material that are not possible with single element colloids alone. The results are explained in terms of effective medium theory.

  7. Hydrogen in the Ti3Al intermetallic compound: Study by the NMR method

    NASA Astrophysics Data System (ADS)

    Soloninin, A. V.; Skripov, A. V.; Buzlukov, A. L.; Aleksashin, B. A.; Medvedev, E. Yu.

    2017-02-01

    The times of nuclear spin-lattice relaxation have been measured and the spectra of NMR for 1H and 27Al in Ti3AlH x hydrogenated intermetallic compounds with hydrogen concentrations of x = 0, 0.31, 0.51, 1.0, 2.0, and 4.32 in a wide range of temperatures (10-500 K) and resonance frequencies (8.2-90 MHz) have been recorded. The analysis of low-temperature relaxation data has shown that the addition of hydrogen with a concentration of x ≥ 2 leads to a significant change in the density of electron states at the Fermi level. It has been found that the hydrogen mobility in Ti3AlH x strongly depends on its concentration. For solid solutions of hydrogen in Ti3Al with x < 1, the mobility of hydrogen atoms on the scale of frequencies of NMR in the investigated temperature range has not been detected. In Ti3AlH x compounds with x ≥ 2, the fast diffusion of hydrogen is observed, which can be related to changes in the structure of these compounds.

  8. Observation of superconductivity in the intermetallic compound β-IrSn4

    NASA Astrophysics Data System (ADS)

    Tran, Vinh Hung; Bukowski, Zbigniew; Wiśniewski, Piotr; Tran, Lan Maria; Zaleski, Andrzej J.

    2013-04-01

    Low-temperature dc-magnetization, ac electrical resistivity and specific heat measurements were performed on single crystals of the intermetallic compound β-IrSn4. The compound crystallizes in the tetragonal MoSn4-type structure (space group I41/acd) and exhibits superconductivity below Tc = 0.9 ± 0.05 K. Further, the magnitude of the ratios ΔCp/(γnkBTc) = 1.29, 2Δ/(kBTc) = 3.55 and of the electron-phonon coupling {\\overline{\\lambda }}_{e-p h}=0.5 imply that superconductivity in β-IrSn4 can be ascribed to a s-wave weak coupling regime. We determined crucial thermodynamic characteristics of the superconducting state. It turned out that depending on the assumption of either a spherical or non-spherical Fermi surface, the superconductivity can be ascribed to either a type-I and type-II/1 or type-II in clean limit, respectively. However, the behavior of the upper critical field and the anisotropic crystalline structure of the studied compound provide strong support to the type-II superconductivity. In the normal state the resistivity exhibits a prominent quadratic temperature dependence, which together with a large Kadowaki-Woods ratio and with the enhanced effective mass indicate that the electrons in β-IrSn4 are strongly correlated.

  9. Observation of superconductivity in the intermetallic compound β-IrSn4.

    PubMed

    Tran, Vinh Hung; Bukowski, Zbigniew; Wiśniewski, Piotr; Tran, Lan Maria; Zaleski, Andrzej J

    2013-04-17

    Low-temperature dc-magnetization, ac electrical resistivity and specific heat measurements were performed on single crystals of the intermetallic compound β-IrSn4. The compound crystallizes in the tetragonal MoSn4-type structure (space group I41/acd) and exhibits superconductivity below Tc = 0.9 ± 0.05 K. Further, the magnitude of the ratios ΔCp/(γnkBTc) = 1.29, 2Δ/(kBTc) = 3.55 and of the electron-phonon coupling λ[overline](e-ph) = 0.5 imply that superconductivity in β-IrSn4 can be ascribed to a s-wave weak coupling regime. We determined crucial thermodynamic characteristics of the superconducting state. It turned out that depending on the assumption of either a spherical or non-spherical Fermi surface, the superconductivity can be ascribed to either a type-I and type-II/1 or type-II in clean limit, respectively. However, the behavior of the upper critical field and the anisotropic crystalline structure of the studied compound provide strong support to the type-II superconductivity. In the normal state the resistivity exhibits a prominent quadratic temperature dependence, which together with a large Kadowaki-Woods ratio and with the enhanced effective mass indicate that the electrons in β-IrSn4 are strongly correlated.

  10. First-principles study of Ni-Al intermetallic compounds under various temperature and pressure

    NASA Astrophysics Data System (ADS)

    Wen, Zhiqin; Zhao, Yuhong; Hou, Hua; Tian, Jinzhong; Han, Peide

    2017-03-01

    The pressure dependence behaviors of structural and mechanical properties as well as the effect of temperature on thermodynamic properties of Ni-Al ordered intermetallic compounds (i. e. Ni3Al, Ni5Al3, NiAl, Ni2Al3 and NiAl3) are investigated in details by implementing first-principles calculations. The calculated lattice parameters, bulk modulus and its pressure derivative are well in agreement with available experimental and theoretical values at zero pressure. All the compounds are mechanically stable with pressure going up to 50 GPa, and the volume change resistance of nickel aluminum alloys can be improved by increasing pressure and Ni concentration. The shear deformation resistance, elastic stiffness and microhardness of nickel aluminum alloys can be strengthened by increasing the content of Ni5Al3 and Ni2Al3, and pressure can also enhance these properties of Ni5Al3, NiAl and Ni2Al3. The ductility of Ni3Al, Ni5Al3 and NiAl can be improved by increasing pressure, while brittle nature turns into ductile nature in 20-30 GPa and 10-20 GPa for Ni2Al3 and NiAl3, respectively. Furthermore, the elastic anisotropy of Ni3Al, Ni5Al3, Ni2Al3 and NiAl3 enhances with pressure, while NiAl shows few change with pressure increasing. In addition, Ni3Al is the most sensitive to pressure change among considered compounds. Finally, the Debye temperature, linear thermal expansion coefficient and heat capacity of these compounds are calculated using the quasi-harmonic Debye model in pressure ranging from 0 to 50 GPa and temperature ranging from 0 to 1200 K to elucidate the relationships between thermodynamic parameters and temperature under various pressure. The results are helpful insights into the study of nickel aluminum alloys.

  11. In situ study on the effect of thermomigration on intermetallic compounds growth in liquid-solid interfacial reaction

    SciTech Connect

    Qu, Lin; Zhao, Ning; Ma, Haitao Zhao, Huijing; Huang, Mingliang

    2014-05-28

    Synchrotron radiation real-time imaging technology was carried out in situ to observe and characterize the effect of thermomigration on the growth behavior of interfacial intermetallic compounds (IMCs) in Cu/Sn/Cu solder joint during soldering. The thermomigration resulted in asymmetrical formation and growth of the interfacial IMCs. Cu{sub 6}Sn{sub 5} and Cu{sub 3}Sn IMCs formed at the cold end and grew rapidly during the whole soldering process. However, only Cu{sub 6}Sn{sub 5} IMC formed at the hot end and remained relatively thin until solidification. The IMCs at the cold end were nearly seven times thicker than that at the hot end after solidification. The Cu dissolution at the cold end was significantly restrained, while that at the hot end was promoted, which supplied Cu atoms to diffuse toward the cold end under thermomigration to feed the rapid IMC growth. Moreover, the thermomigration also caused asymmetrical morphology of the interfacial IMCs at the cooling stage, i.e., the Cu{sub 6}Sn{sub 5} IMC at the cold end transformed into facet structure, while that at the hot end remained scallop-type. The asymmetrical growth behavior of the interfacial IMCs was analyzed from the view point of kinetics.

  12. Irradiation-induced disordering and amorphization of Al3Ti-based intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Park, Jeong-Yong; Kim, Il-Hyun; Motta, Arthur T.; Ulmer, Christopher J.; Kirk, Marquis A.; Ryan, Edward A.; Baldo, Peter M.

    2015-12-01

    An in situ ion-irradiation study, simultaneously examined using transmission electron microscopy, was performed to investigate irradiation-induced disordering and amorphization of Al3Ti-based intermetallic compounds. Thin foil samples of two crystalline structures: D022-structured Al3Ti and L12-structured (Al,Cr)3Ti were irradiated using 1.0 MeV Kr ions at a temperature range from 40 K to 573 K to doses up to 4.06 × 1015 ions/cm2. The results showed that both the compounds underwent an order-disorder transformation under irradiation, where both Al3Ti and (Al,Cr)3Ti ordered structures were fully transformed to the disordered face-centered cubic (FCC) structure except at the highest irradiation temperature of 573 K. A slightly higher irradiation dose was required for order-disorder transformation in case of Al3Ti as compared to (Al,Cr)3Ti at a given temperature. However, their amorphization resistances were different: while the disordered FCC (Al,Cr)3Ti amorphized at the irradiation dose of 6.25 × 1014 ions/cm2 (0.92 dpa) at 40 K and 100 K, the Al3Ti compound with the same disordered FCC structure maintained crystallinity up to 4.06 × 1015 ions/cm2 (5.62 dpa) at 40 K. The critical temperature for amorphization of (Al,Cr)3Ti under Kr ion irradiation is likely between 100 K and room temperature and the critical temperature for disordering between room temperature and 573 K.

  13. A framework for studying dynamics and stability of diffusive-reactive interfaces with application to Cu6Sn5 intermetallic compound growth.

    PubMed

    Udupa, Anirudh; Sadasiva, Subramanya; Subbarayan, Ganesh

    2016-06-01

    Often during phase growth, the rate of accretion, on the one hand, is determined by a competition between bulk diffusion and surface reaction rate. The morphology of the phase interface, on the other hand, is determined by an interplay between surface diffusivity and surface reaction rate. In this study, a framework to predict the growth and the morphology of an interface by modelling the interplay between bulk diffusion, surface reaction rate and surface diffusion is developed. The framework is demonstrated using the example of Cu-Sn intermetallic compound growth that is of significance to modern microelectronic assemblies. In particular, the dynamics and stability of the interface created when Cu and Sn react to form the compound Cu6Sn5 is explored. Prior experimental observations of the Cu6Sn5-Sn interface have shown it to possess either a scalloped, flat or needle-shaped morphology. Diffuse interface simulations are carried out to elucidate the mechanism behind the interface formation. The computational model accounts for the bulk diffusion of Cu through the intermetallic compound, reaction at the interface to form Cu6Sn5, surface diffusion of Cu6Sn5 along the interface and the influence of the electric current density in accelerating the bulk diffusion of Cu. A stability analysis is performed to identify the conditions under which the interface evolves into a flat, scalloped or needle-shaped structure.

  14. Investigation of InBi intermetallic compounds as possible topological insulators

    NASA Astrophysics Data System (ADS)

    Lin, Y. T.; Chen, Q. Y.; Hseih, W. C.; Chang, C. F.; Chuang, F. C.; Liao, H. H.

    2015-03-01

    InBi intermetallic compounds were found to be potentially 2-dimensional topological insulators from first-principle calculations. In our experiment, InBi, In2Bi3andIn3Bi5 were fabricated either in bulk or thin film, by depositing In and Bi into 2 layers by e-beam evaporation of proper thickness ratios for each stoichiometry. The bi-layers were rapid thermal annealed to accomplish the reaction or intermixing well above their temperatures of phase transition. EDS and secondary electron imaging were used to determine the obtained stoichiometry. CVD using a 3-zone furnace was as tested with various combinations of zone temperatures, types and flow rates of carrying gases to investigate the feasibility of epitaxial growth. Samples were characterized by XRD to obtain the crystalline phase, magneto-transport measurements to determine the carrier concentration and mobility using a PPMS to correlate the measured results. We will ponder on the implication of our findings in regards to the possibilities of being a candidate for topological insulator as predicted by the calculations.

  15. Machinability of Intermetallic Compound Fe3Al from the Viewpoint of Tool Wear

    NASA Astrophysics Data System (ADS)

    Sasaki, Tomohiro; Yakou, Takao

    The intermetallic compound Fe3Al was processed by a reactive sintering process, and its machinability from the viewpoint of tool wear was investigated using dry turning. In cutting Fe3Al with a cemented carbide tool, the tool life was approximately one tenth that of cutting carbon tool steel SK3 because of intense flank wear. The tool life for cutting Fe3Al using the cemented carbide P20(WC-TiC-TaC-Co) tool was longer than for cemented carbide K10(WC-Co). In addition, a cermet tool reached its tool life limit by chipping for the whole cutting speed range measured. The roughness of the machined surface of Fe3Al cut using a cemented carbide tool was much smaller than for SK3. However, for cutting using the cermet tool, the roughness showed a sharp rise due to chipping. It was found that the wear rate of the WC particles in the tool material is larger than TiC particles. The results of the study suggest that the cemented carbide P20 is suitable for cutting Fe3Al.

  16. Discovery and characterization of magnetism in sigma-phase intermetallic Fe-Re compounds

    SciTech Connect

    Cieślak, J. Dubiel, S. M.; Tobola, J.; Reissner, M.

    2014-11-14

    Systematic experimental studies (vibrating sample magnetometry) supported by theoretical calculations (electronic structure by spin self-consistent Korringa-Kohn-Rostoker Green's function method) were performed on a series of intermetallic sigma-phase Fe{sub 100−x}Re{sub x} (x = 43–53) compounds. All investigated samples exhibit magnetism with an ordering temperature ranging between ∼65 K for x = 43 and ∼23 K for x = 53. The magnetism was revealed to be itinerant and identified as a spin-glass (SG) possibly having a re-entrant character. The SG was found to be heterogeneous, viz., two regimes could be distinguished as far as irreversibility in temperature dependence of magnetization is concerned: (1) of a weak irreversibility and (2) of a strong one. According to the theoretical calculations, the main contribution to the magnetism comes from Fe atoms occupying all five sub lattices, while Re atoms have rather small magnetic moments. However, the calculated average magnetic moments highly (ferromagnetic ordering model) or moderately (antiparallel ordering model) overestimate the experimental data.

  17. Model-based predictions of solid state intermetallic compound layer growth in hybrid microelectronic circuits

    SciTech Connect

    Vianco, P.T.; Erickson, K.L.; Hopkins, P.L.

    1997-12-31

    A mathematical model was developed to quantitatively describe the intermetallic compound (IMC) layer growth that takes place between a Sn-based solder and a noble metal thick film conductor material used in hybrid microcircuit (HMC) assemblies. The model combined the reaction kinetics of the solder/substrate interaction, as determined from ancillary isothermal aging experiments, with a 2-D finite element mesh that took account of the porous morphology of the thick film coating. The effect of the porous morphology on the IMC layer growth when compared to the traditional 1-D computations was significant. The previous 1-D calculations under-predicted the nominal IMC layer thickness relative to the 2-D case. The 2-D model showed greater substrate consumption by IMC growth and lesser solder consumption that was determined with the 1-D computation. The new 2-D model allows the design engineer to better predict circuit aging and hence, the reliability of HMC hardware that is placed in the field.

  18. Interaction Between the Growth and Dissolution of Intermetallic Compounds in the Interfacial Reaction Between Solid Iron and Liquid Aluminum

    NASA Astrophysics Data System (ADS)

    Chen, Shuhai; Yang, Dongdong; Zhang, Mingxin; Huang, Jihua; Zhao, Xingke

    2016-10-01

    The interfacial reaction between solid steel and liquid aluminum has been widely investigated in past decades; however, some issues, such as the solid/liquid interfacial structure, formation mechanisms of FeAl3 and Fe2Al5, and interaction between the growth and dissolution of intermetallic compounds, are still not fully understood. In this study, a hot-dipping method is designed to investigate the interfacial reaction in the temperature range between 973 K and 1273 K (700 °C 1000 °C) for 10 to 60 seconds. The intensification of the dissolution leads to the transformation of FeAl3/liquid aluminum into Fe2Al5/liquid aluminum in the solid/liquid structure with increasing reaction temperature. The formation of FeAl3 adhered to the interface depends not only on the reaction mechanism but also on precipitation at relatively low temperatures. In contrast, precipitation is the only formation mechanism for FeAl3 at relatively high temperatures. Austenitizing results in the complete transformation of the tongue-like Fe2Al5/Fe interface to a flat shape. The growth of Fe2Al5 with respect to the maximum thickness is governed by the interfacial reaction process, whereas the growth of Fe2Al5 with respect to the average thickness is governed by the diffusion process in the range of 973 K to 1173 K (700 °C to 900 °C) for 10 to 60 seconds. The dissolution of the parent metal is due to the natural dissolution of FeAl3 at low temperatures and Fe2Al5 at high temperatures.

  19. Structural, stability and electronic properties of C15-AB2 (A = Ti, Zr; B = Cr) intermetallic compounds and their hydrides: An ab initio study

    NASA Astrophysics Data System (ADS)

    Sarhaddi, Reza; Arabi, Hadi; Pourarian, Faiz

    2014-05-01

    The structural, stability and electronic properties of C15-AB2 (A = Ti, Zr; B = Cr) isomeric intermetallic compounds were systematically investigated by using density functional theory (DFT) and plane-wave pseudo-potential (PW-PP) method. The macroscopic properties including the lattice constant, bulk modulus and stability for these compounds were studied before and after hydrogenation. For parent compounds, the enthalpy of formation was evaluated with regard to their bulk modules and electronic structures. After hydrogenation of compounds at different interstitial tetrahedral sites (A2B2, A1B3, B4), a volume expansion was found for hydrides. The stability properties of hydrides characterized the A2B2 sites as the site preference of hydrogen atoms for both compounds. The Miedema's "reverse stability" rule is also satisfied in these compounds as lower the enthalpy of formation for the host compound, the more stable the hydride. Analysis of microscopic properties (electronic structures) after hydrogenation at more stable interstitial site (A2B2) shows that the H atoms interact stronger with the weaker (or non) hydride forming element B (Cr) than the hydride forming element A (Ti/Zr). A correlation was also found between the stability of the hydrides and their electronic structure: the deeper the hydrogen band, the less stable the hydride.

  20. Interfacial reaction of intermetallic compounds of ultrasonic-assisted brazed joints between dissimilar alloys of Ti6Al4V and Al4Cu1Mg.

    PubMed

    Ma, Zhipeng; Zhao, Weiwei; Yan, Jiuchun; Li, Dacheng

    2011-09-01

    Ultrasonic-assisted brazing of Al4Cu1Mg and Ti6Al4V using Zn-based filler metal (without and with Si) has been investigated. Before brazing, the Ti6Al4V samples were pre-treated by hot-dip aluminizing and ultrasonic dipping in a molten filler metal bath in order to control the formation of intermetallic compounds between the Ti6Al4V samples and the filler metal. The results show that the TiAl(3) phase was formed in the interface between the Ti6Al4V substrate and the aluminized coating. For the Zn-based filler metal without Si, the Ti6Al4V interfacial area of the brazed joint did not change under the effect of the ultrasonic wave, and only consisted of the TiAl(3) phase. For the Zn-based filler metal with Si, the TiAl(3) phase disappeared and a Ti(7)Al(5)Si(12) phase was formed at the interfacial area of the brazed joints under the effect of the ultrasonic wave. Due to the TiAl(3) phase completely changing to a Ti(7)Al(5)Si(12) phase, the morphology of the intermetallic compounds changed from a block-like shape into a lamellar-like structure. The highest shear strength of 138MPa was obtained from the brazed joint free of the block-like TiAl(3) phase.

  1. Formation of a diffusion-based intermetallic interface layer in friction stir welded dissimilar Al-Cu lap joints

    NASA Astrophysics Data System (ADS)

    Marstatt, R.; Krutzlinger, M.; Luderschmid, J.; Zaeh, M. F.; Haider, F.

    2017-03-01

    The joining of dissimilar metals is an important issue in modern lightweight design. Friction Stir Welding (FSW) is suitable for this task since the solidus temperature is usually not exceeded during the process. As a consequence, dissimilar joints can be produced with a minimum of deteriorating intermetallic phases. The latest studies showed the formation of intermetallic layers at the bonding interface with no significant negative influence on the seam quality. In this study, those intermetallic nanolayers at the interface of aluminium / copper lap joints were analysed. For the experiments, the commercially pure alloys EN AW-1050 and CW008A were chosen. The process temperature changed with respect to the parameter setup and was measured at different locations of the seam. The intermetallic layers at the interface were analysed by scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM). The experiments show that the thickness of the interlayer clearly correlates with the process temperature using an Arrhenius equation. It is supposed, that the rotating probe removes the oxide layers of the metal surfaces and a metallic bonding between the Al- and the Cu-phase is formed. Due to the elevated temperature after the probe has passed, the intermetallic layer has emerged by interdiffusion.

  2. Atomic jump frequencies in intermetallic compounds studied using perturbed angular correlation of gamma rays

    NASA Astrophysics Data System (ADS)

    Newhouse, Randal Leslie

    Atomic jump frequencies were determined in a variety of intermetallic compounds through analysis of nuclear relaxation of spectra measured using the nuclear hyperfine technique, perturbed angular correlation (PAC) of gamma rays. Observed at higher temperatures, this relaxation is attributed to fluctuations in the orientation or magnitude of electric field gradients (EFG) at nuclei of 111In/Cd probe atoms as the atoms make diffusive jumps. Jump frequencies were obtained by fitting dynamically relaxed PAC spectra using either an empirical relaxation function or using ab initio relaxation models created using the program PolyPacFit. Jump frequency activation enthalpies were determined from measurements over a range of temperatures. Diffusion was studied in the following systems: 1) Pseudo-binary alloys having the L12 crystal structure such as In3(La1-xPrx). The goal was to see how jump frequencies were affected by random disorder. 2) The family of layered phases, LanCoIn3n+2 ( n=0,1,2,3…∞). The goal was to see how jump frequencies varied with the spacing of Co layers, which were found to block diffusion. 3) Phases having the FeGa3 structure. The goal was to analyze dynamical relaxation for probe atoms having multiple inequivalent jump vectors. 4) Phases having the tetragonal Al4Ba structure. The goal was to search for effects in the PAC spectra caused by fluctuations in magnitudes of EFGs without fluctuations in orientations. Ab initio relaxation models were developed to simulate and fit dynamical relaxation for PAC spectra of FeGa3, and several phases with the Al4Ba structure in order to determine underlying microscopic jump frequencies. In the course of this work, site preferences also were observed for 111In/Cd probe atoms in several FeGa 3 and Al4Ba phases.

  3. Smart Solution Chemistry to Sn-Containing Intermetallic Compounds through a Self-Disproportionation Process.

    PubMed

    Zhang, Yuelan; Li, Liping; Li, Qi; Fan, Jianming; Zheng, Jing; Li, Guangshe

    2016-09-26

    Developing new methods to synthesize intermetallics is one of the most critical issues for the discovery and application of multifunctional metal materials; however, the synthesis of Sn-containing intermetallics is challenging. In this work, we demonstrated for the first time that a self-disproportionation-induced in situ process produces cavernous Sn-Cu intermetallics (Cu3 Sn and Cu6 Sn5 ). The successful synthesis is realized by introducing inorganic metal salts (SnCl2 ⋅2 H2 O) to NaOH aqueous solution to form an intermediate product of reductant (Na2 SnO2 ) and by employing steam pressures that enhance the reduction ability. Distinct from the traditional in situ reduction, the current reduction process avoided the uncontrolled phase composition and excessive use of organic regents. An insight into the mechanism was revealed for the Sn-Cu case. Moreover, this method could be extended to other Sn-containing materials (Sn-Co, Sn-Ni). All these intermetallics were attempted in the catalytic effect on thermal decompositions of ammonium perchlorate. It is demonstrated that Cu3 Sn showed an outstanding catalytic performance. The superior property might be primarily originated from the intrinsic chemical compositions and cavernous morphology as well. We supposed that this smart solution reduction methodology reported here would provide a new recognition for the reduction reaction, and its modified strategy may be applied to the synthesis of other metals, intermetallics as well as some unknown materials.

  4. Effect of Y2O3 and TiC Reinforcement Particles on Intermetallic Formation and Hardness of Al6061 Composites via Mechanical Alloying and Sintering

    NASA Astrophysics Data System (ADS)

    Chen, Chun-Liang; Lin, Chen-Han

    2015-08-01

    Al6061-based composites reinforced with 2 wt pctY2O3 and 2 wt pctTiC particles produced by mechanical alloying were investigated. The reinforced particles play important roles in the microstructural development and in determining the properties of the alloys. High-energy ball milling can facilitate a solid-state reaction between reinforced particles and the Al matrix, and the reaction kinetics of atomic diffusion can be accelerated enormously by subsequent sintering processing. As a result, complex intermetallic compounds and oxide particles can be formed in the alloy. In this study, the effect of reinforcement on phase formation and mechanical properties of Al6061-based composites has been examined. The results suggest that nano-Y2O3 particles can act as nucleation sites to facilitate formation of Al-Si-Y-O-based oxide particles. The addition of TiC particles can effectively refine the grain structure and encourage formation of iron-rich intermetallic compounds. Nanoindentation was used to understand the local variations in mechanical properties of the Al6061-based composites.

  5. Behavior of alloys of the PtPd intermetallic compound with Hf and Zr in the electrosynthesis of peroxo salts

    SciTech Connect

    Toroptseva, N.T.; Vaseva, A.Yu.

    1988-08-10

    The objective of this study was to investigate the behavior of anodes made of alloys of the PtPd intermetallic compound with Hf and Zr in the synthesis of potassium peroxodicarbonates and peroxoborates. The investigations were based on polarization measurements in different regimes on stationary and rotating electrodes, the determination of the current yield of active oxygen in galvano- and potentiostatic syntheses, and the study of the kinetics of catalytic decomposition of peroxide solutions in the presence of the electrode in the range 289-308 K.

  6. Hydrides of intermetallic compounds with a H/M ratio greater than unity obtained at high hydrogen pressures

    SciTech Connect

    Semenenko, K.N.; Klyamkin, S.N.

    1993-11-01

    Novel hydride phases with H/M > 1 based on Zr{sub 2}Pd, Hf{sub 2}Pd, and Hf{sub 2}Cu (structures of the MoSi{sub 2} type) have been synthesized at high H{sub 2} pressures. The X-ray diffraction investigations of the resulting hydrides have been carried out. Some factors determining the maximum hydrogen content in the hydrides of intermetallic compounds are discussed. A model structure of the hydrides obtained is proposed, which assumes the possibility of direct H-H interactions when the interatomic distances are less than 1 {angstrom}.

  7. Effects of metallic nanoparticle doped flux on the interfacial intermetallic compounds between lead-free solder ball and copper substrate

    SciTech Connect

    Sujan, G.K. Haseeb, A.S.M.A. Afifi, A.B.M.

    2014-11-15

    Lead free solders currently in use are prone to develop thick interfacial intermetallic compound layers with rough morphology which are detrimental to the long term solder joint reliability. A novel method has been developed to control the morphology and growth of intermetallic compound layers between lead-free Sn–3.0Ag–0.5Cu solder ball and copper substrate by doping a water soluble flux with metallic nanoparticles. Four types of metallic nanoparticles (nickel, cobalt, molybdenum and titanium) were used to investigate their effects on the wetting behavior and interfacial microstructural evaluations after reflow. Nanoparticles were dispersed manually with a water soluble flux and the resulting nanoparticle doped flux was placed on copper substrate. Lead-free Sn–3.0Ag–0.5Cu solder balls of diameter 0.45 mm were placed on top of the flux and were reflowed at a peak temperature of 240 °C for 45 s. Angle of contact, wetting area and interfacial microstructure were studied by optical microscopy, field emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. It was observed that the angle of contact increased and wetting area decreased with the addition of cobalt, molybdenum and titanium nanoparticles to flux. On the other hand, wettability improved with the addition of nickel nanoparticles. Cross-sectional micrographs revealed that both nickel and cobalt nanoparticle doping transformed the morphology of Cu{sub 6}Sn{sub 5} from a typical scallop type to a planer one and reduced the intermetallic compound thickness under optimum condition. These effects were suggested to be related to in-situ interfacial alloying at the interface during reflow. The minimum amount of nanoparticles required to produce the planer morphology was found to be 0.1 wt.% for both nickel and cobalt. Molybdenum and titanium nanoparticles neither appear to undergo alloying during reflow nor have any influence at the solder/substrate interfacial reaction. Thus, doping

  8. Stability of molybdenum nanoparticles in Sn-3.8Ag-0.7Cu solder during multiple reflow and their influence on interfacial intermetallic compounds

    SciTech Connect

    Haseeb, A.S.M.A. Arafat, M.M. Johan, Mohd Rafie

    2012-02-15

    This work investigates the effects of molybdenum nanoparticles on the growth of interfacial intermetallic compound between Sn-3.8Ag-0.7Cu solder and copper substrate during multiple reflow. Molybdenum nanoparticles were mixed with Sn-3.8Ag-0.7Cu solder paste by manual mixing. Solder samples were reflowed on a copper substrate in a 250 Degree-Sign C reflow oven up to six times. The molybdenum content of the bulk solder was determined by inductive coupled plasma-optical emission spectrometry. It is found that upon the addition of molybdenum nanoparticles to Sn-3.8Ag-0.7Cu solder, the interfacial intermetallic compound thickness and scallop diameter decreases under all reflow conditions. Molybdenum nanoparticles do not appear to dissolve or react with the solder. They tend to adsorb preferentially at the interface between solder and the intermetallic compound scallops. It is suggested that molybdenum nanoparticles impart their influence on the interfacial intermetallic compound as discrete particles. The intact, discrete nanoparticles, by absorbing preferentially at the interface, hinder the diffusion flux of the substrate and thereby suppress the intermetallic compound growth. - Highlights: Black-Right-Pointing-Pointer Mo nanoparticles do not dissolve or react with the SAC solder during reflow. Black-Right-Pointing-Pointer Addition of Mo nanoparticles results smaller IMC thickness and scallop diameter. Black-Right-Pointing-Pointer Mo nanoparticles influence the interfacial IMC through discrete particle effect.

  9. Review of magnetic properties and magnetocaloric effect in the intermetallic compounds of rare earth with low boiling point metals

    NASA Astrophysics Data System (ADS)

    Ling-Wei, Li

    2016-03-01

    The magnetocaloric effect (MCE) in many rare earth (RE) based intermetallic compounds has been extensively investigated during the last two decades, not only due to their potential applications for magnetic refrigeration but also for better understanding of the fundamental problems of the materials. This paper reviews our recent progress on studying the magnetic properties and MCE in some binary or ternary intermetallic compounds of RE with low boiling point metal(s) (Zn, Mg, and Cd). Some of them exhibit promising MCE properties, which make them attractive for low temperature magnetic refrigeration. Characteristics of the magnetic transition, origin of large MCE, as well as the potential application of these compounds are thoroughly discussed. Additionally, a brief review of the magnetic and magnetocaloric properties in the quaternary rare earth nickel boroncarbides RENi2B2C superconductors is also presented. Project supported by the National Natural Science Foundation of China (Grant Nos. 11374081 and 11004044), the Fundamental Research Funds for the Central Universities, China (Grant Nos. N150905001, L1509006, and N140901001), the Japan Society for the Promotion of Science Postdoctoral Fellowships for Foreign Researchers (Grant No. P10060), and the Alexander von Humboldt (AvH) Foundation (Research stipend to L. Li).

  10. Intermetallic compounds formed at the interface between Cu substrate and an Sn-9Zn-0.5Ag lead-free solder

    SciTech Connect

    Chang, T.-C.; Hon, M.-H.; Wang, M.-C

    2003-04-30

    The intermetallic compounds (IMCs) formed at the interface between Cu substrate and an Sn-9Zn-0.5Ag lead-free solder alloy have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and electron diffraction (ED). The XRD patterns show that the main IMCs formed at the interface of Sn-9Zn-0.5Ag/Cu are {gamma}-Cu{sub 5}Zn{sub 8} and {eta}'-Cu{sub 6}Sn{sub 5}. The Ag{sub 3}Sn IMC with orthorhombic structure was also observed at the Sn-9Zn-0.5Ag/Cu interface by TEM and ED analyses. The interfacial adhesion strength between the Cu substrate and Sn-9Zn-0.5Ag lead-free solder alloy is higher than that of the Sn-9Zn alloy due to the formation of Ag{sub 3}Sn IMC at the interface.

  11. LaAu2 and CeAu2 surface intermetallic compounds grown by high-temperature deposition on Au(111)

    NASA Astrophysics Data System (ADS)

    Ormaza, M.; Fernández, L.; Lafuente, S.; Corso, M.; Schiller, F.; Xu, B.; Diakhate, M.; Verstraete, M. J.; Ortega, J. E.

    2013-09-01

    We report on the crystal structure and electronic bands of LaAu2 and CeAu2 surface intermetallic compounds grown by high-temperature deposition on Au(111). By scanning-tunneling microscopy we study the formation of different alloy phases as a function of growth temperature and lanthanide coverage. We determine the specific growth conditions to achieve monolayers and bilayers of LaAu2 and CeAu2 with high crystalline quality. Due to lattice mismatch with the underlying Au substrate, both LaAu2 and CeAu2 exhibit long-range moiré patterns, which can serve as templates for further nanostructure growth. By angle-resolved photoemission we map the two-dimensional band structure of these surface alloys, discussing the nature of the different spectral features in the light of first-principles calculations.

  12. Kinetics of compound formation in Cu-Sb thin films

    NASA Astrophysics Data System (ADS)

    Halimi, R.; Merabet, A.

    1989-12-01

    Formation processes of intermetallic compounds on annealing, at temperatures from 150°C to 600 ° C, of Cu-Sb two-layer thin films are studied by means of the helium ion backscattering technique and X-ray diffractometry. It is found that at annealing up to 300 °C only the compound Cu 2Sb is formed. During the subsequent heat treatment from 350 °C to 600 °C the final Cu 9Sb 2 phase nucleates and grows at the expense of the Cu 2Sb phase. The structure of the Cu 2Sb compound is tetragonal. The Cu 9Sb 2 phase presents a superstructure of close-packed hexagonal type.

  13. The role of zinc on the chemistry of complex intermetallic compounds

    SciTech Connect

    Xie, Weiwei

    2014-01-01

    Combining experiments and electronic structure theory provides the framework to design and discover new families of complex intermetallic phases and to understand factors that stabilize both new and known phases. Using solid state synthesis and multiple structural determinations, ferromagnetic β-Mn type Co8+xZn12–x was analyzed for their crystal and electronic structures.

  14. Chemistry of intermetallic hydrides

    SciTech Connect

    Reilly, J.J.

    1991-01-01

    Certain intermetallic hydrides are safe, convenient and inexpensive hydrogen storage compounds. A particular advantage of such compounds is the ease with which their properties can be modified by small changes in alloy composition or preparation. This quality can be exploited to optimize their storage properties for particular applications, e.g. as intermetallic hydride electrodes in batteries. We will be concerned herein with the more important aspects of the thermodynamic and structural principles which regulate the behavior of intermetallic hydrogen systems and then illustrate their application using the archetype hydrides of LaNi5, FeTi and Mg alloys. The practical utility of these classes of materials will be briefly noted.

  15. Effect of cooling condition and Ag on the growth of intermetallic compounds in Sn-based solder joints

    NASA Astrophysics Data System (ADS)

    Ma, Haoran; Kunwar, Anil; Guo, Bingfeng; Sun, Junhao; Jiang, Chengrong; Wang, Yunpeng; Song, Xueguan; Zhao, Ning; Ma, Haitao

    2016-12-01

    The intermetallic compound growth in Sn/Cu and Sn-3.5Ag/Cu solder joints undergoing cooling has been in-situ observed using synchrotron radiation X-ray imaging technique. The overall thickness of intermetallic compound attained during cooling condition is dependent on the rates of Cu precipitation or deposition from the bulk solder and Cu diffusion from grain boundary at interface. Although the net increase in IMC thickness contributed predominantly by deposition kinetics is greater for air cooling than in furnace cooling from the start temperature of 300°C for the first 20 min, the former solidifies before 30 min and the latter stays in liquid state for 1 h due to slower cooling rate and attains a bigger IMC of size about 14.5 μm. In context of Sn-3.5Ag solders subjected to air cooling from 275°C, the presence of Ag contributes to the increment in overall IMC thickness during the cooling period. For the improvement in solder joints reliability, faster cooling rate and limiting the Ag content can be employed as the materials design and processing parameters.

  16. Estimation of the composition of intermetallic compounds in LiCl-KCl molten salt by cyclic voltammetry.

    PubMed

    Liu, Ya L; Liu, Kui; Yuan, Li Y; Chai, Zhi F; Shi, Wei Q

    2016-08-15

    In this work, the compositions of Ce-Al, Er-Al and La-Bi intermetallic compounds were estimated by the cyclic voltammetry (CV) technique. At first, CV measurements were carried out at different reverse potentials to study the co-reduction processes of Ce-Al, Er-Al and La-Bi systems. The CV curves obtained were then re-plotted with the current as a function of time, and the coulomb number of each peak was calculated. By comparing the coulomb number of the related peaks, the compositions of the Ce-Al, Er-Al and La-Bi intermetallic compounds formed in the co-reduction process could be estimated. The results showed that Al11Ce3, Al3Ce, Al2Ce and AlCe could be formed by the co-reduction of Ce(iii) and Al(iii). For the co-reduction of Er(iii) and Al(iii), Al3Er2, Al2Er and AlEr were formed. In a La(iii) and Bi(iii) co-existing system in LiCl-KCl melts, LaBi2, LaBi and Li3Bi were the major products as a result of co-reduction.

  17. The characteristics of hot swaged NiAl intermetallic compounds with ternary additions consolidated by HIP techniques

    SciTech Connect

    Ishiyama, S.; Eto, M.; Mishima, Y.; Miura, S.; Suzuki, T.

    1995-12-31

    Stoichiometric and non-stoichiometric NiAl intermetallics with ternary additives, such as Ti, Zr, Hf, V, Nb, Ta, Cr, Mo or Mo/e, W, Mn, Fe, Cu and B, fabricated with the combination of Hot Isostatic Pressing (HIP) and hot swaging techniques have been investigated. The mechanical properties of hot swaged NiAl with various ternary additives, consolidated by ion beam casting or HIP techniques, have been tested at temperatures ranging from R.T. to 1,000 C. It is found that significant tensile elongation at room temperature can be achieved by hot swaged as-HIP`ed NiAl compounds with Mo or Mo/Re additives, whereas cast and hot swaged compounds with Mo addition resulted in some elongation above 400 C.

  18. Structure comparison between Th2Zn17-type and TbCu7-type Sm Fe intermetallic compounds and their nitrides by means of 57Fe-Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Sakai, Yoichi; Omatsuzawa, Ryo; Sakazaki, Iwao; Suzuki, Sayaka; Hashino, Hayato; Saito, Takanobu; Iriyama, Takahiko

    2005-11-01

    Samarium iron intermetallic compounds were prepared by a melt spinning method with low and high wheel speeds, which resulted in a Th2Zn17-type and a TbCu7-type structure, respectively. Structure comparison between these types was investigated for Sm Fe intermetallic compounds and their nitrides by 57Fe-Mössbauer spectroscopy.

  19. First principle investigation of crystal lattice structure, thermodynamics and mechanical properties in ZnZrAl2 intermetallic compound

    NASA Astrophysics Data System (ADS)

    Wei, Zhenyi; Tou, Shushi; Wu, Bo; Bai, Kewu

    2016-12-01

    ZnZrAl2 is a kind of heterogeneous nucleation to promote the refine of grain of ZA43 alloy. ZnZrAl2 intermetallic is also considered as a candidate for superalloys. The crystal lattice structure, alloy thermodynamics and mechanical properties of ZnZrAl2 intermetallic compound were investigated by ab initio calculations based on density functional theory (DFT). In particular, the site preference of atoms in different sublattices was predicted based on alloy thermodynamics. At ground state, the most stable structure is L12 structure with sublattice model (Zn)1a(Zr0.3333Al0.6667)3c or (Zr)1a(Zn0.3333Al0.6667)3c, and the occupying preferences of Zn, Zr and Al atoms are independent with the increasing temperature. The bulk, shear, Young's modulus and the Poisson's ratio of the L12 structure ZnZrAl2 were calculated based on the site occupying configurations. The results show that ZnZrAl2 is a brittle material in nature. Electronic structures analysis revealed that Al-Zr atoms possess a covalent bonding character, while the Zn-Zr atoms have a metallic bonding character. ZnZrAl2 has stable mechanical properties at high temperature. The grain refinement effect of ZnZrAl2 precipitates in Zn-Al alloys were discussed based on crystal lattice match theory.

  20. Study on the Formation and Characterization of the Intermetallics in Friction Stir Welding of Aluminum Alloy to Coated Steel Sheet Lap Joint

    NASA Astrophysics Data System (ADS)

    Das, H.; Ghosh, R. N.; Pal, T. K.

    2014-10-01

    Multimaterial fabrication such as joining of steel and aluminum is currently prominent in a variety of industries. Friction stir welding is a novel solid-state welding process that causes good joint strength between steel and aluminum. However, the phenomenon contributing significant strength at the interface is not yet clear. In the present study, the interface of the friction stir lap-welded aluminum and coated steel sheet having joint strength maximum (71.4 pct of steel base metal) and minimum, respectively, under two parameter combinations, i.e., 1000 rpm 50 mm min-1 and 500 rpm 100 mm min-1, was exclusively characterized by X-ray diffraction, transmission electron microscopy (TEM), concentration profile, and elemental mapping by electron-probe microanalysis. A TEM-assisted EDS study identifies the morphologies of large size Al13Fe4 and small size Fe3Al-type intermetallic compounds at the interface. The diffusion-induced intermetallic growth (thickness) measured from a backscattered image and concentration profile agreed well with the numerically calculated one. The growth of these two phases at 1000 rpm 50 mm min-1 is attributed to the slower cooling rate (~3.5 K/s) with higher diffusion time (44 seconds) along the interface in comparison to the same for 500 rpm 100 mm min-1 with faster cooling rate (~10 K/s) and less diffusion time (13.6 seconds). The formation of thermodynamically stable and hard intermetallic phase Al13Fe4 at 1000 rpm and travel speed 50 mm min-1 in amounts higher than 500 rpm and a travel speed of 100 mm min-1 results in better joint strength, i.e., 71.4 pct, of the steel base metal.

  1. Magnetotransport and magnetothermal properties of the ternary intermetallic compound TbFe2Al10

    NASA Astrophysics Data System (ADS)

    Khandelwal, Ashish; Chattopadhyay, M. K.; Roy, S. B.

    2016-09-01

    We have studied the temperature and field dependences of electrical resistivity and heat capacity of TbFe2Al10, and have also complimented the above studies with low field magnetization measurements. In zero magnetic field, TbFe2Al10 exhibits paramagnetic (PM) to ferrimagnetic (Ferri-I) and Ferri-I to antiferromagnetic (AFM) phase transitions below 17.6 and 10 K respectively. We have found that the electrical resistivity of TbFe2Al10 exhibits a sharp rise across the PM to Ferri-I phase transition in this compound. Our analysis indicates that this sharp rise of electrical resistivity is related to the formation of new zone boundaries (across the PM to Ferri-I phase transition) that reduce the area of the Fermi surface. We have found that TbFe2Al10 exhibits large magnetoresistance (MR) below 100 K. Overall, the MR behaviour of TbFe2Al10 below 17.6 K in different magnetic fields reveals strong competition between AFM and ferromagnetic (FM) correlations, which seems to be quite intrinsic to the magnetic structure of the compound. Our analysis indicates that the large MR and magnetocaloric effect persisting deep inside the PM regime of TbFe2Al10 is mainly related to the presence of FM spin fluctuations and the formation of a Griffiths like (GL) phase consisting of FM clusters within the PM regime. The formation of the GL phase may be mediated by the static crystal defects in the midst of the competing inter and intra layer magnetic interactions.

  2. FP-LAPW based investigation of structural, electronic and mechanical properties of CePb{sub 3} intermetallic compound

    SciTech Connect

    Pagare, Gitanjali Jain, Ekta; Abraham, Jisha Annie; Sanyal, Sankar P.

    2015-08-28

    A theoretical study of structural, electronic, elastic and mechanical properties of CePb{sub 3} intermetallic compound has been investigated systematically using first principles density functional theory. The calculations are carried out within the three different forms of generalized gradient approximation (GGA) and LSDA for the exchange correlation potential. The ground state properties such as lattice parameter (a{sub 0}), bulk modulus (B) and its pressure derivative (B′) are calculated and obtained lattice parameter of this compound shows well agreement with the experimental results. We have calculated three independent second order elastic constants (C{sub 11}, C{sub 12} and C{sub 44}), which has not been calculated and measured yet. From energy dispersion curves, it is found that the studied compound is metallic in nature. Ductility of this compound is analyzed using Pugh’s criteria and Cauchy's pressure (C{sub 11}-C{sub 12}). The mechanical properties such as Young's modulus, shear modulus, anisotropic ratio, Poison's ratio have been calculated for the first time using the Voigt–Reuss–Hill (VRH) averaging scheme. The average sound velocities (v{sub m}), density (ρ) and Debye temperature (θ{sub D}) of this compound are also estimated from the elastic constants.

  3. Syntheses and properties of several metastable and stable hydrides derived from intermetallic compounds under high hydrogen pressure

    NASA Astrophysics Data System (ADS)

    Filipek, S. M.; Paul-Boncour, V.; Liu, R. S.; Jacob, I.; Tsutaoka, T.; Budziak, A.; Morawski, A.; Sugiura, H.; Zachariasz, P.; Dybko, K.; Diduszko, R.

    2016-12-01

    Brief summary of our former work on high hydrogen pressure syntheses of novel hydrides and studies of their properties is supplemented with new results. Syntheses and properties of a number of hydrides (unstable, metastable or stable in ambient conditions) derived under high hydrogen pressure from intermetallic compounds, like MeT2, MeNi5, Me7T3, Y6Mn23 and YMn12 (where Me = zirconium, yttrium or rare earth; T = transition metal) are presented. Stabilization of ZrFe2H4 due to surface phenomena was revealed. Unusual role of manganese in hydride forming processes is pointed out. Hydrogen induced phase transitions, suppression of magnetism, antiferromagnetic-ferromagnetic and metal-insulator or semimetal-metal transitions are described. Equations of state (EOS) of hydrides submitted to hydrostatic pressures up to 30 GPa are presented and discussed.

  4. Fracture Behaviors of Sn-Cu Intermetallic Compound Layer in Ball Grid Array Induced by Thermal Shock

    NASA Astrophysics Data System (ADS)

    Shen, Jun; Zhai, Dajun; Cao, Zhongming; Zhao, Mali; Pu, Yayun

    2014-02-01

    In this work, thermal shock reliability testing and finite-element analysis (FEA) of solder joints between ball grid array components and printed circuit boards with Cu pads were used to investigate the failure mechanism of solder interconnections. The morphologies, composition, and thickness of Sn-Cu intermetallic compounds (IMC) at the interface of Sn-3.0Ag-0.5Cu lead-free solder alloy and Cu substrates were investigated by scanning electron microscopy and transmission electron microscopy. Based on the experimental observations and FEA results, it can be recognized that the origin and propagation of cracks are caused primarily by the difference between the coefficient of thermal expansion of different parts of the packaged products, the growth behaviors and roughness of the IMC layer, and the grain size of the solder balls.

  5. The structure and composition of chromate conversion coatings formed on aluminum-copper alloy AA2024-T3 and thin film analogs of constituent intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Vasquez, Marvin Jaime

    2002-01-01

    A comprehensive suite of spectroscopy have been used to study the composition and structure of Chromate Conversion Coatings (CCC) formed on Aluminum Copper (Al-Cu) alloy AA2024-T3 and constituent Intermetallic Compounds (IMCs). Based on previous work the CCC formed over the IMCs is expected to be thinner and therefore different in structure and composition than the CCC formed on the matrix. The formation of the CCC over the different IMCs is expected to be dependent on the chemistry and the interaction of the IMCs with accelerators such as ferricyanide. Surface chemical and structural data determined by X-ray Photoelectron Spectroscopy (XPS), Synchrotron Infrared Microspectroscopy, X-ray Absorption Near Edge Spectroscopy (XANES), Extended X-ray Absorption Fine Structure (EXAFS), Secondary Ion Mass Spectrometry (SIMS), and Secondary Electron Microscopy/Energy Dispersive Analysis of X-rays (SEM/EDAX) have been developed to refine an existing model for the CCC formed on the AA2024-T3 surface, an Al-Cu aircraft alloy, by considering the composition and structure of the CCC formed on constituent intermetallic compounds (IMCs). The limited corrosion behavior of AA2024-T3 aluminum alloy is generally attributed to the presence of a variety of constituent IMC. These IMC particles are of the order of 1--20 mum which makes their direct analysis exceedingly difficult and has lead to a limited understanding of their surface chemical properties relative to CCC formation. To overcome this limitation, it was necessary to develop for the first time large area samples composed of compositionally homogenous thin films of the various IMCs found on the AA2024-T3 surface, which were galvanically attached to thin films of Al-4.2wt%Cu (representative of the AA2024-T3 matrix). This was performed in a two-step process: Disks of IMC compositions were formed by Reactive Arc Melting (RAM), followed by ultra-fast laser ablation of the RAM IMCs resulting in the formation of homogenous thin films

  6. Ab initio calculations on elastic properties in L12 structure Al3X and X3Al-type (X=transition or main group metal) intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Tian, T.; Wang, X. F.; Li, W.

    2013-03-01

    As high-temperature structural materials, L12 intermetallic compounds have attracted the strong interest from both fundamental and industrial aspects. Understanding of elastic property is a basis for the complete investigations of mechanical behavior of L12 alloys. In an effort to explore the electronic origin of elastic properties of L12 intermetallics, we have performed a systematic study on elastic constants for single crystals, and Young's modulus, shear modulus, bulk modulus and Poisson's ratio for poly-crystals of 22 known Al3X and X3Al-type (X=transition or main group metal) intermetallics using the ab initio calculations. Based on the calculations of elastic constants and extreme (both positive and negative) Poisson's ratios, we found a pronounced correlation between the extreme Poisson's ratio and the elastic anisotropy, i.e., approximate 40% of the investigated L12 intermetallics exhibit intrinsic auxetic behavior. Furthermore, based on the distribution of bonding charge densities, we revealed that the ductility and extreme Poisson's ratios were attributable to the directionality of bonds of these alloys. Our findings provide a new method to predict mechanical behavior of intermetallics.

  7. Effect of chromium on the formation of intermetallic phases in hot-dipped aluminide Cr-Mo steels

    NASA Astrophysics Data System (ADS)

    Cheng, Wei-Jen; Wang, Chaur-Jeng

    2013-07-01

    Cr-Mo steels with different chromium contents were coated by hot-dipping into molten baths containing pure aluminum and Al-10 wt.% Si for 180 s. The effect of chromium content in the steels on the formation of the intermetallic phases in the aluminide coatings was studied. The results show that all the aluminide coatings can be distinguished into an outer pure aluminum or Al-Si topcoat and an inner intermetallic layer. The intermetallic layers, resulting from the steels hot-dipped in pure aluminum, have the same phase constitution, an outer minor FeAl3 and an inner major Fe2Al5. In the aluminide coatings on the steels with 0 and 2.25 wt.% chromium after hot-dipping in Al-10 wt.% Si, the intermetallic layers were composed of an outer layer of τ5(H)-Al7(Fe,Cr)2Si and an inner one of FeAl3/τ1-(Al,Si)5Fe3/Fe2Al5, while a small amount of polyhedral τ5(H)-Al7(Fe,Cr)2Si and plate-shaped τ6-Al4FeSi were observed in the Al-Si topcoats. In the aluminide coatings on the steels with 5 and 9 wt.% chromium after hot-dipping in Al-10 wt.% Si, the intermetallic layers were composed of only a τ5(H)-Al7(Fe,Cr)2Si phase. A large amount of scattered granular τ5(C)-Al7(Fe,Cr)2Si and a small amount of plate-shaped τ4-Al3FeSi2 and τ6-Al4FeSi were also found in the Al-Si topcoats. When the chromium content reached 5 wt.%, the amount of steel, which dissolved when samples were hot-dipped in Al-10 wt.% Si, increased. Also, the rate of dissolving went up as chromium content went up. The increase of dissolution is because the interdiffusion between steels and Al-10 wt.% Si bath was enhanced by the formation of scattered granular τ5(C)-Al7(Fe,Cr)2Si, which was stabilized by chromium.

  8. Hall Effect in R_2Fe_14B Rare-Earth Intermetallic Compounds

    NASA Astrophysics Data System (ADS)

    Stankiewicz, Jolanta; Bartolomé, Juan

    2004-03-01

    We have studied the variation of the a.c. resistivity and of the low-field Hall effect in a single Gd_2Fe_14B crystal over a wide temperature range(4-750 K). The magnetic field dependence of the resistivity up to 5 T was also measured at several temperatures. Using results we have obtained previously for single crystals with R = Y, Nd, and Tm, we find that, away from magnetic transition regions, the anomalous Hall resistivity is proportional to the square of total resistivity, as predicted for side-jump scattering. Below the Curie temperature, the Hall effect arising from skew scattering is alike for all compounds except for Gd, where it is much larger. Coulomb interactions between conductions electrons and localized 4f electrons fail to account for such behavior since they do not give rise to asymmetric scattering for S-state ions. Other mechanisms, mainly covalent mixing interactions and the formation of virtual 5d states, including their spin-orbit interaction, are also considered.

  9. Ba 5Ti 12Sb 19+x, a polar intermetallic compound with a stuffed γ-brass structure

    NASA Astrophysics Data System (ADS)

    Bie, Haiying; Mar, Arthur

    2009-11-01

    The polar intermetallic compound Ba 5Ti 12Sb 19+x ( x⩽0.2) has been synthesized by reaction of the elements. Single-crystal X-ray diffraction analysis revealed that it adopts a new structure type (Ba 5Ti 12Sb 19.102(6), space group P43¯m, Z=2, a=12.4223(11) Å, V=1916.9(3) Å 3). The set of Ba and Sb sites corresponds to the structure of Cu 9Al 4, a γ-brass type with a primitive cell. A complex three-dimensional framework of Ti atoms, in the form of linked planar Ti 9 clusters, is stuffed within the γ-brass-type Ba-Sb substructure. Notwithstanding its relationship to the γ-brass structure, the compound does not appear to conform to the Hume-Rothery electron concentration rules. Band structure calculations on an idealized Ba 5Ti 12Sb 19 model suggest that the availability of bonding states above the Fermi level is responsible for the partial occupation, but only to a limited degree, of an additional Sb site within the structure. Magnetic measurements indicated Pauli paramagnetic behaviour.

  10. Quantum many-body intermetallics: Phase stability of Fe3Al and small-gap formation in Fe2VAl

    NASA Astrophysics Data System (ADS)

    Kristanovski, Oleg; Richter, Raphael; Krivenko, Igor; Lichtenstein, Alexander I.; Lechermann, Frank

    2017-01-01

    Various intermetallic compounds harbor subtle electronic correlation effects. To elucidate this fact for the Fe-Al system, we perform a realistic many-body investigation based on a combination of density functional theory with dynamical mean-field theory in a charge self-consistent manner. A better characterization and understanding of the phase stability of bcc-based D 03-Fe3Al through an improved description of the correlated charge density and the magnetic energy is achieved. Upon replacement of one Fe sublattice with V, the Heusler compound Fe2VAl is realized, known to display bad-metal behavior and increased specific heat. Here we document a charge-gap opening at low temperatures in line with previous experimental work. The gap structure does not match conventional band theory and is reminiscent of (pseudo)gap characteristics in correlated oxides.

  11. Manifestation of spin-charge fluctuations in the spectral and thermodynamic properties of quasi-two-dimensional rare-earth intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Val'kov, V. V.; Zlotnikov, A. O.

    2017-02-01

    In the framework of the modified periodic Anderson model with exchange interaction in the subsystem of localized states, it is shown that spin-charge fluctuations in quasi-two-dimensional intermetallic compounds with rare-earth ions in the mixed valence state significantly affect both the spectrum of magnetic excitations and the conditions at which the antiferromagnetic phase is realized. The spectral characteristics of the phase were obtained by the method of the diagram technique for Hubbard operators in the one-loop approximation, which allows to account for the spin-charge fluctuation contributions to the components of the mass and the force operators. The developed theory allowed to quantitatively describe the pressure dependence of the Néel temperature observed in a quasi-two-dimensional antiferromagnetic heavy-fermion intermetallic compound CeRhIn5.

  12. Abnormal Intermetallic Compound Evolution in Ni/Sn/Ni and Ni/Sn-9Zn/Ni Micro Solder Joints Under Thermomigration

    NASA Astrophysics Data System (ADS)

    Zhao, N.; Deng, J. F.; Zhong, Y.; Huang, M. L.; Ma, H. T.

    2017-04-01

    Interfacial reactions in Ni/Sn/Ni and Ni/Sn-9Zn/Ni micro solder joints during thermomigration (TM) have been studied by reflowing solder joints on a hot plate. Asymmetrical growth and transformation of interfacial intermetallic compounds (IMCs) were clearly observed. The growth of the Ni3Sn4 IMC in the Ni/Sn/Ni solder joints was always fast at the cold end and relatively slow at the hot end. Only asymmetrical growth of the Ni5Zn21 IMC in the Ni/Sn-9Zn/Ni solder joints occurred at the beginning because Zn was the dominant TM species; however, asymmetrical transformation of the Ni5Zn21 IMC also occurred under the combined effect of Zn depletion and Ni dissolution and migration, resulting in formation of a thin τ-phase layer at the hot end and a thick τ-phase/Ni5Zn21/τ-phase sandwich structure at the cold end. TM of Ni and Zn atoms was identified towards the cold end, being responsible for the abnormal IMC evolution. Addition of Zn was found to slow the TM-induced IMC growth and Ni dissolution.

  13. Massive spalling of Cu-Zn and Cu-Al intermetallic compounds at the interface between solders and Cu substrate during liquid state reaction

    NASA Astrophysics Data System (ADS)

    Kotadia, H. R.; Panneerselvam, A.; Mokhtari, O.; Green, M. A.; Mannan, S. H.

    2012-04-01

    The interfacial intermetallic compound (IMC) formation between Cu substrate and Sn-3.8Ag-0.7Cu-X (wt.%) solder alloys has been studied, where X consists of 0-5% Zn or 0-2% Al. The study has focused on the effect of solder volume as well as the Zn or Al concentration. With low solder volume, when the Zn and Al concentrations in the solder are also low, the initial Cu-Zn and Al-Cu IMC layers, which form at the solder/substrate interface, are not stable and spall off, displaced by a Cu6Sn5 IMC layer. As the total Zn or Al content in the system increases by increasing solder volume, stable CuZn or Al2Cu IMCs form on the substrate and are not displaced. Increasing concentration of Zn has a similar effect of stabilizing the Cu-Zn IMC layer and also of forming a stable Cu5Zn8 layer, but increasing Al concentration alone does not prevent spalling of Al2Cu. These results are explained using a combination of thermodynamic- and kinetics-based arguments.

  14. Magnetic Properties of Some Gadolinium, Erbium, Dysprosium, Manganese Substituted Samarium-2 Cobalt-17 Intermetallic Compounds.

    DTIC Science & Technology

    1979-08-01

    that excellent temperature compensation could be achieved in these compounds in the teinper~ture (cont’d) ~‘ DD I ? ) 1Q3 L°’TI°M °’ INOV BI...following prop— erties: energy products in excess of 30 MGOe, low reversible tem- perature coefficients of magnetization , c~, and linear demagnetiza...Sm2(Co,Fe) i7 compounds significantly enhances their coercivities and energy products. Thus, we have been investigating the magnetic properties of these

  15. Nanoclusters based on pentagondodecahedra with shells in the form of D32, D42, and D50 deltahedra in crystal structures of intermetallic compounds

    SciTech Connect

    Pankova, A. A.; Ilyushin, G. D.; Blatov, V. A.

    2012-01-15

    The TOPOS software package has been used to form a database of intermetallic compounds containing pentagondodecahedral d clusters (528 crystal structures of intermetallic compounds, 111 topological types, and 47 space symmetry groups). On the whole, 606 atomic d configurations have been selected which are described by 14 point symmetry groups. Examples of nanoclusters are presented which are precursors of the crystal structures of intermetallic compounds with the outer shell in the form of deltahedra D, which are formed above dodecahedra. These nanoclusters are identified in the automatic mode of structural data processing: D32 (K{sub 8}In{sub 6}Ge{sub 40}, Cs{sub 30}Na{sub 3}Sn{sub 162}), D{sub 42} (Ru{sub 3}Be{sub 17}, Y{sub 3}Cd{sub 18}, Ca{sub 3}(Cd{sub 17}Al)), and D{sub 50} (Yb{sub 3}Zn{sub 18}, Ce{sub 3}(Au{sub 14}Sn{sub 3}), Pr{sub 3}Cd{sub 18}, Eu{sub 4}Cd{sub 25}), where 32, 42, and 50 are the numbers of atoms in the shell. Similar deltahedra were found previously in icosahedral nanoclusters (precursors of intermetallic compounds). Structures with the dodecahedral nanocluster precursors containing D42 and D50 deltahedra are approximants of MCd{sub 5.7} (M = Yb or Ca) quasicrystals and belong to the family of MCd{sub 6} (M = Ce, Pr, Nd, Sm, Eu, Gd, Dy, Yb, Y, or Ca).

  16. First-principles study of Al2Sm intermetallic compound on structural, mechanical properties and electronic structure

    NASA Astrophysics Data System (ADS)

    Lin, Jingwu; Wang, Lei; Hu, Zhi; Li, Xiao; Yan, Hong

    2017-02-01

    The structural, thermodynamic, mechanical and electronic properties of cubic Al2Sm intermetallic compound are investigated by the first-principles method on the basis of density functional theory. In light of the strong on-site Coulomb repulsion between the highly localized 4f electrons of Sm atoms, the local spin density approximation approach paired with additional Hubbard terms is employed to achieve appropriate results. Moreover, to examine the reliability of this study, the experimental value of lattice parameter is procured from the analysis of the TEM image and diffraction pattern of Al2Sm phase in the AZ31 alloy to verify the authenticity of the results originated from the computational method. The value of cohesive energy reveals Al2Sm to be a stable in absolute zero Kelvin. According to the stability criteria, the subject of this work is mechanically stable. Afterward, elastic moduli are deduced by performing Voigt-Reuss-Hill approximation. Furthermore, elastic anisotropy and anisotropy of sound velocity are discussed. Finally, the calculation of electronic density of states is implemented to explore the underlying mechanism of structural stability.

  17. Micromagnetic analysis of the hardening mechanisms of nanocrystalline MnBi and nanopatterned FePt intermetallic compounds.

    PubMed

    Kronmüller, H; Yang, J B; Goll, D

    2014-02-12

    The uniaxial intermetallic compounds of L10-FePt and the low temperature NiAs structure of MnBi are suitable alloys for application as high-density recording materials or as high-coercivity permanent magnets. Single domain particles of these materials are characterized by coercive fields above 1 T over a large temperature range. In particular MnBi shows a coercive field of 2 T at 450 K. Its extraordinary magnetic properties in the temperature range up to 600 K are due to an increase of the magnetocrystalline anisotropy constant from 1.2 MJ m(-3) at 300 K to 2.4 MJ m(-3) at 450 K. In spite of the large coercivities obtained for both type of materials their experimental values deviate considerably from the theoretical values Hc = 2K1/Js valid for a homogeneous rotation process in spherical particles. As is well known these discrepancies are due to the deteriorating effects of the microstructure. For an analysis of the coercive fields the Stoner-Wohlfarth theory has to be expanded with respect to higher anisotropy constants and to microstructural effects such as misaligned grains and grain surfaces with reduced anisotropy constants. It is shown that the temperature dependence and the angular dependence of Hc for FePt as well as MnBi can be quantitatively interpreted by taking into account the above mentioned intrinsic and microstructural effects.

  18. The magnetic behavior of the intermetallic compound NdMn2Ge2 studied by magnetization and hyperfine interactions measurements

    NASA Astrophysics Data System (ADS)

    Bosch-Santos, B.; Carbonari, A. W.; Cabrera-Pasca, G. A.; Saxena, R. N.; Freitas, R. S.

    2015-05-01

    The magnetic behavior of the intermetallic compound NdMn2Ge2 was investigated by bulk magnetization measurements and measurements of hyperfine interactions using perturbed γ-γ angular correlation (PAC) spectroscopy. Magnetization measurements indicate the presence of four magnetic transitions associated with the Mn and Nd magnetic sublattices. At high temperatures, magnetic measurements show a change in the slope of the magnetization due to an antiferromagnetic transition around TN ˜ 425 K and a well defined ferromagnetic transition at TC ˜ 320 K. Moreover, at ˜210 K a peak is observed in the magnetization curve, which is assigned to the reorientation of the Mn spin, and at ˜25 K an increase in the magnetic moment is also observed, which is ascribed to the ordering of Nd ions. PAC measurements using 140La(140Ce) and 111In(111Cd) probe nuclei allowed the determination of the temperature dependence of the magnetic hyperfine field (Bhf) at Nd and Mn sites, respectively. PAC results with 111Cd probe nuclei at Mn sites show that the dependence of Bhf with temperature follows the expected behavior for the host magnetization associated with the magnetic ordering of Mn ions. From these results, the antiferromagnetic transition followed by a ferromagnetic ordering is clearly observed. PAC results with 140Ce probe nuclei at Nd sites, however, showed a strong deviation from the Brillouin function, which is attributed to the Ce 4f-electron contribution to Bhf.

  19. Synthesis, crystal structure, and magnetic properties of novel intermetallic compounds R2Co2SiC (R = Pr, Nd).

    PubMed

    Zhou, Sixuan; Mishra, Trinath; Wang, Man; Shatruk, Michael; Cao, Huibo; Latturner, Susan E

    2014-06-16

    The intermetallic compounds R2Co2SiC (R = Pr, Nd) were prepared from the reaction of silicon and carbon in either Pr/Co or Nd/Co eutectic flux. These phases crystallize with a new stuffed variant of the W2CoB2 structure type in orthorhombic space group Immm with unit cell parameters a = 3.978(4) Å, b = 6.094(5) Å, c = 8.903(8) Å (Z = 2; R1 = 0.0302) for Nd2Co2SiC. Silicon, cobalt, and carbon atoms form two-dimensional flat sheets, which are separated by puckered layers of rare-earth cations. Magnetic susceptibility measurements indicate that the rare earth cations in both analogues order ferromagnetically at low temperature (TC ≈ 12 K for Nd2Co2SiC and TC ≈ 20 K for Pr2Co2SiC). Single-crystal neutron diffraction data for Nd2Co2SiC indicate that Nd moments initially align ferromagnetically along the c axis around ∼12 K, but below 11 K, they tilt slightly away from the c axis, in the ac plane. Electronic structure calculations confirm the lack of spin polarization for Co 3d moments.

  20. Solid-State Phase Equilibria and Intermetallic Compounds of the Si-V-Zr Ternary System

    NASA Astrophysics Data System (ADS)

    Pan, Yanfang; Ye, Haimei; Chen, Xiaoxian; Jiang, Wenping; Yang, Wenchao; Zhan, Yongzhong

    2016-12-01

    Phase relations in the Si-V-Zr ternary system at 973 K (700 °C) were experimentally investigated using X-ray powder diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The isothermal section at 973 K (700 °C) is governed by seventeen three-phase regions, thirty-two two-phase regions, and sixteen single-phase regions. Ten binary compounds and one ternary compound (SiVZr) were confirmed. There are two new ternary compounds found in this work for the first time. One of them (Si4V3Zr2) was found in the stoichiometric composition around V 38 pct, Si 50 pct, and Zr 12 pct. The existence of another one (V17Si12Zr3) was observed while analyzing the XRD results of large quantities of equilibrated samples in the region around 54 at. pct V, 33 at. pct Si, and 13 at. pct Zr.

  1. Metamagnetism-enhanced magnetocaloric effect in the rare earth intermetallic compound Ho5Ge4

    NASA Astrophysics Data System (ADS)

    Nirmala, R.; Morozkin, A. V.; Rajivgandhi, R.; Nigam, A. K.; Quezado, S.; Malik, S. K.

    2016-11-01

    Magnetic and magnetocaloric properties of polycrystalline Ho5Ge4 (orthorhombic, Sm5Ge4-type, Space group Pnma, No. 62, oP36) compound have been studied. This compound orders antiferromagnetically at ~24 K (TN). From the magnetization vs field isotherms obtained close to the magnetic transition temperature, magnetocaloric effect (MCE) has been estimated. The isothermal magnetic entropy change (ΔSM) reaches a maximum value of ~-27 J/kg-K at ~30 K for a field change of 140 kOe. A metamagnetic transition is observed in the field dependent magnetization data at temperatures below 20 K, for critical fields above 20 kOe, giving rise to a ferromagnetic order and hence a large MCE. The magnetic moment value at 2.5 K is ~8μB/Ho3+ in 90 kOe field.

  2. Formation of intermetallic phases in AlSi7Fe1 alloy processed under microgravity and forced fluid flow conditions and their influence on the permeability

    NASA Astrophysics Data System (ADS)

    Steinbach, S.; Ratke, L.; Zimmermann, G.; Budenkova, O.

    2016-03-01

    Ternary Al-6.5wt.%Si-0.93wt.%Fe alloy samples were directionally solidified on-board of the International Space Station ISS in the ESA payload Materials Science Laboratory (MSL) equipped with Low Gradient Furnace (LGF) under both purely diffusive and stimulated convective conditions induced by a rotating magnetic field. Using different analysis techniques the shape and distribution of the intermetallic phase β-Al5SiFe in the dendritic microstructure was investigated, to study the influence of solidification velocity and fluid flow on the size and spatial arrangement of intermetallics. Deep etching as well as 3-dimensional computer tomography measurements characterized the size and the shape of β-Al5SiFe platelets: Diffusive growth results in a rather homogeneous distribution of intermetallic phases, whereas forced flow promotes an increase in the amount and the size of β-Al5SiFe platelets in the centre region of the samples. The β-Al5SiFe intermetallics can form not only simple platelets, but also be curved, branched, crossed, interacting with dendrites and porosity located. This leads to formation of large and complex groups of Fe-rich intermetallics, which reduce the melt flow between dendrites leading to lower permeability of the mushy zone and might significantly decrease feeding ability in castings.

  3. Chemical hydrogenation of La(Fe,Si) family of intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Wlodarczyk, P.; Polak, M.; Hawelek, L.; Kowalczyk, M.; Hreczka, M.; Kolano-Burian, A.

    2016-11-01

    In the present work, the chemical hydrogenation process of La(Fe,Si)13 compounds has been shown. It was found, that the La(Fe,Si) compound can be easily saturated with hydrogen by performing reaction with 0.6 M hydrochloric acid (HCl) for 2 h. After reaction, the heat treatment process is necessary to make hydrogenated powder homogenous. For the LaFe11.8Si1.2 micronized (<50 μm) and hydrogenated powder, the strength of the magnetocaloric effect was estimated by means of magnetocalorimetric measurements on plates consolidated with PVDF thermoplastic polymer. Magnetic entropy change was calculated by use of magnetization data acquired at magnetic fields with induction up to 2T. The adiabatic temperature change is equal to 3 K in magnetic field change 0-1.7T at 335 K, while magnetic entropy change is equal 13 J/kg*K at 2T. The structural homogeneity of initial and hydrogenated powders was validated by powder X-ray diffraction method. The amount of hydrogen in the hydrogenated compounds was evaluated using thermogravimetry method (4 H atoms per formula unit LaFe11.8Si1.2).

  4. Fabrication and Investigation of Intermetallic Compound-Glassy Phase Composites having Tensile Ductility

    DTIC Science & Technology

    2012-08-09

    with Mg-Y-Cu BGA, MgY phase also has a cP2 B2 structure), Mg-Y-Ag (AgMg phase also has a cP2 B2 structure and is ductile) and Y-Cu-Zn and some other...result were obtained is connected with cP2 TiNi phase which demonstrates martensitic transformations. Choice of alloys and sample preparation...1. The tentative compositions at which bulk glassy phase formation and possible formation of cP2 crystal-glassy composites are Cu-Y (starting from

  5. Polar intermetallic compounds of the silicon and arsenic family elements and their ternary hydrides and fluorides

    SciTech Connect

    Leon-Escamilla, E.A.

    1996-10-17

    An investigation has been made on the effects of hydrogen and fluoride in the solid state chemistry of alkaline-earth and divalent rare-earth metal pnictide (Pn) and tetrelide (Tt) phases A{sub 5}(Pn,Tt,){sub 3}Z{sub x}, where A = Ca, Sr, Ba, Sm, Eu, Yb; Pn = As, Sb, Bi; Tt = Si, Ge, Sn, Pb and Z = H, F. Several trivalent rare-earth-metal pnictides, RE{sub 5}Pn{sub 3} (RE = Y, La, Gd, Tb, Dy, Ho, Er, Tm) and alkaline-earth-metal trielides, A{sub 5}Tr{sub 3}Z{sub x} (Tr = Ga, In, Tl) have been included in an effort to complete observed structural trends. Two main experimental techniques were followed throughout this work, (a) reactions in absence of hydrogen or under continuous high vacuum, and (b) reactions with binary metal hydrides, AH{sub x}, in closed containers. The results demonstrate that all the phases reported with the {beta}-Yb{sub 5}Sb{sub 3}-type structure in the A{sub 5}Pn{sub 3} systems are hydrogen-stabilized compounds. Reactions in absence of hydrogen lead to compounds with the Mn{sub 5}Si{sub 3}-type structure. The structure type {beta}-Yb{sub 5}Sb{sub 3} (= Ca{sub 5}SB{sub 3}F) was found to be characteristic of ternary systems and inaccurately associated with phases that form in the Y{sub 5}Bi{sub 3}-type. A new series of isomorphous Zintl compounds with the Ca{sub 16}Sb{sub 11}-type structure were prepared and studied as well. All the alkaline-earth-metal tetrelides, A{sub 5}Tt{sub 3}, that crystallize in the Cr{sub 5}B{sub 3}-type structure can be interstitially derivatized by hydrogen or fluoride. Binary and ternary compounds were characterized by Guinier powder patterns, single crystal X-ray and powder neutron diffraction techniques. In an effort to establish property-structure relationships, electrical resistivity and magnetic measurements were performed on selected systems, and the results were explained in terms of the Zintl concepts, aided by extended Hueckel band calculations.

  6. Processing, phase equilibria and environmental degradation of molybdenum (silicom,aluminum)(2) intermetallic compound

    NASA Astrophysics Data System (ADS)

    Eason, Paul Duane

    The Mo(Si,Al)2 C40 compound was chosen for investigation as a possible high temperature structural material. To produce the C40 phase, several processing routes were explored with emphasis on obtaining microstructure/property relationships (i.e. control of grain size and minimization of secondary phases). To facilitate processing of single phase material, the phase equilibria of the Mo-Si-Al ternary system were reevaluated with respect to the phases adjacent to the C40 compound. An anomalous environmental degradation appeared to be the primary obstacle to further study of the compound and was investigated accordingly. Several processing routes were assessed for the production of dense, nearly single-phase Mo(Si,Al)2. Hot powder compaction was chosen as the method of sample production as is the case with many refractory silicide based materials. Therefore, variations in the processing techniques came from the choice of precursor materials and methods of powder production. Mechanical alloying, arc-melting and comminution, and blending of both elemental and compound powders were all employed to produce charges for hot uniaxial pressing. The final compacts were compared on the basis of density, grain size and presence of secondary phases. Establishment of a Mo-Si-Al ternary isothermal phase diagram at 1400°C was performed. Multiphase alloy compositions were selected to identify the phase boundaries of the C40, C54, T1 and Mo3Al8 phase fields, as well as to verify the existence of the C54 phase at 1400°C. The alloys were equilibrated by heat treatment and analyzed for phase identification and quantitative compositional information. The environmental degradation phenomenon was approached as a classical "pest" with an emphasis of study on grain boundary chemistry and atmospheric dependence of attack. Both Auger spectroscopy and electron microscopy revealed carbon-impurity-induced grain boundary segregation responsible for the embrittlement and material loss. Means of

  7. Coherent cluster atomic ordering in the Fe-27Al intermetallic compound

    NASA Astrophysics Data System (ADS)

    Balagurov, A. M.; Bobrikov, I. A.; Mukhametuly, B.; Sumnikov, S. V.; Golovin, I. S.

    2016-10-01

    Neutron diffraction studies of the Fe0.735Al0.265 compound are performed in a wide temperature range (20-900°C) in order to determine its structural states and the mechanism of ordering of atoms. The combination of high-resolution diffraction and the real-time detection of diffraction spectra makes it possible to establish that, in contrast to traditional notions, the structure of this compound at room temperature is a phase with only a partially ordered arrangement of Fe and Al in a unit cell. A completely ordered phase (such as Fe3Al) is present in the form of mesoscopic ( 200Å) clusters coherently incorporated into the disordered matrix of the main phase. After the transition of the sample to a disordered state ( T> 740°C) and slow cooling to room temperature, the size of structurally ordered clusters increases to 900 Å. A high contrast in the coherent neutron scattering lengths of iron and gallium nuclei allows the accurate determination of the temperature dependence of the occupancy factors of sites by Fe and Al atoms up to a phase transition to the disordered state.

  8. Metamagnetism and giant magnetoresistance of the rare-earth intermetallic compounds R2Ni2Pb (R=Er,Ho,Dy)

    NASA Astrophysics Data System (ADS)

    Chinchure, Aravind D.; Muñoz Sandoval, E.; Mydosh, J. A.

    2002-07-01

    We have measured the magnetization and magnetoresistance for a series of rare-earth (R=Er,Ho,Dy) plumbide intermetallic compounds, R2Ni2Pb. These materials form in an unusual orthorhombic structure with space group Cmmm. After multiple magnetic transitions, the ground state exhibits a steplike series of large-moment metamagnetic transitions in low fields (1-2 T) concomitant with switchinglike properties of the magnetoresistance where sharp changes of up to 30% are found. We relate these properties to the layered magnetic structure of the compound.

  9. First principles study of structural, electronic, mechanical and thermal properties of A15 intermetallic compounds Ti3X (X=Au, Pt, Ir)

    NASA Astrophysics Data System (ADS)

    Rajagopalan, M.; Rajiv Gandhi, R.

    2012-12-01

    The structural, electronic, elastic, mechanical and thermal properties of Ti3Au, Ti3Pt and Ti3Ir intermetallic compounds crystallizing in A15 structure have been studied using density functional theory within generalized gradient approximation (GGA) for the exchange correlation potential. Elastic properties such as Young's modulus (E), rigidity modulus (G), bulk modulus (B), Poisson's ratio (σ) and elastic anisotropic factor (A) have been calculated. From the present study it is noted that Ti3Ir is the hardest compound among the three materials studied due to its larger bulk modulus. Also, it is more ductile in nature.

  10. Crystallographic features of the structure of a martensite packet of the NiMn intermetallic compound

    NASA Astrophysics Data System (ADS)

    Khlebnikova, Yu. V.; Egorova, L. Yu.; Rodionov, D. P.; Belosludtseva, E. S.; Kazantsev, V. A.

    2016-06-01

    Optical microscopy, scanning electron microscopy, and X-ray diffraction are used to show that a pseudosingle crystal forms upon cooling of an alloy Ni49Mn51 single crystal below the temperature of the β→θ (bcc → fct) transformation. At room temperature, this pseudosingle crystal has the structure of tetragonal L10 martensite with parameters a = 0.3732 nm and c = 0.3537 nm and a tetragonality c/ a = 0.94775. The temperatures of the forward and reverse B2 → L10 transformations are determined. The crystallographic features of martensite packet formation are analyzed. As shown by EBSD, neighboring martensite packets always have three kinds of tetragonal martensite plates, which are in a twin position and have different tetragonality axis directions. Repeated heating and quenching of the pseudosingle crystal result in recrystallization with the formation of coarse grains. The packet structure of the tetragonal martensite is retained in this case, and the sizes of the packets formed within a grain decrease by a factor of 2-3 as compared to the initial pseudosingle crystal.

  11. Solid state phase equilibria and intermetallic compounds of the Al-Cr-Ho system

    SciTech Connect

    Pang, Mingjun; Zhan, Yongzhong; Du, Yong

    2013-02-15

    The solid state phase equilibria of the Al-Cr-Ho ternary system at 500 Degree-Sign C were experimentally investigated. The phase relations at 500 Degree-Sign C are governed by 14 three-phase regions, 29 two-phase regions and 15 single-phase regions. The existences of 10 binary compounds and 2 ternary phases have been confirmed. Al{sub 11}Cr{sub 2}, Al{sub 11}Cr{sub 4} and Al{sub 17}Ho{sub 2} were not found at 500 Degree-Sign C. Crystal structures of Al{sub 9}Cr{sub 4} and Al{sub 8}Cr{sub 4}Ho were determined by the Rietveld X-ray powder data refinement. Al{sub 9}Cr{sub 4} was found to exhibit cubic structure with space group I4-bar 3m (no. 217) and lattice parameters a=0.9107(5) nm. Al{sub 8}Cr{sub 4}Ho crystallizes in ThMn{sub 12} structure type with space group I4/mmm (no. 139) and lattice parameters a=0.8909(4) nm, c=0.5120(5) nm. It is concluded that the obtained Al{sub 4}Cr phase in this work should be {mu}-Al{sub 4}Cr by comparing with XRD pattern of the hexagonal {mu}-Al{sub 4}Mn compound. - Graphical abstract: The solid state phase equilibria of the Al-Cr-Ho ternary system at 500 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Al-Cr-Ho system has been investigated. Black-Right-Pointing-Pointer Al{sub 9}Cr{sub 4} has cubic structure with space group I4-bar 3m. Black-Right-Pointing-Pointer Al{sub 8}Cr{sub 4}Ho crystallizes in ThMn{sub 12} type with space group I4/mmm. Black-Right-Pointing-Pointer Al{sub 4}Cr phase is {mu}-type at 500 Degree-Sign C.

  12. Study of the feasibility of producing Al-Ni intermetallic compounds by mechanical alloying

    NASA Astrophysics Data System (ADS)

    Mohammed, Kahtan S.; Naeem, Haider T.; Iskak, Siti Nadira

    2016-08-01

    Mechanical alloying (MA) was employed to synthesize Al-Zn-Mg-Cu alloys of high weight percentage of the nickel component from the elemental powders of constituents via high-energy ball milling. The mixed powders underwent 15 h of milling time at 350 rpm speed and 10: 1 balls/powder weight ratio. The samples were cold-compacted and sintered thereafter. The sintered compacts underwent homogenization treatments at various temperatures conditions and were aged at 120°C for 24 h (T6). The milled powders and heat-treated Al alloy products were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The crystallite sizes and microstrains of the alloyed powder were estimated via measuring the broadening of XRD peaks using the Williamson-Hall equation. The results have revealed that optimum MA time of 15 h has led to the formation of Al-based solid solutions of Zn, Mg, Cu, and Ni. The outcomes showed that the Vickers hardness of the sintered Al-Zn-Mg-Cu compacts of Ni alloys was enhanced following aging at T6 tempering treatments. Higher compression strength of Al-alloys with the addition of 15% nickel was obtained next to the aging treatment.

  13. Kinetics of the Formation of Intermetallic Phases in HP-Type Heat-Resistant Alloys at Long-Term High-Temperature Exposure

    NASA Astrophysics Data System (ADS)

    Kondrat'ev, Sergey Yu.; Anastasiadi, Grigoriy P.; Petrov, Sergey N.; Ptashnik, Alina V.

    2017-01-01

    The kinetics of formation and morphology of the intermetallic phases in the structure of heat-resistant as-cast HP40NbTi alloys in the course of long high-temperature exposure have been studied with the help of light and electron microscopy, electron microprobe, and X-ray diffraction. During exposure of 2 to 1000 hours at 1423 K (1150 °C), intermetallic phase with conditional formula Cr7Ni5Si3N3FeNb is formed in the alloy. The analysis of the kinetics of intermetallic phase's growth for an impact assessment of certain metal substitutional elements (niobium, chromium, silicon) on the size of the formed particles was performed. Formation and growth of the intermetallic phases with high silicon content in the alloy structure on the boundaries between niobium and chromium carbides (NbC and M23C6) and matrix γ-phase provide a diffusion barrier for oxygen in oxidizing environment. This may create partial protection against oxidation of hardening carbide phases in the structure and promote increasing of the serviceability of the HP series alloys under operating conditions in the petrochemical industry.

  14. The effect of intermetallic compound morphology on Cu diffusion in Sn-Ag and Sn-Pb solder bump on the Ni/Cu Under-bump metallization

    NASA Astrophysics Data System (ADS)

    Jang, Guh-Yaw; Duh, Jenq-Gong

    2005-01-01

    The eutectic Sn-Ag solder alloy is one of the candidates for the Pb-free solder, and Sn-Pb solder alloys are still widely used in today’s electronic packages. In this tudy, the interfacial reaction in the eutectic Sn-Ag and Sn-Pb solder joints was investigated with an assembly of a solder/Ni/Cu/Ti/Si3N4/Si multilayer structures. In the Sn-3.5Ag solder joints reflowed at 260°C, only the (Ni1-x,Cux)3Sn4 intermetallic compound (IMC) formed at the solder/Ni interface. For the Sn-37Pb solder reflowed at 225°C for one to ten cycles, only the (Ni1-x,Cux)3Sn4 IMC formed between the solder and the Ni/Cu under-bump metallization (UBM). Nevertheless, the (Cu1-y,Niy)6Sn5 IMC was observed in joints reflowed at 245°C after five cycles and at 265°C after three cycles. With the aid of microstructure evolution, quantitative analysis, and elemental distribution between the solder and Ni/Cu UBM, it was revealed that Cu content in the solder near the solder/IMC interface played an important role in the formation of the (Cu1-y,Niy)6Sn5 IMC. In addition, the diffusion behavior of Cu in eutectic Sn-Ag and Sn-Pb solders with the Ni/Cu UBM were probed and discussed. The atomic flux of Cu diffused through Ni was evaluated by detailed quantitative analysis in an electron probe microanalyzer (EPMA). During reflow, the atomic flux of Cu was on the order of 1016-1017 atoms/cm2sec in both the eutectic Sn-Ag and Sn-Pb systems.

  15. Crystal structure and chemical bonding of novel Li-containing polar intermetallic compound La{sub 11}Li{sub 12}Ge{sub 16}

    SciTech Connect

    Jung, Yaho; Nam, Gnu; Jeon, Jieun; Kim, Youngjo; You, Tae-Soo

    2012-12-15

    A novel Li-containing polar intermetallic compound La{sub 11}Li{sub 12}Ge{sub 16} has been synthesized using the high-temperature reaction method and characterized by both powder and single-crystal X-ray diffractions. The title compound crystallized in the orthorhombic crystal system (space group Immm, Z=2, Pearson symbol oI78) with fifteen crystallographically unique atomic positions in the asymmetric unit, and the lattice parameters are refined as a=4.5244(4) A, b=6.9932(6) A, and c=53.043(5) A. The complex crystal structure of the title compound can be described as a 2:1 intergrowth of two closely related compounds: La{sub 2}Li{sub 2}Ge{sub 3} (Ce{sub 2}Li{sub 2}Ge{sub 3}-type) and La{sub 3}Li{sub 4}Ge{sub 4} (Zr{sub 3}Cu{sub 4}Si{sub 4}-type) acting like 'building-blocks' along the c-axis. Six La sites are categorized into three distinct types based on the local coordination environment showing the coordination numbers of 12-14. Three unique Li sites are placed in the centers of local tetrahedra formed by four Ge atoms which eventually construct Ge{sub 2} dimers or 1-dimensional cis-/trans-Ge chains. Theoretical investigations using the tight-binding linear muffin-tin orbital (LMTO) method provide rationales for an improved structural stability and for unique local coordination geometries established by anionic elements including [LiGe{sub 4}] tetrahedra, cis-/trans-Ge chain and Ge{sub 2} dimers. - Graphical abstract: Reported is a novel ternary Li-containing polar intermetallic compound La{sub 11}Li{sub 12}Ge{sub 16}. The complex crystal structure can be viewed as a simple combination of two closely related known compounds acting as 'building-blocks', La{sub 2}Li{sub 2}G{sub 3} and La{sub 3}Li{sub 4}Ge{sub 4}, in a 2:1 stoichiometric ratio. Highlights: Black-Right-Pointing-Pointer A novel Li-containing polar intermetallic compound La{sub 11}Li{sub 12}Ge{sub 16} was synthesized. Black-Right-Pointing-Pointer The complex crystal structure was easily explained as

  16. PyDII: A python framework for computing equilibrium intrinsic point defect concentrations and extrinsic solute site preferences in intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Ding, Hong; Medasani, Bharat; Chen, Wei; Persson, Kristin A.; Haranczyk, Maciej; Asta, Mark

    2015-08-01

    Point defects play an important role in determining the structural stability and mechanical behavior of intermetallic compounds. To help quantitatively understand the point defect properties in these compounds, we developed PyDII, a Python program that performs thermodynamic calculations of equilibrium intrinsic point defect concentrations and extrinsic solute site preferences in intermetallics. The algorithm implemented in PyDII is built upon a dilute-solution thermodynamic formalism with a set of defect excitation energies calculated from first-principles density-functional theory methods. The analysis module in PyDII enables automated calculations of equilibrium intrinsic antisite and vacancy concentrations as a function of composition and temperature (over ranges where the dilute solution formalism is accurate) and the point defect concentration changes arising from addition of an extrinsic substitutional solute species. To demonstrate the applications of PyDII, we provide examples for intrinsic point defect concentrations in NiAl and Al3 V and site preferences for Ti, Mo and Fe solutes in NiAl.

  17. Synthesis of Xenon and Iron/Nickel Intermetallic Compounds Under the Thermodynamic Conditions of the Earth's Core.

    NASA Astrophysics Data System (ADS)

    Stavrou, E.; Zaug, J. M.; Crowhurst, J.; Lobanov, S.; Goncharov, A. F.; Prakapenka, V.; Prescher, C.; Yao, Y.; Liu, H.; Dai, Z.; Oleynik, I.; Steele, B.; Cong, K. N.

    2015-12-01

    The lower Xe abundance in Earth's atmosphere, in comparison to other noble gases like Ar and Kr, is one of the most challenging open questions in geosciences [1]. The origin of the so-called "missing Xe paradox" is usually attributed to the inclusion of Xe in the interior of Earth[2]. Although Xe is known to form compounds (e.g. with hydrogen, oxygen), none of them can be related with Earth's interior. Indeed, only a very low amount of Xe can be incorporated in silica at <1 GPa and 500K [3]. On the other hand, experimental attempts have failed to trace possible formation of Fe-Xe compounds up to 155 GPa and bellow 2500K [4]. A very recent theoretical study, suggests that Xe-Ni and Xe-Fe compounds can form at thermodynamic conditions representative of Earth's outer core [5]. Here we explored the possible formation of stable compounds in the Xe-Fe/Ni system at thermodynamic conditions representative of Earth's outer core starting from the following mixtures: a) Xe-Fe, b) Xe-Ni and c) Xe and an Fe/Ni alloy representative of Earth's core (ca 6% Ni). Using in situ synchrotron X-ray diffraction and Raman spectroscopy we report the formation of: a) a XeNi3 compound, in the form of a CrNi3-type FCC solid solution, above 150 GPa and 1500K, b) a Xe(Fe/Ni)3 compound, tentatively characterized as an orthorhombic NbPd3-type solid solution, above 190 GPa and 2000K and c) a still not completely characterized XeFexcompound above 180 GPa and 2000K. This work provides a plausible explanation of the "missing Xe paradox", and underscores the importance of understanding the novel rules of high-pressure chemistry for an improved understanding of the structure and chemistry of the Earth's core. [1] E. Anders, E. and T. Owen, Science 198, 453 (1977). [2] Caldwell, W. A. et al.,Science 277, 930 (1997). [3] C. Sanloup et al.,Science 310, 1174(2005). [4] D. Nishio-Hamane et al.,Geophys. Res. Lett. 37, L04302 (2010). [5] L. Zhu et al., Nature chemistry 6, 664 (2014).

  18. Photoemission Study of the Rare Earth Intermetallic Compounds: RNi2Ge2 (R=Eu, Gd)

    SciTech Connect

    Park, Jongik

    2004-01-01

    EuNi2Ge2 and GdNi2Ge2 are two members of the RT2X2 (R = rare earth, T = transition metal and X = Si, Ge) family of intermetallic compounds, which has been studied since the early 1980s. These ternary rare-earth intermetallic compounds with the tetragonal ThCr2Si2 structure are known for their wide variety of magnetic properties, Extensive studies of the RT2X2 series can be found in Refs [ 1,2,3]. The magnetic properties of the rare-earth nickel germanides RNi2Ge2 were recently studied in more detail [4]. The purpose of this dissertation is to investigate the electronic structure (both valence band and shallow core levels) of single crystals of EuNi2Ge2 and GdNi2Ge2 and to check the assumptions that the f electrons are non-interacting and, consequently, the rigid-band model for these crystals would work [11], using synchrotron radiation because, to the best of our knowledge, no photoemission measurements on those have been reported. Photoemission spectroscopy has been widely used to study the detailed electronic structure of metals and alloys, and especially angle-resolved photoemission spectroscopy (ARPES) has proven to be a powerful technique for investigating Fermi surfaces (FSs) of single-crystal compounds.

  19. Effects of TiFe Intermetallic Compounds on the Tensile Behavior of Ti-4Al-4Fe-0.25Si Alloy

    NASA Astrophysics Data System (ADS)

    Lee, Sang Won; Kim, Kyong Min; Park, Chan Hee; Hong, Jea Keun; Yeom, Jong-Taek; Shih, Donald S.

    2017-02-01

    The effect of the B2 (ordered BCC) intermetallic compound TiFe on the tensile behavior of the Ti-4Al-4Fe-0.25Si alloy was investigated. The nucleation mechanism of TiFe was dependent on the solution temperature, and the solution treatment and aging temperatures were also important to the final alloy. The presence of intra-granular TiFe, which nucleated at α' (HCP) sites during aging, resulted in alloy brittleness. Alternatively, the presence of inter-granular TiFe, which nucleated only at nano-sized α (HCP) sites during aging, resulted in an excellent combination of strength and ductility compared to the original microstructure.

  20. Synthesis and characterization of Fe-Ti-Sb intermetallic compounds: Discovery of a new Slater-Pauling phase

    NASA Astrophysics Data System (ADS)

    Naghibolashrafi, N.; Keshavarz, S.; Hegde, Vinay I.; Gupta, A.; Butler, W. H.; Romero, J.; Munira, K.; LeClair, P.; Mazumdar, D.; Ma, J.; Ghosh, A. W.; Wolverton, C.

    2016-03-01

    Compounds of Fe, Ti, and Sb were prepared using arc melting and vacuum annealing. Fe2TiSb , expected to be a full Heusler compound crystallizing in the L 21 structure, was shown by XRD and SEM analyses to be composed of weakly magnetic grains of nominal composition Fe1.5TiSb with iron-rich precipitates in the grain boundaries. FeTiSb, a composition consistent with the formation of a half-Heusler compound, also decomposed into Fe1.5TiSb grains with Ti-Sb rich precipitates and was weakly magnetic. The dominant Fe1.5TiSb phase appears to crystallize in a defective L 21 -like structure with iron vacancies. Based on this finding, a first-principles DFT-based binary cluster expansion of Fe and vacancies on the Fe sublattice of the L 21 structure was performed. Using the cluster expansion, we computationally scanned >103 configurations and predict a novel, stable, nonmagnetic semiconductor phase to be the zero-temperature ground state. This new structure is an ordered arrangement of Fe and vacancies, belonging to the space group R 3 m , with composition Fe1.5TiSb , i.e., between the full- and half-Heusler compositions. This phase can be visualized as alternate layers of L 21 phase Fe2TiSb and C 1b phase FeTiSb, with layering along the [111] direction of the original cubic phases. Our experimental results on annealed samples support this predicted ground-state composition, but further work is required to confirm that the R 3 m structure is the ground state.

  1. Structural, electronic and elastic properties of the B2-ScM (M =Au, Hg and Tl) intermetallic compounds: Ab initio calculations

    NASA Astrophysics Data System (ADS)

    Mousa, Ahmad A.; Khalifeh, Jamil M.

    2015-10-01

    Structural, electronic, elastic and mechanical properties of ScM (M =Au, Hg and Tl) intermetallic compounds are studied using the full potential-linearized augmented plane wave (FP-LAPW) method based on the density functional theory (DFT), within the generalized gradient approximation (GGA) and the local density approximation (LDA) to the exchange-correlation approximation energy as implemented in the Wien2k code. The ground state properties including lattice parameters, bulk modulus and elastic constants were all computed and compared with the available previous theoretical and experimental results. The lattice constant was found to increase in contrast to the bulk modulus which was found to decrease with every substitution of the cation (M) starting from Au till Tl in ScM. Both the electronic band structure and density-of-states (DOS) calculations show that these compounds possess metallic properties. The calculated elastic constants (C11, C12 and C44) confirmed the elastic stability of the ScM compounds in the B2-phase. The mechanical properties and ductile behaviors of these compounds are also predicted based on the calculated elastic constants.

  2. Reactive spreading: Adsorption, ridging and compound formation

    SciTech Connect

    Saiz, E.; Cannon, R.M.; Tomsia, A.P.

    2000-09-11

    Reactive spreading, in which a chemically active element is added to promote wetting of noble metals on nonmetallic materials, is evaluated. Theories for the energetics and kinetics of the necessary steps involved in spreading are outlined and compared to the steps in compound formation that typically accompany reactive wetting. These include: fluid flow, active metal adsorption, including nonequilibrium effects, and triple line ridging. All of these can be faster than compound nucleation under certain conditions. Analysis and assessment of recently reported experiments on metal/ceramic systems lead to a focus on those conditions under which spreading proceeds ahead of the actual formation of a new phase at the interface. This scenario may be more typical than believed, and perhaps the most effective situation leading to enhanced spreading. A rationale for the pervasive variability and hysteresis observed during high temperature wetting also emerges.

  3. Calculation of alloying effect on formation enthalpy of TiCu intermetallics from first-principles calculations for designing Ti-Cu-system metallic glasses

    NASA Astrophysics Data System (ADS)

    Shirasawa, Naoya; Takigawa, Yorinobu; Uesugi, Tokuteru; Higashi, Kenji

    2016-01-01

    The effect of alloying on the formation enthalpy of TiCu intermetallics was investigated via first-principles calculations to propose a new design method for Ti-Cu-system metallic glasses. The calculation results showed good agreement with the reported experimental results that Ni, Pd, Sn and Zr improve this system's glass-forming ability. According to the calculation results, a Ti-Zr-Cu-Ga system was designed as a potential new bulk Ti-based metallic glass, and a bulk sample with a 2-mm diameter was fabricated.

  4. Investigations of intermetallic alloy hydriding mechanisms. Annual progress report, May 1 1979-April 30, 1980

    SciTech Connect

    Livesay, B.R.; Larsen, J.W.

    1980-05-01

    Investigations are being conducted on mechanisms involved with the hydrogen-metal interactions which control the absorption and desorption processes in intermetallic compounds. The status of the following investigations is reported: modeling of hydride formation; microbalance investigations; microstructure investigations; flexure experiments; resistivity experiments; and nuclear backscattering measurements. These investigations concern fundamental hydrogen interaction mechanisms involved in storage alloys.

  5. Investigation of modification of hydrogenation and structural properties of LaNi{sub 5} intermetallic compound induced by substitution of Ni by Pd

    SciTech Connect

    Prigent, J.; Joubert, J.-M.; Gupta, M.

    2011-01-15

    The hydrogenation properties of the LaNi{sub 5} (CaCu{sub 5} type, hP6, P6/mmm) and Pd substituted derivatives LaNi{sub 5-x}Pd{sub x} compounds have been studied in the whole homogeneity range of the solid solution (0.25{<=}x{<=}1.5). The pressure versus hydrogen content isotherms show several plateaus and an increase of the plateau pressure as a function of palladium concentration. The volume increase of the Pd substituted alloys should have resulted in a lowering, and not an increase, of the plateau pressure, according to the conventional models based on the size effect. In order to elucidate the origin of this anomalous behavior, both an experimental and a theoretical ab initio electronic structure investigation have been carried out. Experimentally, the nature and the structural properties of the hydrides have been studied by both in situ and ex situ neutron diffraction. The crystal structures of the three hydride phases are reported (LaNi{sub 3.5}Pd{sub 1.5}D{sub 1.96}, filled-up CaCu{sub 5} type, P6/mmm; LaNi{sub 4}PdD{sub 2.72}, LaNi{sub 2}(Ni{sub 0.75}Pt{sub 0.25}){sub 3}H{sub 2.61} type, oI128, Ibam; LaNi{sub 4.75}Pd{sub 0.25}D{sub 5.67}, partly ordered CaCu{sub 5} type, P6mm). In addition, the phase diagram of LaNi{sub 5-x}Pd{sub x}-H system has been investigated. The electronic and thermodynamic properties of both intermetallic compounds and the hydrides have been studied by ab initio electronic structure calculations. The theoretical results are in good agreement with our experimental data, and show that electronic interactions play a major role in the hydrogenation behavior of these Pd substituted intermetallic compounds, and that these effects cannot be accounted for by a simplistic model based on the size effect alone. -- Graphical abstract: Phase diagram of the system LaNi{sub 5-x}Pd{sub x}-D{sub 2} (absorption) at 25 {sup o}C and 25 bar. Display Omitted

  6. Structure Defect Property Relationships in Binary Intermetallics

    NASA Astrophysics Data System (ADS)

    Medasani, Bharat; Ding, Hong; Chen, Wei; Persson, Kristin; Canning, Andrew; Haranczyk, Maciej; Asta, Mark

    2015-03-01

    Ordered intermetallics are light weight materials with technologically useful high temperature properties such as creep resistance. Knowledge of constitutional and thermal defects is required to understand these properties. Vacancies and antisites are the dominant defects in the intermetallics and their concentrations and formation enthalpies could be computed by using first principles density functional theory and thermodynamic formalisms such as dilute solution method. Previously many properties of the intermetallics such as melting temperatures and formation enthalpies were statistically analyzed for large number of intermetallics using structure maps and data mining approaches. We undertook a similar exercise to establish the dependence of the defect properties in binary intermetallics on the underlying structural and chemical composition. For more than 200 binary intermetallics comprising of AB, AB2 and AB3 structures, we computed the concentrations and formation enthalpies of vacancies and antisites in a small range of stoichiometries deviating from ideal stoichiometry. The calculated defect properties were datamined to gain predictive capabilities of defect properties as well as to classify the intermetallics for their suitability in high-T applications. Supported by the US DOE under Contract No. DEAC02-05CH11231 under the Materials Project Center grant (Award No. EDCBEE).

  7. Hyperfine field at Mn in the intermetallic compound LaMnSi2 measured by PAC using 111Cd nuclear probe

    NASA Astrophysics Data System (ADS)

    Domienikan, C.; Bosch-Santos, B.; Cabrera Pasca, G. A.; Saxena, R. N.; Carbonari, A. W.

    2015-04-01

    Magnetic hyperfine field at Mn site has been measured in the orthorhombic intermetallic compound LaMnSi2 with PAC spectroscopy using radioactive 111In- 111Cd nuclear probe. Samples of LaMnSi2 were prepared by melting pure metallic components in stoichiometric proportion in an arc furnace under argon atmosphere. The samples were sealed in a quartz tube under helium atmosphere, annealed at 1000 °C for 60 h and quenched in water. Samples were analyzed with X-ray diffraction method. 111In was introduced in the samples by thermal diffusion at 1000 °C for 60 h. PAC measurements were carried out with a six BaF2 detector spectrometer at several temperatures between 50 K and 410 K. Results show well defined quadrupole and magnetic interactions at all temperatures. The magnetic hyperfine field (Bhf) measured at 50 K is 7.1(1) T. The temperature dependence of Bhf follows the normal Brillouin-like behavior expected for a simple ferromagnetic ordering. The ferromagnetic transition temperature (Tc) was determined to be 401(1) K.

  8. Effect of microstructure and texture on the magnetic and magnetocaloric properties of the melt-spun rare earth intermetallic compound DyNi

    NASA Astrophysics Data System (ADS)

    Rajivgandhi, R.; Chelvane, J. Arout; Nigam, A. K.; Park, Je-Geun; Malik, S. K.; Nirmala, R.

    2016-11-01

    Magnetization measurements have been carried out on the melt-spun ribbon sample of the rare earth intermetallic compound DyNi (Orthorhombic, FeB-type, Space group Pnma) and its magnetic and magnetocaloric properties are compared with those of the arc-melted analog. The arc-melted DyNi orders ferromagnetically at around 61 K (TC) whereas the melt-spun DyNi orders ferromagnetically at about 47 K. The maximum isothermal magnetic entropy change, ∆Smmax , near TC of the arc-melted and the melt-spun DyNi is found to be -32.7 J/kg K and -22.4 J/kg K, respectively, for a field change of 140 kOe. For low magnetic field changes of ~20 kOe, the relative cooling power (RCP) is ~660 J/kg for the arc melted DyNi and ~460 J/kg for the melt-spun ribbon. The reduction in TC and magnetocaloric effect may be attributed to the microstructure-induced anisotropy developed during the melt-spinning process.

  9. Anisotropy in the paramagnetic phase of RAl/sub 2/ cubic intermetallic compounds (R = Tb, Dy, and Er)

    SciTech Connect

    del Moral, A.; Ibarra, M.R.; Abell, J.S.; Montenegro, J.F.D.

    1987-05-01

    In this paper it is shown that the anisotropy in the paramagnetic phase is a useful characteristic when used to single out high-rank susceptibility tensor components in the paramagnetic regime of cubic crystals. Application of this technique to RAl/sub 2/ compounds (R = Tb,Dy,Er) allows the determination of longitudinal and transverse (in the form of linear combinations) fourth- and sixth-rank paramagnetic susceptibilities. The use of the fourth-rank longitudinal susceptibility allows quadrupolar pair interactions in these compounds to be probed.

  10. Low-Temperature Synthesis Routes to Intermetallic Superconductors

    SciTech Connect

    Schaak, Raymond E

    2008-01-08

    Over the past few years, our group has gained expertise at developing low-temperature solution-based synthetic pathways to complex nanoscale solids, with particular emphasis on nanocrystalline intermetallic compounds. Our synthetic capabilities are providing tools to reproducibly generate intermetallic nanostructures with simultaneous control over crystal structure, composition, and morphology. This DOE-funded project aims to expand these capabilities to intermetallic superconductors. This could represent an important addition to the tools that are available for the synthesis and processing of intermetallic superconductors, which traditionally utilize high-temperature, high-pressure, thin film, or gas-phase vacuum deposition methods. Our current knowledge of intermetallic superconductors suggests that significant enhancements could result from the inherent benefits of low-temperature solution synthesis, e.g. metastable phase formation, control over nanoscale morphology to facilitate size-dependent property studies, robust and inexpensive processability, low-temperature annealing and consolidation, and impurity incorporation (for doping, stoichiometry control, flux pinning, and improving the critical fields). Our focus is on understanding the superconducting properties as a function of synthetic route, crystal structure, crystallite size, and morphology, and developing the synthetic tools necessary to accomplish this. This research program can currently be divided into two classes of superconducting materials: intermetallics (transition metal/post transition metal) and metal carbides/borides. Both involve the development and exploitation of low-temperature synthesis routes followed by detailed characterization of structures and properties, with the goal of understanding how the synthetic pathways influence key superconducting properties of selected target materials. Because of the low-temperature methods used to synthesize them and the nanocrystalline morphologies

  11. The magnetic behavior of the intermetallic compound NdMn{sub 2}Ge{sub 2} studied by magnetization and hyperfine interactions measurements

    SciTech Connect

    Bosch-Santos, B. Carbonari, A. W.; Cabrera-Pasca, G. A.; Saxena, R. N.; Freitas, R. S.

    2015-05-07

    The magnetic behavior of the intermetallic compound NdMn{sub 2}Ge{sub 2} was investigated by bulk magnetization measurements and measurements of hyperfine interactions using perturbed γ–γ angular correlation (PAC) spectroscopy. Magnetization measurements indicate the presence of four magnetic transitions associated with the Mn and Nd magnetic sublattices. At high temperatures, magnetic measurements show a change in the slope of the magnetization due to an antiferromagnetic transition around T{sub N} ∼ 425 K and a well defined ferromagnetic transition at T{sub C} ∼ 320 K. Moreover, at ∼210 K a peak is observed in the magnetization curve, which is assigned to the reorientation of the Mn spin, and at ∼25 K an increase in the magnetic moment is also observed, which is ascribed to the ordering of Nd ions. PAC measurements using {sup 140}La({sup 140}Ce) and {sup 111}In({sup 111}Cd) probe nuclei allowed the determination of the temperature dependence of the magnetic hyperfine field (B{sub hf}) at Nd and Mn sites, respectively. PAC results with {sup 111}Cd probe nuclei at Mn sites show that the dependence of B{sub hf} with temperature follows the expected behavior for the host magnetization associated with the magnetic ordering of Mn ions. From these results, the antiferromagnetic transition followed by a ferromagnetic ordering is clearly observed. PAC results with {sup 140}Ce probe nuclei at Nd sites, however, showed a strong deviation from the Brillouin function, which is attributed to the Ce 4f-electron contribution to B{sub hf}.

  12. Effect of Cross-Interaction between Ni and Cu on Growth Kinetics of Intermetallic Compounds in Ni/Sn/Cu Diffusion Couples during Aging

    NASA Astrophysics Data System (ADS)

    Hong, K. K.; Ryu, J. B.; Park, C. Y.; Huh, J. Y.

    2008-01-01

    The solid-state, cross-interaction between the Ni layer on the component side and the Cu pad on the printed circuit board (PCB) side in ball grid array (BGA) solder joints was investigated by employing Ni(15 μm)/Sn(65 μm)/Cu ternary diffusion couples. The ternary diffusion couples were prepared by sequentially electroplating Sn and Ni on a Cu foil and were aged isothermally at 150, 180, and 200°C. The growth of the intermetallic compound (IMC) layer on the Ni side was coupled with that on the Cu side by the mass flux across the Sn layer that was caused by the difference in the Ni content between the (Cu1- x Ni x )6Sn5 layer on the Ni side and the (Cu1- y Ni y )6Sn5 layer on the Cu side. As the consequence of the coupling, the growth rate of the (Cu1- x Ni x )6 Sn5 layer on the Ni side was rapidly accelerated by decreasing Sn layer thickness and increasing aging temperature. Owing to the cross-interaction with the top Ni layer, the growth rate of the (Cu1- y Ni y )6Sn5 layer on the Cu side was accelerated at 150°C and 180°C but was retarded at 200°C, while the growth rate of the Cu3Sn layer was always retarded. The growth kinetic model proposed in an attempt to interpret the experimental results was able to reproduce qualitatively all of the important experimental observations pertaining to the growth of the IMC layers in the Ni/Sn/Cu diffusion couple.

  13. e/a determination for 4d- and 5d-transition metal elements and their intermetallic compounds with Mg, Al, Zn, Cd and In

    NASA Astrophysics Data System (ADS)

    Mizutani, U.; Sato, H.; Inukai, M.; Zijlstra, E. S.

    2013-08-01

    The present work is devoted to the determination of the effective electrons per atom ratio e/a by means of first-principles full-potential linearized augmented plane wave-Fourier method for elements from Rb to Ag in Period 5 and from Cs to Au in Period 6 of the periodic table and is regarded as a continuation of the preceding work done for elements from K to Cu in Period 4. The value of e/a was determined by reading off the square of the Fermi diameter, ? from the dispersion relation for electrons outside the Muffin-Tin spheres. A straightforward reading of the ordinate at the Fermi level, i.e. local reading method was validated for Rb and Cs in Group 1, Sr in Group 2, Y in Group 3, Pd and Pt in Group 10 and Ag and Au in Group 11. Instead, the nearly free electron (NFE) method was found to be indispensable for TM elements from Zr to Rh in Period 5 and those from Ba to Ir in Period 6. The composition dependence of e/a values for intermetallic compounds in X-TM (X = Mg, Al, Zn, Cd and In) alloy systems was also studied. The new Hume-Rothery electron concentration rule was established by constructing e/uc, the number of electrons per unit cell, vs. square of critical reciprocal lattice vector, ? , diagram for structurally complex metallic alloys having a pseudogap at the Fermi level. A proper use of either the local reading- or the NFE-e/a for the elements as indicated above is found to be essential.

  14. NFE approximation for the e/a determination for 3d-transition metal elements and their intermetallic compounds with Al and Zn

    NASA Astrophysics Data System (ADS)

    Sato, H.; Inukai, M.; Zijlstra, E. S.; Mizutani, U.

    2013-08-01

    First-principles full-potential linearized augmented plane wave (FLAPW) band calculations with subsequent FLAPW-Fourier analyses have been performed for elements from K to Cu in period 4 of the periodic table to determine the effective electrons per atom ratio (e/a). For the series of 3d-transition metals (TM), the determination of the square of the Fermi diameter ? , from which e/a is derived, has been recognized not to be straightforward because of the presence of a huge anomaly associated with the TM-d states across the Fermi level in the energy dispersion relation for electrons outside the muffin-tin sphere. The nearly free electron (NFE) approximation is newly devised to circumvent this difficulty. The centre of gravity energy ? is calculated from the energy distribution of the square of the Fourier coefficients for the FLAPW state ? . The NFE dispersion relation is constructed for the set of ? and ? in combination with the tetrahedron method. The resulting e/a values are distributed over positive numbers in the vicinity of unity for elements from Ti to Co. Instead, the e/a values for the early elements K, Ca and Sc and the late TM elements Ni and Cu were determined to be close to one, two, three, 0.50 and unity, respectively, using our previously designed local reading method. In addition, the composition dependence of e/a values for intermetallic compounds in X-TM (X = Al and Zn) alloy systems was studied to justify an appropriate choice between the local reading and NFE methods for respective elements.

  15. Controlling Interfacial Reactions and Intermetallic Compound Growth at the Interface of a Lead-free Solder Joint with Layer-by-Layer Transferred Graphene.

    PubMed

    Ko, Yong-Ho; Lee, Jong-Dae; Yoon, Taeshik; Lee, Chang-Woo; Kim, Taek-Soo

    2016-03-02

    The immoderate growth of intermetallic compounds (IMCs) formed at the interface of a solder metal and the substrate during soldering can degrade the mechanical properties and reliability of a solder joint in electronic packaging. Therefore, it is critical to control IMC growth at the solder joints between the solder and the substrate. In this study, we investigated the control of interfacial reactions and IMC growth by the layer-by-layer transfer of graphene during the reflow process at the interface between Sn-3.0Ag-0.5Cu (in wt %) lead-free solder and Cu. As the number of graphene layers transferred onto the surface of the Cu substrate increased, the thickness of the total IMC (Cu6Sn5 and Cu3Sn) layer decreased. After 10 repetitions of the reflow process for 50 s above 217 °C, the melting temperature of Sn-3.0Ag-0.5Cu, with a peak temperature of 250 °C, the increase in thickness of the total IMC layer at the interface with multiple layers of graphene was decreased by more than 20% compared to that at the interface of bare Cu without graphene. Furthermore, the average diameter of the Cu6Sn5 scallops at the interface with multiple layers of graphene was smaller than that at the interface without graphene. Despite 10 repetitions of the reflow process, the growth of Cu3Sn at the interface with multiple layers of graphene was suppressed by more than 20% compared with that at the interface without graphene. The multiple layers of graphene at the interface between the solder metal and the Cu substrate hindered the diffusion of Cu atoms from the Cu substrate and suppressed the reactions between Cu and Sn in the solder. Thus, the multiple layers of graphene transferred at the interface between dissimilar metals can control the interfacial reaction and IMC growth occurring at the joining interface.

  16. R5T4 compounds - unique multifunctional intermetallics for basic research and applications

    SciTech Connect

    Mudryk, Yaroslav

    2016-10-01

    The unique properties of the rare-earth elements and their alloys have brought them from relative obscurity to high profile use in common high-tech applications. The broad technological impact of these remarkable materials may have never been known by the general public if not for the supply concerns that placed the rare-earth materials on the front page of newspapers and magazines. Neodymium and dysprosium, two essential components of Nd2Fe14B-based high-performance permanent magnets, have drawn much attention and have been deemed critical materials for many energy-related applications. Ironically, the notoriety of rare-earth elements and their alloys is the result of a global movement to reduce their use in industrial applications and, thus, ease concerns about their supply and ultimately to reduce their position in high-tech supply chains. Research into the applications of lanthanide alloys has been de-emphasized recently due to the perception that industry is moving away from the use of rare-earth elements in new products. While lanthanide supply challenges justify efforts to diversify the supply chain, a strategy to completely replace the materials overlooks the reasons rare earths became important in the first place -- their unique properties are too beneficial to ignore. Rare-earth alloys and compounds possess truly exciting potential for basic science exploration and application development such as solid-state caloric cooling. In this brief review, we touch upon several promising systems containing lanthanide elements that show important and interesting magnetism-related phenomena.

  17. Formation of multinary intermetallics from reduction of perovskites by aluminum flux: M(3)Au(6+)(x)()Al(26)Ti (M = Ca, Sr, Yb), a stuffed variant of the BaHg(11) type.

    PubMed

    Latturner, Susan E; Kanatzidis, Mercouri G

    2004-01-12

    New intermetallic phases were synthesized by reacting oxidic perovskites and gold metal in aluminum flux. The combination of MTiO(3) (M = Ca, Sr, Ba) and Au metal in excess molten aluminum produces quaternary compounds M(3)Au(6+)(x)()Al(26)Ti with a stuffed BaHg(11) structure type. An analogue with M = Yb was also synthesized; it shows mixed valent behavior.

  18. Effects of the pouring temperature on the formation of the bonding zone between AZ91 and AlSi17 in the compound casting process

    NASA Astrophysics Data System (ADS)

    Mola, R.; Bucki, T.; Dziadoń, A.

    2017-02-01

    The compound casting process was used to join AZ91 magnesium alloy to AlSi17 aluminium alloy. Liquid AZ91 was poured onto a solid AlSi17 insert placed in a steel mould heated to 370 °C. The experimental results showed that the temperature of the AZ91 melt affected the formation of the bonding zone between the two alloys. A continuous bonding zone was formed by applying a pouring temperature of 650 °C. The use of higher temperatures, i.e. 680 °C and 700 °C, did not lead to the formation of a continuous metallurgical transition zone at the AZ91/AlSi17 interface. The bonding zone was analysed using an optical microscope and a scanning electron microscope equipped with an energy dispersive X-ray (EDS) detector. The structural constituents of the bonding zone near the AlSi17 alloy were: an Al3Mg2 intermetallic phase, primary Si particles surrounded by a rim of an Mg2Si intermetallic phase and fine Mg2Si particles. The area of the bonding zone that was adjacent to the AZ91 alloy had a eutectic structure composed of an Mg17Al12 intermetallic phase and a solid solution of Al and Si in Mg.

  19. Theoretical screening of intermetallic ThMn12-type phases for new hard-magnetic compounds with low rare earth content

    PubMed Central

    Körner, Wolfgang; Krugel, Georg; Elsässer, Christian

    2016-01-01

    We report on theoretical investigations of intermetallic phases derived from the ThMn12-type crystal structure. Our computational high-throughput screening (HTS) approach is extended to an estimation of the anisotropy constant K1, the anisotropy field Ha and the energy product (BH)max. The calculation of K1 is fast since it is based on the crystal field parameters and avoids expensive total-energy calculations with many k-points. Thus the HTS approach allows a very efficient search for hard-magnetic materials for which the magnetization M and the coercive field Hc connected to Ha represent the key quantities. Besides for NdFe12N which has the highest magnetization we report HTS results for several intermetallic phases based on Cerium which are interesting as alternative hard-magnetic phases because Cerium is a less ressource-critical element than Neodymium. PMID:27098547

  20. Local magnetic moment formation at 119Sn Mössbauer impurity in RCo2 (R=Gd,Tb,Dy,Ho,Er) Laves phase compounds

    NASA Astrophysics Data System (ADS)

    de Oliveira, A. L.; de Oliveira, N. A.; Troper, A.

    2008-04-01

    In this work, we theoretically study the local magnetic moment formation and the systematics of the magnetic hyperfine fields at a Mösbauer Sn119 impurity diluted at the R site (R=Gd,Tb,Dy,Ho,Er) of the cubic Laves phase intermetallic compounds RCo2. One considers that the magnetic hyperfine fields have two contributions, (i) the contribution from R ions, calculated via an extended Daniel-Friedel [J. Phys. Chem. Solids 24, 1601 (1963)] model, and (ii) the contribution from the induced magnetic moments arising from the Co neighboring sites. Our calculated self-consistent total magnetic hyperfine fields are in a good agreement with recent experimental data.

  1. Chemistry and Properties of Complex Intermetallics from Metallic Fluxes

    SciTech Connect

    Kanatzidis, Mercouri G.

    2015-03-28

    This project investigated the reaction chemistry and synthesis of new intermetallic materials with complex compositions and structures using metallic fluxes as solvents. It was found that the metallic fluxes offer several key advantages in facilitating the formation and crystal growth of new materials. The fluxes mostly explored were liquid aluminum, gallium and indium. The main purpose of this project was to exploit the potential of metallic fluxes as high temperature solvent for materials discovery in the broad class of intermetallics. This work opened new paths to compound formation. We discovered many new Si (or Ge)-based compounds with novel structures, bonding and physicochemical properties. We created new insights about the reaction chemistry that is responsible for stabilizing the new materials. We also studied the structural and compositional relationships to understand their properties. We investigated the use of Group-13 metals Al, Ga and In as solvents and have generated a wide variety of new results including several new ternary and quaternary materials with fascinating structures and properties as well as new insights as to how these systems are stabilized in the fluxes. The project focused on reactions of metals from the rare earth element family in combination with transition metals with Si and Ge. For example molten gallium has serves both as a reactive and non-reactive solvent in the preparation and crystallization of intermetallics in the system RE/M/Ga/Ge(Si). Molten indium behaves similarly in that it too is an excellent reaction medium, but it gives compounds that are different from those obtained from gallium. Some of the new phase identified in the aluminide class are complex phases and may be present in many advanced Al-matrix alloys. Such phases play a key role in determining (either beneficially or detrimentally) the mechanical properties of advanced Al-matrix alloys. This project enhanced our basic knowledge of the solid state chemistry

  2. The μ3 model of acids and bases: extending the Lewis theory to intermetallics.

    PubMed

    Stacey, Timothy E; Fredrickson, Daniel C

    2012-04-02

    A central challenge in the design of new metallic materials is the elucidation of the chemical factors underlying the structures of intermetallic compounds. Analogies to molecular bonding phenomena, such as the Zintl concept, have proven very productive in approaching this goal. In this Article, we extend a foundational concept of molecular chemistry to intermetallics: the Lewis theory of acids and bases. The connection is developed through the method of moments, as applied to DFT-calibrated Hückel calculations. We begin by illustrating that the third and fourth moments (μ(3) and μ(4)) of the electronic density of states (DOS) distribution tune the properties of a pseudogap. μ(3) controls the balance of states above and below the DOS minimum, with μ(4) then determining the minimum's depth. In this way, μ(3) predicts an ideal occupancy for the DOS distribution. The μ(3)-ideal electron count is used to forge a link between the reactivity of transition metals toward intermetallic phase formation, and that of Lewis acids and bases toward adduct formation. This is accomplished through a moments-based definition of acidity which classifies systems that are electron-poor relative to the μ(3)-ideal as μ(3)-acidic, and those that are electron-rich as μ(3)-basic. The reaction of μ(3) acids and bases, whether in the formation of a Lewis acid/base adduct or an intermetallic phase, tends to neutralize the μ(3) acidity or basicity of the reactants. This μ(3)-neutralization is traced to the influence of electronegativity differences at heteroatomic contacts on the projected DOS curves of the atoms involved. The role of μ(3)-acid/base interactions in intermetallic phases is demonstrated through the examination of 23 binary phases forming between 3d metals, the stability range of the CsCl type, and structural trends within the Ti-Ni system.

  3. The effect of pH on the corrosion behavior of intermetallic compounds Ni{sub 3}(Si,Ti) and Ni{sub 3}(Si,Ti) + 2Mo in sodium chloride solutions

    SciTech Connect

    Priyotomo, Gadang Nuraini, Lutviasari; Kaneno, Yasuyuki

    2015-12-29

    The corrosion behavior of the intermetallic compounds, Ni{sub 3}(Si,Ti) (L1{sub 2}: single phase) and Ni{sub 3}(Si,Ti) + 2Mo (L1{sub 2} and (L12 + Ni{sub ss}) mixture region), has been investigated using an immersion test, electrochemical method and surface analytical method (SEM; scanning electron microscope and EDAX: Energy Dispersive X-ray) in 0.5 kmol/m{sup 3} NaCl solutions at various pH. The corrosion behavior of nickel alloy C-276 was studied under the same experimental conditions as a reference. It was found that the uniform attack was observed on Ni{sub 3}(Si,Ti) for the immersion test at lower pH, while the pitting attack was observed on this compound for this test at neutral solution. Furthermore, Ni{sub 3}(Si,Ti)+2Mo had the preferential dissolution of L1{sub 2} compared to (L1{sub 2} + Ni{sub ss}) mixture region at lower pH, while pitting attack occurred in (L1{sub 2} + Ni{sub ss}) mixture region at neutral solution. For both intermetallic compounds, the magnitude of pitting and uniform attack decrease with increasing pH of solutions. From the immersion test and polarization curves, the corrosion resistance of Ni{sub 3}(Si,Ti)+2Mo is lower than that of Ni{sub 3}(Si,Ti), while the nickel alloy C-276 is the highest one at various pH of solutions. On the other hand, in the lower pH of solutions, the corrosion resistance of tested materials decreased significantly compared to those in neutral and higher pH of solutions.

  4. Structure Formation Mechanisms during Solid Ti with Molten Al Interaction

    NASA Astrophysics Data System (ADS)

    Gurevich, L.; Pronichev, D.; Trunov, M.

    2016-02-01

    The study discuses advantages and disadvantages of previously proposed mechanisms of the formation of structure between solid Ti and molten Al and presents a new mechanism based on the reviewed and experimental data. The previously proposed mechanisms were classified into three groups: mechanisms of precipitation, mechanisms of destruction and mechanisms of chemical interaction between intermetallics and melt. The reviewed mechanisms did not explain the formation of heterogeneous interlayer with globular aluminide particles and thin layers of pure Al, while the present study reveals variation in the solid Ti/molten Al reaction kinetics during various phases of laminated metal-intermetallic composite formation. The proposed mechanism considers formed during composite fabrication thin oxide interlayers between Ti and Al evolution and its impact on the intermetallic compound formation and explains the initial slow rate of intermetallic interlayer formation and its subsequent acceleration when the oxide foils are ruptured.

  5. Magnesium silicide intermetallic alloys

    NASA Astrophysics Data System (ADS)

    Li, Gh.; Gill, H. S.; Varin, R. A.

    1993-11-01

    Methods of induction melting an ultra-low-density magnesium silicide (Mg2Si) intermetallic and its alloys and the resulting microstructure and microhardness were studied. The highest quality ingots of Mg2Si alloys were obtained by triple melting in a graphite crucible coated with boron nitride to eliminate reactivity, under overpressure of high-purity argon (1.3 X 105 Pa), at a temperature close to but not exceeding 1105 °C ± 5 °C to avoid excessive evaporation of Mg. After establishing the proper induction-melting conditions, the Mg-Si binary alloys and several Mg2Si alloys macroalloyed with 1 at. pct of Al, Ni, Co, Cu, Ag, Zn, Mn, Cr, and Fe were induction melted and, after solidification, investigated by optical microscopy and quantitative X-ray energy dispersive spectroscopy (EDS). Both the Mg-rich and Si-rich eutectic in the binary alloys exhibited a small but systematic increase in the Si content as the overall composition of the binary alloy moved closer toward the Mg2Si line compound. The Vickers microhardness (VHN) of the as-solidified Mg-rich and Si-rich eutectics in the Mg-Si binary alloys decreased with increasing Mg (decreasing Si) content in the eutectic. This behavior persisted even after annealing for 75 hours at 0.89 pct of the respective eutectic temperature. The Mg-rich eutectic in the Mg2Si + Al, Ni, Co, Cu, Ag, and Zn alloys contained sections exhibiting a different optical contrast and chemical composition than the rest of the eutectic. Some particles dispersed in the Mg2Si matrix were found in the Mg2Si + Cr, Mn, and Fe alloys. The EDS results are presented and discussed and compared with the VHN data.

  6. Influence of Aluminum on the Formation Behavior of Zn-Al-Fe Intermetallic Particles in a Zinc Bath

    NASA Astrophysics Data System (ADS)

    Park, Joo Hyun; Park, Geun-Ho; Paik, Doo-Jin; Huh, Yoon; Hong, Moon-Hi

    2012-01-01

    The shape, size, and composition of dross particles as a function of aluminum content at a fixed temperature were investigated for aluminum added to the premelted Zn-Fe melt simulating the hot-dip galvanizing bath by a sampling methodology. In the early stage, less than 30 minutes after Al addition, local supersaturation and depletion of the aluminum concentration occurred simultaneously in the bath, resulting in the nucleation and growth of both Fe2Al5Zn x and FeZn13. However, the aluminum was homogenized continuously as the reaction proceeded, and fine and stable FeZn10Al x formed after 30 minutes. An Al-depleted zone (ADZ) mechanism was newly proposed for the "η→η+ζ→δ" phase transformations. The ζ phase bottom dross partly survived for a relatively long period, i.e., 2 hours in this work, whereas the η phase disappeared after 30 minutes. In the early stage of dross formation, both Al-free large particles as well as high-Al tiny particles were formed. The dross particle size decreased slightly with increased reaction time before reaching a plateau. The opposite tendency was observed when the Al content was 0.130 mass pct; with a relatively high Al content, the nucleation of tiny η phase dross was significantly enhanced because of the high degree of supersaturation. This unstable η phase dissolved continuously and underwent simple transformation to the stable δ phase. The relationship between nucleation potential and supersaturation ratio of species is discussed based on the thermodynamics of classical nucleation theory.

  7. Formation of highly oxidized multifunctional organic compounds from anthropogenic volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Molteni, Ugo; Baltensperger, Urs; Bianchi, Federico; Dommen, Josef; El Haddad, Imad; Frege, Carla; Klein, Felix; Rossi, Michel

    2016-04-01

    Recent studies have shown that highly oxidized multifunctional organic compounds (HOMs) from biogenic volatile organic compounds are important for new particle formation and early particle growth (e.g., Ehn et al., 2014). The formation mechanism has extensively been studied for biogenic precursors like alpha-pinene and was shown to proceed through an initial reaction with either OH radicals or ozone followed by radical propagation in a mechanism that involves O2 attack and hydrogen abstraction (Crounse et al., 2013). While the same processes can be expected for anthropogenic volatile organic compounds (AVOC), few studies have investigated these so far. Here we present the formation of HOMs from a variety of aromatic compounds after reaction with OH. All the compounds analyzed show HOM formation. AVOC could therefore play an important role in new particle formation events that have been detected in urban areas. References Crounse, J.D. et al., Autoxidation of organic compounds in the atmosphere. J. Phys.Chem. Lett. 4, 3513-3520 (2013). Ehn, M., et al. A large source of low-volatility secondary organic aerosol, Nature 506, 476-479 (2014).

  8. Development of intermetallic-hardened abrasion-resistant weld hardfacing alloys

    SciTech Connect

    School, M.R.

    1986-01-01

    Chromium and cobalt are strategic materials in the US and both are major constituents in many weld hardfacing alloys. Substitution for these materials or alternatives to their use was a primary direction of this investigation which was conducted in conjunction with the US Bureau of Mines. Minimization of the use of strategic materials was the criteria guiding the development of intermetallic-hardened abrasion resistant weld hardfacing materials. Other criteria were that the new alloy contain a hard intermetallic compound in an FCC matrix, and that these intermetallic compounds be stable at room temperature. A survey of ternary systems was made and the Fe-Mo-Ni system was selected to provide a basis for alloy development. Fe-Mo-Ni alloys synthesized by arc-melting and similar alloys made by welding possessed similar microstructures, a (Fe, Ni){sub 7}Mo{sub 6} intermetallic plus austenite eutectic in an austenitic matrix. These materials exhibited poor abrasive resistance. Silicon additions to the alloy promoted formation of a Laves phase FeMoSi intermetallic which helped increase the abrasive wear resistance. Through a series of alloy chemistry iterations a final composition of Fe-20Mo-15Ni-5Si was selected. Heat treatment of this alloy at 550 to 650 C caused second phase precipitation in the matrix and raised the hardness about 14 points HRC to 50 HRC. The alloy's wear rate, measured with the pin-on-drum abrasive wear test, was 6.3 to 6.5 mg/m. However this was twice the wear rate observed in commercial high-carbon high-chromium alloys. Based on examination of the alloy microstructures, their chemistry, and an analysis of the Fe-Mo-Si phase system; directions for further research are to increase the molybdenum and silicon content to produce a Fe-20Mo-10Ni-15Si composition.

  9. Process and apparatus for formation of photovoltaic compounds

    DOEpatents

    Hall, Robert B.; Rocheleau, Richard E.

    1985-01-01

    The invention relates to a process and apparatus for formation and deposition of thin films on a substrate, in a vacuum, by evaporation of the elements to form a Zn.sub.x Cd.sub.1-x S compound having a preselected fixed ratio of cadmium to zinc, characterized by the evaporation of cadmium and zinc at a rate the ratio of which is proportional to the stoichiometric ratio of those elements in the intended compound and evaporation of sulfur at a rate at least twice the combined rates of cadmium and zinc, and at least twice that required by the stoichiometry of the intended compound.

  10. Integrating giant microwave absorption with magnetic refrigeration in one multifunctional intermetallic compound of LaFe(11.6)Si(1.4)C(0.2)H(1.7).

    PubMed

    Song, Ning-Ning; Ke, Ya-Jiao; Yang, Hai-Tao; Zhang, Hu; Zhang, Xiang-Qun; Shen, Bao-Gen; Cheng, Zhao-Hua

    2013-01-01

    Both microwave absorption and magnetocaloric effect (MCE) are two essential performances of magnetic materials. We observe that LaFe(11.6)Si(1.4)C(0.2)H(1.7) intermetallic compound exhibits the advantages of both giant microwave absorption exceeding -42 dB and magnetic entropy change of -20 Jkg(-1)K(-1). The excellent electromagnetic wave absorption results from the large magnetic loss and dielectric loss as well as the efficient complementarity between relative permittivity and permeability. The giant MCE effect in this material provides an ideal technique for cooling the MAMs to avoid temperature increase and infrared radiation during microwave absorption. Our finding suggests that we can integrate the giant microwave absorption with magnetic refrigeration in one multifunctional material. This integration not only advances our understanding of the correlation between microwave absorption and MCE, but also can open a new avenue to exploit microwave devices and electromagnetic stealth.

  11. SrZn{sub 2}Sn{sub 2} and Ca{sub 2}Zn{sub 3}Sn{sub 6} - two new Ae-Zn-Sn polar intermetallic compounds (Ae: alkaline earth metal)

    SciTech Connect

    Stegmaier, Saskia; Faessler, Thomas F.

    2012-08-15

    SrZn{sub 2}Sn{sub 2} and Ca{sub 2}Zn{sub 3}Sn{sub 6}, two closely related new polar intermetallic compounds, were obtained by high temperature reactions of the elements. Their crystal structures were determined with single crystal XRD methods, and their electronic structures were analyzed by means of DFT calculations. The Zn-Sn structure part of SrZn{sub 2}Sn{sub 2} comprises (anti-)PbO-like {l_brace}ZnSn{sub 4/4}{r_brace} and {l_brace}SnZn{sub 4/4}{r_brace} layers. Ca{sub 2}Zn{sub 3}Sn{sub 6} shows similar {l_brace}ZnSn{sub 4/4}{r_brace} layers and {l_brace}Sn{sub 4}Zn{r_brace} slabs constructed of a covalently bonded Sn scaffold capped by Zn atoms. For both phases, the two types of layers are alternatingly stacked and interconnected via Zn-Sn bonds. SrZn{sub 2}Sn{sub 2} adopts the SrPd{sub 2}Bi{sub 2} structure type, and Ca{sub 2}Zn{sub 3}Sn{sub 6} is isotypic to the R{sub 2}Zn{sub 3}Ge{sub 6} compounds (R=La, Ce, Pr, Nd). Band structure calculations indicate that both SrZn{sub 2}Sn{sub 2} and Ca{sub 2}Zn{sub 3}Sn{sub 6} are metallic. Analyses of the chemical bonding with the electron localization function (ELF) show lone pair like basins at Sn atoms and Zn-Sn bonding interactions between the layers for both title phases, and covalent Sn-Sn bonding within the {l_brace}Sn{sub 4}Zn{r_brace} layers of Ca{sub 2}Zn{sub 3}Sn{sub 6}. - Graphical abstract: Crystal structures of the new Ae-Zn-Sn polar intermetallic phases SrZn{sub 2}Sn{sub 2} and Ca{sub 2}Zn{sub 3}Sn{sub 6}. Highlights: Black-Right-Pointing-Pointer New polar intermetallic phases SrZn{sub 2}Sn{sub 2} and Ca{sub 2}Zn{sub 3}Sn{sub 6}. Black-Right-Pointing-Pointer Obtained by high temperature reactions of the elements. Black-Right-Pointing-Pointer Single crystal XRD structure determination and DFT electronic structure calculations. Black-Right-Pointing-Pointer Closely related crystal and electronic structures. Black-Right-Pointing-Pointer Metallic conductivity coexisting with lone pairs and covalent bonding

  12. Structure and magnetism of new rare-earth-free intermetallic compounds: Fe3+xCo3-xTi2 (0 ≤ x ≤ 3)

    DOE PAGES

    Balasubramanian, Balamurugan; Das, Bhaskar; Nguyen, Manh Cuong; ...

    2016-11-28

    Here, we report the fabrication of a set of new rare-earth-free magnetic compounds, which form the Fe3Co3Ti2-type hexagonal structure with P-6m2 symmetry. Neutron powder diffraction shows a significant Fe/Co anti-site mixing in the Fe3Co3Ti2 structure, which has a strong effect on the magnetocrystalline anisotropy as revealed by first-principle calculations. Increasing substitution of Fe atoms for Co in the Fe3Co3Ti2 lattice leads to the formation of Fe4Co2Ti2, Fe5CoTi, and Fe6Ti2 with significantly improved permanent-magnet properties. A high magnetic anisotropy (13.0 Mergs/cm3) and saturation magnetic polarization (11.4 kG) are achieved at 10 K by altering the atomic arrangements and decreasing Fe/Co occupancymore » disorder.« less

  13. Hydroxyl radical-induced formation of highly oxidized organic compounds

    NASA Astrophysics Data System (ADS)

    Berndt, Torsten; Richters, Stefanie; Jokinen, Tuija; Hyttinen, Noora; Kurtén, Theo; Otkjær, Rasmus V.; Kjaergaard, Henrik G.; Stratmann, Frank; Herrmann, Hartmut; Sipilä, Mikko; Kulmala, Markku; Ehn, Mikael

    2016-12-01

    Explaining the formation of secondary organic aerosol is an intriguing question in atmospheric sciences because of its importance for Earth's radiation budget and the associated effects on health and ecosystems. A breakthrough was recently achieved in the understanding of secondary organic aerosol formation from ozone reactions of biogenic emissions by the rapid formation of highly oxidized multifunctional organic compounds via autoxidation. However, the important daytime hydroxyl radical reactions have been considered to be less important in this process. Here we report measurements on the reaction of hydroxyl radicals with α- and β-pinene applying improved mass spectrometric methods. Our laboratory results prove that the formation of highly oxidized products from hydroxyl radical reactions proceeds with considerably higher yields than previously reported. Field measurements support these findings. Our results allow for a better description of the diurnal behaviour of the highly oxidized product formation and subsequent secondary organic aerosol formation in the atmosphere.

  14. Hydroxyl radical-induced formation of highly oxidized organic compounds

    PubMed Central

    Berndt, Torsten; Richters, Stefanie; Jokinen, Tuija; Hyttinen, Noora; Kurtén, Theo; Otkjær, Rasmus V.; Kjaergaard, Henrik G.; Stratmann, Frank; Herrmann, Hartmut; Sipilä, Mikko; Kulmala, Markku; Ehn, Mikael

    2016-01-01

    Explaining the formation of secondary organic aerosol is an intriguing question in atmospheric sciences because of its importance for Earth's radiation budget and the associated effects on health and ecosystems. A breakthrough was recently achieved in the understanding of secondary organic aerosol formation from ozone reactions of biogenic emissions by the rapid formation of highly oxidized multifunctional organic compounds via autoxidation. However, the important daytime hydroxyl radical reactions have been considered to be less important in this process. Here we report measurements on the reaction of hydroxyl radicals with α- and β-pinene applying improved mass spectrometric methods. Our laboratory results prove that the formation of highly oxidized products from hydroxyl radical reactions proceeds with considerably higher yields than previously reported. Field measurements support these findings. Our results allow for a better description of the diurnal behaviour of the highly oxidized product formation and subsequent secondary organic aerosol formation in the atmosphere. PMID:27910849

  15. Thermal barrier coating system with intermetallic overlay bond coat

    SciTech Connect

    Duderstadt, E.C.; Nagaraj, B A.

    1993-08-24

    A superalloy article is described having a thermal barrier coating system thereon, comprising: a substrate made of a material selected from the group consisting of a nickel-based superalloy and a cobalt-based superalloy; and a thermal barrier coating system on the substrate, the thermal barrier coating system including an intermetallic bond coat overlying the substrate, the bond coat being selected from the group consisting of a nickel aluminide and a platinum aluminide intermetallic compound, a thermally grown aluminum oxide layer overlying the intermetallic bond coat, and a ceramic topcoat overlying the aluminum oxide layer.

  16. Heats of Formation and Bond Energies in Group III Compounds

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Allendorf, Mark D.; Melius, Carl F.; Arnold, James O. (Technical Monitor)

    1999-01-01

    We present heats of formation and bond energies for Group-III compounds obtained from calculations of molecular ground-state I electronic energies. Data for compounds of the form MXn are presented, where M = B, Al, Ga, and In, X = He H, Cl, and CH3, and n = 1-3. Energies for the B, Al, and Ga compounds are obtained from G2 predictions, while those for the In compounds are obtained from CCSD(T)/CBS calculations; these are the most accurate calculations for indium-containing compounds published to date. In most cases, the calculated thermochemistry is in good agreement with published values derived from experiments for those species that have well-established heats of formation. Bond energies obtained from the heats of formation follow the expected trend (Cl much greater than CH3 approx. H). However, the CH3M-(CH3)2 bond energies obtained for trimethylgallium and trimethylindium are considerably stronger (greater than 15 kcal/mol) than currently accepted values.

  17. Kinetics of the Formation of Intercalation Compounds in Crystalline Graphite

    NASA Technical Reports Server (NTRS)

    Sharma, P. K.; Hickey, G. S.

    1995-01-01

    Crystalline graphite has a structure that can be best described as an ordered stack of flat aromatic layers. It is known to form intercalation compounds with bromine and nitric acid. Their formation was studied using thermal measurements and analytical techniques. Samples of graphite treated with either bromine or nitric acid were prepared by contacting these reagents with powdered graphite.

  18. Weldability of intermetallic alloys

    SciTech Connect

    David, S.A. )

    1990-01-01

    Ordered intermetallic alloys are a unique class of material that have potential for structural applications at elevated temperatures. The paper describes the welding and weldability of these alloys. The alloys studied were nickel aluminide (Ni[sub 3]Al), titanium aluminide (Ti[sub 3]Al), and iron aluminide.

  19. Erosion of a TiAl intermetallic alloy under conditions simulating plasma disruptions

    NASA Astrophysics Data System (ADS)

    Kalin, B. A.; Yakushin, V. L.; Polsky, V. I.; Dzhumaev, P. S.; Fedotov, V. T.; Sevryukov, O. N.; Golikov, M. Yu.; Zolotarev, M. V.

    2009-04-01

    Radiation erosion and thermal stability of TiAl-based intermetallic alloys produced by vacuum-arc melting, compacting of microcrystal powders with binder and impregnantion by melt, and their brazed joints with bronze have been investigated under irradiation by high-temperature pulsed hydrogen plasma flows (the flow energy density Q = 0.2-0.9 MJ/m 2, the pulse duration 15 μs, the number of pulses 1-21) which simulate the expected plasma disruptions in a fusion reactor. It has been found that the erosion coefficients and thermal stability of alloys are determined by the way of their fabrication, and compacted intermetallides have a higher thermal stability in comparison with the cast ones. The brazed joints of the intermetallic compound with bronze under irradiation by pulsed hydrogen plasma up to the energy density Q = 0.75 MJ/m 2 have a high thermal stability and formation of cracks was not observed.

  20. Vacancy formation and extraction energies in semiconductor compounds and alloys

    NASA Technical Reports Server (NTRS)

    Berding, M. A.; Sher, A.; Chen, A.-B.

    1990-01-01

    A model for calculating the extraction energies and vacancy-formation energies in diamond-cubic and zinc-blende semiconductors is developed on the basis of Harrison's (1980, 1983) tight-binding theory. The extraction energies provide a reference from which other final states of the removed atoms can be calculated. The results of calculations show that, in a given compound, the calculated extraction energies are larger for the anion than for the cation, with the difference between the cation and the anion being larger in the II-VI than in the III-V compounds. This is in agreement with experimental results.

  1. Short-range order of undercooled melts of PdZr2 intermetallic compound studied by X-ray and neutron scattering experiments

    NASA Astrophysics Data System (ADS)

    Klein, S.; Holland-Moritz, D.; Herlach, D. M.; Mauro, N. A.; Kelton, K. F.

    2013-05-01

    The short-range order in undercooled melts of the intermetallic Zr2Pd glass-forming alloy is investigated by combining electrostatic levitation (ESL) with high-energy X-ray diffraction and neutron diffraction. Experimentally determined structure factors are measured and analyzed with respect to various structures of short-range order. The comparative X-ray and neutron scattering experiments allow for investigations of topological and chemical short-range order. Based on these studies, no preference of a specific short-range order is found for the liquid Zr2Pd glass-forming alloy, even in the metastable state of the deeply undercooled melt. This is in agreement with an earlier report from X-ray diffraction and molecular-dynamics studies of a Zr75.5Pd24.5 liquid, which showed a broad distribution of cluster types. The results for the Zr2Pd liquid are discussed with respect to the glass-forming ability of this melt.

  2. Effects of Annealing, Thermomigration, and Electromigration on the Intermetallic Compounds Growth Kinetics of Cu/Sn-2.5Ag Microbump.

    PubMed

    Kim, Seung-Hyun; Park, Gyu-Tae; Park, Jong-Jin; Park, Young-Bae

    2015-11-01

    The effects of annealing, thermomigration (TM), and electromigration (EM) on the intermetallic com- pound (IMC) growth kinetics of Cu/Sn-2.5Ag microbumps were investigated using in-situ scanning electron microscopy at 120-165 degrees C with a current density of 1.5 x 10(5) A/cm2. The IMC growth kinetics was controlled by a diffusion-dominant mechanism and a chemical-reaction-dominant mechanism with annealing and current-stressing conditions, respectively. Before all of the Sn was fully transformed into IMCs, the activation energies of the Cu3Sn IMCs were 0.54 eV, 0.50 eV, and 0.40 eV for annealing, TM, and EM, respectively, which is closely related to the acceleration effect of the interfacial reaction by electron wind force under current stressing. After all of the Sn was fully transformed into IMCs by reacting with Cu, the Cu3Sn IMC growth rates of the three structures became similar due to the reduced and similar diffusion rates inside the IMCs with and without current stressing.

  3. Investigation of nitrogenous compound formation in biomass gasification

    SciTech Connect

    Ishimura, D.M.; Masutani, S.M.; Kinoshita, C.M.

    1994-12-31

    Gasification of high nitrogen content biomass can produce large quantities of nitrogenous compounds that pose potential risks to the environment and human health, and can compromise the performance of related energy conversion processes. Few studies of nitrogenous compound formation in gasification have been reported and little is known about the evolution of fuel-bound nitrogen from biomass fuels. To address these deficiencies, Leucaena, a nitrogen-fixing tree and possible energy crop with 2-3% nitrogen content, was gasified in a bench-scale, indirectly-heated, fluidized bed gasifier to determine the effects of operating conditions on nitrogeneous compound formation. Gas chromatography, and ion-selective electrode and chemiluminescence analyzers were used to measure concentrations of major gas species (e.g., CO, CO{sub 2}, H{sub 2}, CH{sub 4}, and N{sub 2}), NH{sub 3}, HCN, NO{sub x}, and nitrogeneous tar species as functions of gasifier temperature (700{degrees}C to 900{degrees}C), equivalence ration (0.2 to 0.4), and residence time (2.3 to 6.7 s). Nitrogeneous compounds were inventoried, and fundamental conclusions, based on the findings of these tests, are proposed.

  4. Integrating giant microwave absorption with magnetic refrigeration in one multifunctional intermetallic compound of LaFe11.6Si1.4C0.2H1.7

    PubMed Central

    Song, Ning-Ning; Ke, Ya-Jiao; Yang, Hai-Tao; Zhang, Hu; Zhang, Xiang-Qun; Shen, Bao-Gen; Cheng, Zhao-Hua

    2013-01-01

    Both microwave absorption and magnetocaloric effect (MCE) are two essential performances of magnetic materials. We observe that LaFe11.6Si1.4C0.2H1.7 intermetallic compound exhibits the advantages of both giant microwave absorption exceeding −42 dB and magnetic entropy change of −20 Jkg−1K−1. The excellent electromagnetic wave absorption results from the large magnetic loss and dielectric loss as well as the efficient complementarity between relative permittivity and permeability. The giant MCE effect in this material provides an ideal technique for cooling the MAMs to avoid temperature increase and infrared radiation during microwave absorption. Our finding suggests that we can integrate the giant microwave absorption with magnetic refrigeration in one multifunctional material. This integration not only advances our understanding of the correlation between microwave absorption and MCE, but also can open a new avenue to exploit microwave devices and electromagnetic stealth. PMID:23887357

  5. Theoretics-directed effect of copper or aluminum content on the ductility characteristics of Al-based (Al3Ti, AlTi, AlCu, AlTiCu2) intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Li, Yong; Ma, Xiao-Juan; Liu, Qi-Jun; Kong, Ge-Xing; Ma, Hai-Xia; Wang, Wen-Peng; Wang, Yi-Gao; Jiao, Zhen; Liu, Fu-Sheng; Liu, Zheng-Tang

    2016-11-01

    First-principle simulations have been applied to investigate the effect of copper (Cu) or aluminum (Al) content on the ductility of Al3Ti, AlTi, AlCu, and AlTiCu2 alloys. The mechanical stable and elastic properties of Al-based intermetallic compounds are researched by density functional theory with the generalized gradient approximation (DFT-GGA). The calculated lattice constants are in conformity with the previous experimental and theoretical data. The deduced elastic constants show that the investigated Al3Ti, AlTi, AlCu, and AlTiCu2 structures are mechanically stable. Shear modulus, Young’s modulus, Poisson’s ratio, and the ratio B/G have also been figured out by using reckoned elastic constants. A further analysis of Young’s modulus and Poisson’s ratio reveals that the third added element copper content has significant effects on the Al-Ti-based ICs ductile character. Project supported by the National Natural Science Foundation of China (Grant Nos. 41674088, 11574254, 11272296, and 11547311), the National Basic Research Program of China (Grant No. 2011CB808201), the Fundamental Research Fund for the Central Universities, China (Grant Nos. 2682014ZT30 and 2682014ZT31), and the Fund of the State Key Laboratory of Solidification Processing in Northwestern Polytechnical University, China (Grant No. SKLSP201511).

  6. Recent advances in ordered intermetallics

    SciTech Connect

    Liu, C.T.

    1992-12-31

    This paper briefly summarizes recent advances in intermetallic research and development. Ordered intermetallics based on aluminides and silicides possess attractive properties for structural applications at elevated temperatures in hostile environments; however, brittle fracture and poor fracture resistance limit their use as engineering materials in many cases. In recent years, considerable efforts have been devoted to the study of the brittle fracture behavior of intermetallic alloys; as a result, both intrinsic and extrinsic factors governing brittle fracture have been identified. Recent advances in first-principles calculations and atomistic simulations further help us in understanding atomic bonding, dislocation configuration, and alloying effects in intermetallics. The basic understanding has led to the development of nickel, iron, and titanium aluminide alloys with improved mechanical and metallurgical properties for structural use. Industrial interest in ductile intermetallic alloys is high, and several examples of industrial involvement are mentioned.

  7. Recent advances in ordered intermetallics

    SciTech Connect

    Liu, C.T.

    1994-12-31

    Ordered intermetallic alloys based on aluminides and silicides offer many advantages for structural use at high temperatures in hostile environments. Attractive properties include excellent oxidation and corrosion resistance, light weight, and superior strength at high temperatures. The major concern for structural use of intermetallics was their low ductility and poor fracture resistance at ambient temperatures. For the past 10 years, considerable effort was devoted to R&D of ordered intermetallic alloys, and progress has been made on understanding intrinsic and extrinsic factors controlling brittle fracture in intermetallic alloys based on aluminides and silicides. Parallel effort on alloy design has led to the development of a number of ductile and strong intermetallic alloys based on Ni{sub 3}Al, NiAl, Fe{sub 3}Al, FeAl, Ti{sub 3}Al, and TiAl systems for structural applications.

  8. Food volatile compounds facilitating HII mesophase formation: solubilization and stability.

    PubMed

    Amar-Zrihen, Natali; Aserin, Abraham; Garti, Nissim

    2011-05-25

    Four lipophilic food volatile molecules of different chemical characteristics, phenylacetaldehyde, 2,6-dimethyl-5-heptenal, linalool, and trans-4-decenal, were solubilized into binary mixtures of monoolein/water, facilitating the formation of reverse hexagonal (H(II)) mesophases at room temperature without the need of solvents or triglycerides. Some of the flavor compounds are important building blocks of the hexagonal mesostructure, preventing phase transition with aging. The solubilization loads were relatively high: 12.6, 10.0, 12.6, and 10.0 wt % for phenylacetaldehyde, 2,6-dimethyl-5-heptenal, linalool, and trans-4-decenal, respectively. Phenylacetaldehyde formed mixtures of lamellar and cubic phases. Linalool, 2,6-dimethyl-5-heptenal, and trans-4-decenal induced structural shift from lamellar directly to H(II) mesophase, remaining stable at room temperature. Lattice parameters were found to increase with water content and to decrease with temperature and/or food volatile content. trans-4-Decenal produces more stable H(II) mesophase compared to linalool-loaded mesophase. At 40-60 °C, depending on the chemical structure and on the solubilization location of the food volatile compounds, the H(II) mesophase transforms to isotropic micellar phase, facilitating the release of the food volatile compounds. Molecular interactions suggest the existence of two consecutive stages in the solubilization process.

  9. Calculations of the magnetic properties of R2M14B intermetallic compounds (R=rare earth, M=Fe, Co)

    NASA Astrophysics Data System (ADS)

    Ito, Masaaki; Yano, Masao; Dempsey, Nora M.; Givord, Dominique

    2016-02-01

    The hard magnetic properties of "R-M-B" (R=rare earth, M=mainly Fe) magnets derive from the specific intrinsic magnetic properties encountered in Fe-rich R2M14B compounds. Exchange interactions are dominated by the 3d elements, Fe and Co, and may be modeled at the macroscopic scale with good accuracy. Based on classical formulae that relate the anisotropy coefficients to the crystalline electric field parameters and exchange interactions, a simple numerical approach is used to derive the temperature dependence of anisotropy in various R2Fe14B compounds (R=Pr, Nd, Dy). Remarkably, a unique set of crystal field parameters give fair agreement with the experimentally measured properties of all compounds. This implies reciprocally that the properties of compounds that incorporate a mixture of different rare-earth elements may be predicted accurately. This is of special interest for material optimization that often involves the partial replacement of Nd with another R element and also the substitution of Co for Fe.

  10. Intermetallic compounds of the heaviest elements and their homologs: The electronic structure and bonding of MM', where M =Ge, Sn, Pb, and element 114, and M'=Ni, Pd, Pt, Cu, Ag, Au, Sn, Pb, and element 114

    NASA Astrophysics Data System (ADS)

    Pershina, V.; Anton, J.; Fricke, B.

    2007-10-01

    Fully relativistic (four-component) density-functional theory calculations were performed for intermetallic dimers MM', where M =Ge, Sn, Pb, and element 114, and M'=group 10 elements (Ni, Pd, and Pt) and group 11 elements (Cu, Ag, and Au). PbM and 114M, where M are group 14 elements, were also considered. The results have shown that trends in spectroscopic properties—atomization energies De, vibrational frequencies ωe, and bond lengths Re, as a function of M', are similar for compounds of Ge, Sn, Pb, and element 114, except for De of PbNi and 114Ni. They were shown to be determined by trends in the energies and space distribution of the valence ns(M ') atomic orbitals (AOs). According to the results, element 114 should form the weakest bonding with Ni and Ag, while the strongest with Pt due to the largest involvement of the 5d(Pt) AOs. In turn, trends in the spectroscopic properties of MM' as a function of M were shown to be determined by the behavior of the np1/2(M ) AOs. Overall, De of the element 114 dimers are about 1eV smaller and Re are about 0.2a.u. larger than those of the corresponding Pb compounds. Such a decrease in bonding of the element 114 dimers is caused by the large SO splitting of the 7p orbitals and a decreasing contribution of the relativistically stabilized 7p1/2(114) AO. On the basis of the calculated De for the dimers, adsorption enthalpies of element 114 on the corresponding metal surfaces were estimated: They were shown to be about 100-150kJ/mol smaller than those of Pb.

  11. CROSS-DISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY: Structural Feature and Solute Trapping of Rapidly Grown Ni3Sn Intermetallic Compound

    NASA Astrophysics Data System (ADS)

    Qin, Hai-Yan; Wang, Wei-Li; Wei, Bing-Bo

    2009-11-01

    The rapid dendritic growth of primary Ni3Sn phase in undercooled Ni-30.9%Sn-5%Ge alloy is investigated by using the glass fluxing technique. The dendritic growth velocity of Ni3Sn compound is measured as a function of undercooling, and a velocity of 2.47 m/s is achieved at the maximum undercooling of 251 K (0.17TL). The addition of the Ge element reduces its growth velocity as compared with the binary Ni75Sn25 alloy. During rapid solidification, the Ni3Sn compound behaves like a normal solid solution and it displays a morphological transition of “coarse dendrite-equiaxed grain-vermicular structure" with the increase of undercooling. Significant solute trapping of Ge atoms occurs in the whole undercooling range.

  12. The structural, elastic and optical properties of ScM (M = Rh, Cu, Ag, Hg) intermetallic compounds under pressure by ab initio simulations

    NASA Astrophysics Data System (ADS)

    Ali, Md. Lokman; Rahaman, Md. Zahidur; Rahman, Md. Atikur

    2016-11-01

    The influence of pressure on the structural and elastic properties of ScM (M = Rh, Cu, Ag, Hg) compounds has been investigated by using ab initio approach pseudopotential plane-wave method based on the density functional theory within the generalized gradient approximation (GGA). The optical properties have been investigated under zero pressure. It is found that the optimized lattice parameters for all metals are in good agreement with the experimental data and other available theoretical values. We obtained three independent elastic constants Cij (C11,C12 and C44) and various elastic parameters such as bulk modulus B, shear modulus G, Young’s modulus E,B/G, Poisson’s ratio ν and anisotropy factor A as a function of pressure. In addition, the mechanical stability and ductile/brittle nature are also investigated from the calculated elastic constants. The study of optical properties reveals that all of these compounds possess good absorption coefficient in the high energy region and the refractive index of all these compounds is higher in the low energy region and gradually decreased in the high energy region. All these calculations have been carried out using the CASTEP computer code.

  13. Photoinduced formation of N2 molecules in ammonium compounds.

    PubMed

    Aziz, Emad F; Gråsjö, Johan; Forsberg, Johan; Andersson, Egil; Söderström, Johan; Duda, Laurent; Zhang, Wenhua; Yang, Jinglong; Eisebitt, Stefan; Bergström, Christel; Luo, Yi; Nordgren, Joseph; Eberhardt, Wolfgang; Rubensson, Jan-Erik

    2007-10-04

    Via fluorescence yield (FY) and resonant inelastic scattering spectroscopy in the soft X-ray range we find that soft X-rays induce formation of N2 molecules in solid NH4Cl and in related compounds. The nitrogen molecules form weak bonds in NH4Cl, so that a substantial fraction of the molecules remains in the sample. From measurements of the FY as a function of exposure and temperature, the rates for the photochemical processes are estimated. At elevated temperatures (363 K), several nitrogen atoms are removed from the sample per incoming photon. At lower temperatures (233 K), the rate is reduced to around 0.02 nitrogen atoms for each incoming photon. Virtually all these atoms form N2 molecules which are bound in the sample. The generality and implications of these results are briefly discussed.

  14. Formation of xenon-nitrogen compounds at high pressure

    PubMed Central

    Howie, Ross T.; Turnbull, Robin; Binns, Jack; Frost, Mungo; Dalladay-Simpson, Philip; Gregoryanz, Eugene

    2016-01-01

    Molecular nitrogen exhibits one of the strongest known interatomic bonds, while xenon possesses a closed-shell electronic structure: a direct consequence of which renders both chemically unreactive. Through a series of optical spectroscopy and x-ray diffraction experiments, we demonstrate the formation of a novel van der Waals compound formed from binary Xe-N2 mixtures at pressures as low as 5 GPa. At 300 K and 5 GPa Xe(N2)2-I is synthesised, and if further compressed, undergoes a transition to a tetragonal Xe(N2)2-II phase at 14 GPa; this phase appears to be unexpectedly stable at least up to 180 GPa even after heating to above 2000 K. Raman spectroscopy measurements indicate a distinct weakening of the intramolecular bond of the nitrogen molecule above 60 GPa, while transmission measurements in the visible and mid-infrared regime suggest the metallisation of the compound at ~100 GPa. PMID:27748357

  15. Formation of volatile sulfur compounds and metabolism of methionine and other sulfur compounds in fermented food.

    PubMed

    Landaud, Sophie; Helinck, Sandra; Bonnarme, Pascal

    2008-01-01

    The formation of volatile sulfur compounds (VSC) in fermented food is a subject of interest. Such compounds are essential for the aroma of many food products like cheeses or fermented beverages, in which they can play an attractive or a repulsive role, depending on their identity and their concentration. VSC essentially arise from common sulfur-bearing precursors, methionine being the most commonly found. In the first section of this paper, the main VSC found in cheese, wine, and beer are reviewed. It is shown that a wide variety of VSC has been evidenced in these food products. Because of their low odor threshold and flavor notes, these compounds impart essential sensorial properties to the final product. In the second section of this review, the main (bio)chemical pathways leading to VSC synthesis are presented. Attention is focused on the microbial/enzymatic phenomena-which initiate sulfur bearing precursors degradation-leading to VSC production. Although chemical reactions could also play an important role in this process, this aspect is not fully developed in our review. The main catabolic pathways leading to VSC from the precursor methionine are presented.

  16. Compound eye formation in the termite Incisitermes minor (Isoptera: Kalotermitidae).

    PubMed

    Rose, Taylor C; Ediger, Emily F; Lehman-Schletewitz, Joy; McClane, Nathan W; Schweigert, Kristen C; Alzweideh, Saif; Wadsworth, Lauren; Husseneder, Claudia; Morris, Joshua W; Ziesmann, Jurgen

    2015-07-01

    The postembryonic development and caste differentiation patterns of lower termites have been described multiple times in a variety of different species. However, most of these studies focused on gross ontogeny, without carefully describing the maturation of any particular organ or organ system. The few studies that have attempted to correlate caste development and organ differentiation have produced somewhat inconsistent results, especially in the area of eye formation. Therefore, in order to help further elucidate the relationship between eye formation and postembryonic differentiation in lower termites, we studied eye development in the termite, Incisitermes minor (Hagen). Eye formation in I. minor began in the earliest larvae, with only an eye primordium. However, in all later larval stages, characteristic eye structures were observed and were shown to progressively differentiate through larval and nymphal stages. Curiously, pigmentation began with three to eight groups of cells in early larvae and the number of these pigmented groups increased along the developmental time course. Ultimately, a uniformly pigmented eye area was formed by the early nymphal stage. The overall eye area also gradually increased along with normal caste development, but the characteristic lenses seen in a prototypical insect compound eye did not completely form until after the final nymphal stage. Electrophysiological measurements provided clear evidence that eyes were indeed functional at all stages of development where pigment was present. Based upon this data, the eye development pattern in I. minor appeared to follow a divergent pathway from holometabolous insects and an intermediate pathway between typical hemimetabolous eye development and the heterochronic shift observed in other termite species.

  17. Large magnetocaloric effect and near-zero thermal hysteresis in the rare earth intermetallic Tb1-x Dy x Co2 compounds

    NASA Astrophysics Data System (ADS)

    Zeng, Yuyang; Tian, Fanghua; Chang, Tieyan; Chen, Kaiyun; Yang, Sen; Cao, Kaiyan; Zhou, Chao; Song, Xiaoping

    2017-02-01

    We report the magnetocaloric effect in a Tb1-x Dy x Co2 compound which exhibits a wide working temperature window around the Curie temperature (T C) and delivers a large refrigerant capacity (RC) with near-zero thermal hysteresis. Specifically, the wide full width at half maxima ({δ\\text{WFHM}} ) can reach up to 62 K and the RC value changes from 216.5 to 274.3 J Kg-1 when the external magnetic field increases to 5 T. Such magnetocaloric effects are attributed to a magnetic and structural transition from a paramagnetic and cubic phase to a ferromagnetic (M S along [1 1 1] direction) and rhombohedral phase or ferromagnetic (M S along [0 0 1] direction) and tetragonal phase.

  18. Magnetic behavior of the neptunium intermetallic compound NpCo2Si2 under high pressure: A Mössbauer study

    NASA Astrophysics Data System (ADS)

    Potzel, W.; Moser, J.; Kalvius, G. M.; de Novion, C. H.; Spirlet, J. C.; Gal, J.

    1981-12-01

    High-pressure Mössbauer studies of 237Np in the tetragonal compound NpCo2Si2 are reported. The pressure dependence of the hyperfine field (Beff), the isomer shift (S), and the Néel temperature (TN) have been measured for pressures up to 35 kbar, at temperatures from 1.4 to 77 K. While Beff remains constant, both S and TN change markedly. The constancy of Beff fits well into the picture of localized 5f moments. The variation of TN is treated within the rigidspin model of Ruderman, Kittel, and Arrott. The prediction of a linear relation between T12N and S is consistent with the reported results.

  19. Crystal structure and magnetic properties of new Fe3Co3 X 2 (X  =  Ti, Nb) intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Zhang, Jie; Nguyen, Manh Cuong; Balasubramanian, Balamurugan; Das, Bhaskar; Sellmyer, David J.; Zeng, Zhi; Ho, Kai-Ming; Wang, Cai-Zhuang

    2016-05-01

    The structure and magnetic properties of new magnetic Fe3Co3 X 2 (X  =  Ti, Nb) compounds are studied by genetic algorithm, first-principles density functional theory (DFT) calculations, and experiments. The atomic structure of a hexagonal structure with P-6m2 symmetry is determined. The simulated x-ray diffraction (XRD) spectra of the P-6m2 structures agree well with experimental XRD data for both Fe3Co3Ti2 and Fe3Co3Nb2. The magnetic properties of these structures as well as the effect of the disorder of Fe and Co on their magnetic properties are also investigated. The magnetocrystalline anisotropy energy is found to be very sensitive to the occupancy disorder between Fe and Co.

  20. New icosahedral nanoclusters in crystal structures of intermetallic compounds: Topological types of 50-atom deltahedra D50 in samson phases β-Mg2Al3 and ɛ-Mg23Al30

    NASA Astrophysics Data System (ADS)

    Blatov, V. A.; Ilyushin, G. D.

    2012-12-01

    A database of intermetallic compounds has been compiled using the TOPOS program package. This database includes 514 topological types, containing 12- and 13-atom icosahedral i clusters. An isolated group of 1649 i clusters is described by 14 point groups and their maximum symmetry D 3 d (bar 3 m) and T h ( m bar 3) is established, respectively, in 47 and 25 types of crystal structures. A structural analysis of the outer quasispherical shells showed that local 63-atom i configurations 1@12@50, which contain 50 atoms in the second layer, are implemented in 8 out of 19 cases. Examples of new topologically different types of 50-atom D50 deltahedra in the Samson phases ɛ-Mg23Al30 and β-Mg2Al3 are presented. Four topologically different sites with coordination numbers of 5, 6, 6, or 7 are established in the ɛ shell and seven sites with coordination numbers of 5, 5, 6, 6, 6, 6, or 7 are found in the β shell. The inner i clusters for the β-Mg2Al3 structure (with the symmetry bar 3 m) and the ɛ-Mg23Al30 structure (with the symmetry bar 3) have a similar chemical composition, i.e., Mg7Al6 and Mg6Al7, and their 50-atom shells are chemically identical to 18Mg + 32Al. The configurations found supplement the series of known two-layer icosahedral Bergman and Mackay clusters in the form of deltahedra with 32- and 42-atom shells.

  1. Undercooling Behavior and Intermetallic Compound Coalescence in Microscale Sn-3.0Ag-0.5Cu Solder Balls and Sn-3.0Ag-0.5Cu/Cu Joints

    NASA Astrophysics Data System (ADS)

    Zhou, M. B.; Ma, X.; Zhang, X. P.

    2012-11-01

    The microstructure of microscale solder interconnects and soldering defects have long been known to have a significant influence on the reliability of electronic packaging, and both are directly related to the solidification behavior of the undercooled solder. In this study, the undercooling behavior and solidification microstructural evolution of Sn-3.0Ag-0.5Cu solder balls with different diameters (0.76 mm, 0.50 mm, and 0.30 mm) and the joints formed by soldering these balls on Cu open pads of two diameters (0.48 mm and 0.32 mm) on a printed circuit board (PCB) substrate were characterized by differential scanning calorimetry (DSC) incorporated into the reflow process. Results show that the decrease in diameter of the solder balls leads to an obvious increase in the undercooling of the balls, while the undercooling of the solder joints shows a dependence on both the diameter of the solder balls and the diameter ratio of solder ball to Cu pad (i.e., D s/ D p), and the diameter of the solder balls has a stronger influence on the undercooling of the joints than the dimension of the Cu pad. Coarse primary intermetallic compound (IMC) solidification phases were formed in the smaller solder balls and joints. The bulk Ag3Sn IMC is the primary solidification phase in the as-reflowed solder balls. Due to the interfacial reaction and dissolution of Cu atoms into the solder matrix, the primary Ag3Sn phase can be suppressed and the bulk Cu6Sn5 IMC is the only primary solidification phase in the as-reflowed solder joints.

  2. Determination of the intersublattice exchange interactions in GdCo12-xFexB6 (x = 0-3) intermetallic compounds by high field magnetization measurements

    NASA Astrophysics Data System (ADS)

    Diop, L. V. B.; Isnard, O.; Skourski, Y.; Ballon, G.

    2013-05-01

    High field magnetization measurements up to 60 T on free powder samples from GdCo12-xFexB6 (x = 0-3) compounds are reported. The data were used to evaluate the microscopic exchange interaction integral, JGd-3d, between Gd and 3d (Co,Fe) spins. The systems are ferrimagnets; they order magnetically between TC = 95 K for x = 3 and TC = 165 K for x = 0. The low temperature magnetization curves as well as the temperature dependence of intrinsic magnetic parameters are determined by magnetic measurements in pulsed magnetic field. The average magnetic moment ⟨μCo+Fe⟩ per mean transition metal atom (Co + Fe) is small and increases with increasing Fe concentration from 0.44 μΒ for x = 0 to 0.51 μΒ for x = 3 at T = 4 K. From high field magnetization curves, a value of JGd-3d/kB = -4.65 K is derived for x = 0, whereas mean field approximation yields a much larger 3d-3d exchange integral of JCo-Co/kB = 105 K. The obtained results reveal an increase of -JGd-3d/kB with Fe concentration. For x = 0.5, the intersublattice coefficient nGd-3d is found to keep an almost constant value of 5.87 ± 0.13 T*f.u.*μB-1 whatever the temperature in the 2 to 60 K range.

  3. Synthesis, structure, and bonding in K12Au21Sn4. A polar intermetallic compound with dense Au20 and open AuSn4 layers

    SciTech Connect

    Li, Bin; Kim, Sung-Jin; Miller, Gordon J.; and Corbett, John D.

    2009-10-29

    The new phase K{sub 12}Au{sub 21}Sn{sub 4} has been synthesized by direct reaction of the elements at elevated temperatures. Single crystal X-ray diffraction established its orthorhombic structure, space group Pmmn (No. 59), a = 12.162(2); b = 18.058(4); c = 8.657(2) {angstrom}, V = 1901.3(7) {angstrom}{sup 3}, and Z = 2. The structure consists of infinite puckered sheets of vertex-sharing gold tetrahedra (Au{sub 20}) that are tied together by thin layers of alternating four-bonded-Sn and -Au atoms (AuSn{sub 4}). Remarkably, the dense but electron-poorer blocks of Au tetrahedra coexist with more open and saturated Au-Sn layers, which are fragments of a zinc blende type structure that maximize tetrahedral heteroatomic bonding outside of the network of gold tetrahedra. LMTO band structure calculations reveal metallic properties and a pseudogap at 256 valence electrons per formula unit, only three electrons fewer than in the title compound and at a point at which strong Au-Sn bonding is optimized. Additionally, the tight coordination of the Au framework atoms by K plays an important bonding role: each Au tetrahedra has 10 K neighbors and each K atom has 8-12 Au contacts. The appreciably different role of the p element Sn in this structure from that in the triel members in K{sub 3}Au{sub 5}In and Rb{sub 2}Au{sub 3}Tl appears to arise from its higher electron count which leads to better p-bonding (valence electron concentrations = 1.32 versus 1.22).

  4. First-principles investigation of the structural stability and electronic properties of Pd doped monoclinic Cu6Sn5 intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Shao, Wei-Quan; Lu, Wen-Cai; Chen, Sha-Ou

    2014-12-01

    Tri-layer Au/Pd/Ni(P) films have been widely used as surface finish over the Cu pads in high-end packaging applications. It was found that a thin (Cu,Pd)6Sn5 IMC layer was beneficial in effective reducing inter-diffusion between a Cu substrate and a solder, and therefore the growth of the IMC layer and the EM (electromigration) processes. In this study, the structural properties and phase stability of monoclinic Cu6Sn5-based structures with Pd substitutions were studied by using the first-principles method. The (Cu,Pd)6Sn5 structure with the 4e site substituted by Pd has the lowest heat of formation and is the most stable among (Cu,Pd)6Sn5 structures. Hybridization of Pd-d and Sn-p states is a dominant factor for stability improvement. Moreover, Pd atoms concentration corresponding to the most stable structure of (Cu,Pd)6Sn5 was found to be 1.69 %, which is consistent with the experimental results.

  5. High-resolution mass spectrometry of nitrogenous compounds of the Colorado Green River formation oil shale.

    NASA Technical Reports Server (NTRS)

    Simoneit, B. R.; Schnoes, H. K.; Haug, P.; Burlingame, A. L.

    1971-01-01

    Basic nitrogenous compounds isolated from extracts of Green River Formation oil shale were analyzed. The major homologous constituents found were the compositional types - namely, quinolines, tetrahydrequinolines with minor amounts of pyridines and indoles series and traces of more aromatized nitrogen compounds. These results are correlated with nitrogen compounds isolated from Green River Formation retort oil and are a survey of the unaltered nitrogen compounds indigeneous to the shale.

  6. Ultrahigh temperature intermetallic alloys

    SciTech Connect

    Brady, M.P.; Zhu, J.H.; Liu, C.T.; Tortorelli, P.F.; Wright, J.L.; Carmichael, C.A.

    1998-11-01

    A new family of Cr-Cr{sub 2}Ta intermetallic alloys based on Cr-(6--10)Ta (at.%) is under development for structural use in oxidizing environments in the 1,000-1,300 C (1,832--2,372 F) temperature range. Development objectives relate to high temperature strength and oxidation resistance and room temperature fracture toughness. The 1,200 C (2,192 F) strength goals have been met: yield and fracture strengths of 275 MPa (40 ksi) and 345 MPa (50 ksi), respectively, were achieved. Progress in attaining reasonable fracture toughness of Cr-Cr{sub 2}Ta alloys has been made; current alloys exhibit room-temperature values of about 10--12 MPa{radical}m (1.1 MPa{radical}m = 1 ksi{radical}in.). Oxidation rates of these alloys at 950 C (1,742 F) in air are in the range of those reported for chromia-forming alloys. At 1,100 C (2,012 F) in air, chromia volatility was significant but, nevertheless, no scale spallation and positive weight gains of 1--5 mg/cm{sup 2} have been observed during 120-h, 6-cycle oxidation screening tests. These mechanical and oxidative properties represent substantial improvement over Cr-Cr{sub 2}Nb and Cr-Cr{sub 2}Zr alloys previously developed.

  7. Intermetallic insertion anodes for lithium batteries.

    SciTech Connect

    Thackeray, M. M.; Vaughey, J.; Johnson, C. S.; Kepler, K. D.

    1999-11-12

    Binary intermetallic compounds containing lithium, or lithium alloys, such as Li{sub x}Al, Li{sub x}Si and Li{sub x}Sn have been investigated in detail in the past as negative electrode materials for rechargeable lithium batteries. It is generally acknowledged that the major limitation of these systems is the large volumetric expansion that occurs when lithium reacts with the host metal. Such large increases in volume limit the practical use of lithium-tin electrodes in electrochemical cells. It is generally recognized that metal oxide electrodes, MO{sub y}, in lithium-ion cells operate during charge and discharge by means of a reversible lithium insertion/extraction process, and that the cells offer excellent cycling behavior when the crystallographic changes to the unit cell parameters and unit cell volume of the Li{sub x}MO{sub y} electrode are kept to a minimum. An excellent example of such an electrode is the spinel Li{sub 4}Ti{sub 5}O{sub 12}, which maintains its cubic symmetry without any significant change to the lattice parameter (and hence unit cell volume) during lithium insertion to the rock-salt composition Li{sub 7}Ti{sub 5}O{sub 12}. This spinel electrode is an example of a ternary Li{sub x}MO{sub y} system in which a binary MO{sub y} framework provides a stable host structure for lithium. With this approach, the authors have turned their attention to exploring ternary intermetallic systems Li{sub x}MM{prime} in the hope of finding a system that is not subject to the high volumetric expansion that typifies many binary systems. In this paper, the authors present recent data of their investigations of lithium-copper-tin and lithium-indium-antimonide electrodes in lithium cells. The data show that lithium can be inserted reversibly into selected intermetallic compounds with relatively small expansion of the lithiated intermetallic structures.

  8. Phase equilibria, formation, crystal and electronic structure of ternary compounds in Ti-Ni-Sn and Ti-Ni-Sb ternary systems

    SciTech Connect

    Romaka, V.V.; Rogl, P.; Romaka, L.; Stadnyk, Yu.; Melnychenko, N.; Grytsiv, A.; Falmbigl, M.; Skryabina, N.

    2013-01-15

    The phase equilibria of the Ti-Ni-Sn and Ti-Ni-Sb ternary systems have been studied in the whole concentration range by means of X-ray and EPM analyses at 1073 K and 873 K, respectively. Four ternary intermetallic compounds TiNiSn (MgAgAs-type), TiNi{sub 2-x}Sn (MnCu{sub 2}Al-type), Ti{sub 2}Ni{sub 2}Sn (U{sub 2}Pt{sub 2}Sn-type), and Ti{sub 5}NiSn{sub 3} (Hf{sub 5}CuSn{sub 3}-type) are formed in Ti-Ni-Sn system at 1073 K. The TiNi{sub 2}Sn stannide is characterized by homogeneity in the range of 50-47 at% of Ni. The Ti-Ni-Sb ternary system at 873 K is characterized by formation of three ternary intermetallic compounds, Ti{sub 0.8}NiSb (MgAgAs-type), Ti{sub 5}Ni{sub 0.45}Sb{sub 2.55} (W{sub 5}Si{sub 3}-type), and Ti{sub 5}NiSb{sub 3} (Hf{sub 5}CuSn{sub 3}-type). The solubility of Ni in Ti{sub 0.8}NiSb decreases number of vacancies in Ti site up to Ti{sub 0.91}Ni{sub 1.1}Sb composition. - Graphical abstract: Isothermal section of the Ti-Ni-Sn phase diagram and DOS distribution in hypothetical TiNi{sub 1+x}Sn solid solution. Highlights: Black-Right-Pointing-Pointer Ti-Ni-Sn phase diagram was constructed at 1073 K. Black-Right-Pointing-Pointer Four ternary compounds are formed: TiNiSn, TiNi{sub 2-x}Sn, Ti{sub 2}Ni{sub 2}Sn, and Ti{sub 5}NiSn{sub 3}. Black-Right-Pointing-Pointer Three ternary compounds exist in Ti-Ni-Sb system at 873 K. Black-Right-Pointing-Pointer The TiNi{sub 2}Sb compound is absent.

  9. What Plurals and Compounds Reveal about Constraints in Word Formation

    ERIC Educational Resources Information Center

    Jaensch, Carol; Heyer, Vera; Gordon, Peter; Clahsen, Harald

    2014-01-01

    Morphological systems are constrained in how they interact with each other. One case that has been widely studied in the psycholinguistic literature is the avoidance of plurals inside compounds (e.g. *"rats eater" vs. "rat eater") in English and other languages, the so-called "plurals-in-compounds effect." Several…

  10. Multi-component intermetallic electrodes for lithium batteries

    DOEpatents

    Thackeray, Michael M; Trahey, Lynn; Vaughey, John T

    2015-03-10

    Multi-component intermetallic negative electrodes prepared by electrochemical deposition for non-aqueous lithium cells and batteries are disclosed. More specifically, the invention relates to composite intermetallic electrodes comprising two or more compounds containing metallic or metaloid elements, at least one element of which can react with lithium to form binary, ternary, quaternary or higher order compounds, these compounds being in combination with one or more other metals that are essentially inactive toward lithium and act predominantly, but not necessarily exclusively, to the electronic conductivity of, and as current collection agent for, the electrode. The invention relates more specifically to negative electrode materials that provide an operating potential between 0.05 and 2.0 V vs. metallic lithium.

  11. Intermetallic R-phase in maraging steels of the Fe-Cr-Ni-Co-Mo system

    NASA Astrophysics Data System (ADS)

    Tarasenko, L. V.; Titov, V. I.

    2006-07-01

    Concentration and temperature conditions of formation of intermetallic R-phase in margining steels of the Fe-Cr-Ni-Co-Mo system are studied with the help of methods of physicochemical phase analysis and x-ray diffraction analysis. The role of chemical elements in the formation of the multicomponent R-phase is determined. A hypothesis employing the Kasper dimensional principle is suggested for multicomponent intermetallics formed in steels.

  12. Fundamentals of mechanical behavior in structural intermetallics: A synthesis of atomistic and continuum modeling

    SciTech Connect

    Yoo, M.H.; Fu, C.L.

    1993-08-01

    After a brief account of the recent advances in computational research on mechanical behavior of structural intermetallics, currently unresolved problems and critical issues are addressed and the knowledge base for potential answers to these problems is discussed. As large-scale problems (e.g., dislocation core structures, grain boundaries, and crack tips) are treated by atomistic simulations, future development of relevant interatomic potentials should be made consistent with the results of first-principles calculations. The bulk and defect properties calculated for intermetallic compounds, both known and as yet untested, can furnish insights to alloy designers in search of new high-temperature structural intermetallics.

  13. Cold Sprayed Intermetallic Thermal Barrier Coatings

    NASA Astrophysics Data System (ADS)

    Leshchinsky, Evgeny

    Conventional thermal barrier coating (TBC) systems consist of a duplex structure with a metallic bond coat and a ceramic heat-isolative topcoat. Several recent research activities are concentrated on the development of improved multilayer bond coat and TBC materials. This study represents an investigation performed for the aluminum based bond coats, especially those with reduced thermal conductivities. Using alternative TBC materials, such as metal alloys and intermetallics, their processing methods can be further optimized to achieve the best thermal physical parameters. One example is the ten-layer system in which cold sprayed aluminum based intermetallics are synthesized. These systems demonstrated improved heat insulation and thermal fatigue capabilities compared to conventional TBC. The microstructures and properties of the laminar coatings were characterized by SEM, EDS, XRD; micromechanical and durability tests were performed to define the structure and coating formation mechanisms. Application prospects for HCCI engines are discussed. Fuel energy can be utilized more efficiently with the concept of low heat rejection engines with applied TBC.

  14. Structural plasticity: how intermetallics deform themselves in response to chemical pressure, and the complex structures that result.

    PubMed

    Berns, Veronica M; Fredrickson, Daniel C

    2014-10-06

    Interfaces between periodic domains play a crucial role in the properties of metallic materials, as is vividly illustrated by the way in which the familiar malleability of many metals arises from the formation and migration of dislocations. In complex intermetallics, such interfaces can occur as an integral part of the ground-state crystal structure, rather than as defects, resulting in such marvels as the NaCd2 structure (whose giant cubic unit cell contains more than 1000 atoms). However, the sources of the periodic interfaces in intermetallics remain mysterious, unlike the dislocations in simple metals, which can be associated with the exertion of physical stresses. In this Article, we propose and explore the concept of structural plasticity, the hypothesis that interfaces in complex intermetallic structures similarly result from stresses, but ones that are inherent in a defect-free parent structure, rather than being externally applied. Using DFT-chemical pressure analysis, we show how the complex structures of Ca2Ag7 (Yb2Ag7 type), Ca14Cd51 (Gd14Ag51 type), and the 1/1 Tsai-type quasicrystal approximant CaCd6 (YCd6 type) can all be traced to large negative pressures around the Ca atoms of a common progenitor structure, the CaCu5 type with its simple hexagonal 6-atom unit cell. Two structural paths are found by which the compounds provide relief to the Ca atoms' negative pressures: a Ca-rich pathway, where lower coordination numbers are achieved through defects eliminating transition metal (TM) atoms from the structure; and a TM-rich path, along which the addition of spacer Cd atoms provides the Ca coordination environments greater independence from each other as they contract. The common origins of these structures in the presence of stresses within a single parent structure highlights the diverse paths by which intermetallics can cope with competing interactions, and the role that structural plasticity may play in navigating this diversity.

  15. Systematics of Mössbauer hyperfine parameters in Np intermetallics

    NASA Astrophysics Data System (ADS)

    Kalvius, G. M.; Gal, J.; Asch, L.; Potzel, W.

    1992-05-01

    Data for intermetallic compounds of neptunium obtained with the 60 keV Mössbauer resonance of237Np are reviewed. Measurements of temperature, pressure and field dependencies are available. The main questions addressed are: (a) the degree of delocalization of 5f-electrons, (b) the formal charge state of Np, and (c) the influence of the ligand on the neptunium electronic structure. For this purpose, we present an evaluation of systematic behavior concerning mainly the hyperfine field and isomer shift in the cubic Laves phase materials NpX2, the NaCl-type monochalcogenides and monopnictides, and intermetallics with AuCu3 and ThCr2Si2 structures. Analogies to corresponding rare-earth compounds will be pointed out.

  16. Formation of Compound Semiconductors by Electrochemical Atomic Layer Epitaxy (ECALE)

    DTIC Science & Technology

    1992-05-26

    by using Underpotential Deposition (UPD). UPD is a phenomena where an atomic layer of an element deposits at a potential prior to that needed to...atomic layers of the constituent elements. Atomic layers are formed in ECALE by using Underpotential Deposition (UPD). UPD is a phenomena where an atomic...atomic layers of the constituent elements which make up a compound. Deposition is limited to an atomic layer by the use of underpotential deposition (UPD

  17. Intermetallic phase detection in lead-free solders using synchrotron x-ray diffraction

    NASA Astrophysics Data System (ADS)

    Jackson, Gavin J.; Lu, Hua; Durairaj, Raj; Hoo, Nick; Bailey, Chris; Ekere, Ndy N.; Wright, Jon

    2004-12-01

    The high-intensity, high-resolution x-ray source at the European Synchrotron Radiation Facility (ESRF) has been used in x-ray diffraction (XRD) experiments to detect intermetallic compounds (IMCs) in lead-free solder bumps. The IMCs found in 95.5Sn3.8Ag0.7Cu solder bumps on Cu pads with electroplated-nickel immersion-gold (ENIG) surface finish are consistent with results based on traditional destructive methods. Moreover, after positive identification of the IMCs from the diffraction data, spatial distribution plots over the entire bump were obtained. These spatial distributions for selected intermetallic phases display the layer thickness and confirm the locations of the IMCs. For isothermally aged solder samples, results have shown that much thicker layers of IMCs have grown from the pad interface into the bulk of the solder. Additionally, the XRD technique has also been used in a temperature-resolved mode to observe the formation of IMCs, in situ, during the solidification of the solder joint. The results demonstrate that the XRD technique is very attractive as it allows for nondestructive investigations to be performed on expensive state-of-the-art electronic components, thereby allowing new, lead-free materials to be fully characterized.

  18. Investigating secondary aerosol formation from agricultural amines and reduced sulfur compounds

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Gas phase amines and reduced sulfur compounds are often co-emitted from agricultural processes. Amines have been recently recognized as potentially major sources of agricultural aerosol formation, while the reduced sulfur compounds are largely ignored. There is a severe lack of knowledge and under...

  19. Intermetallic-Based High-Temperature Materials

    SciTech Connect

    Sikka, V.K.

    1999-04-25

    The intermetallic-based alloys for high-temperature applications are introduced. General characteristics of intermetallics are followed by identification of nickel and iron aluminides as the most practical alloys for commercial applications. An overview of the alloy compositions, melting processes, and mechanical properties for nickel and iron aluminizes are presented. The current applications and commercial producers of nickel and iron aluminizes are given. A brief description of the future prospects of intermetallic-based alloys is also given.

  20. Formation of stable radicals in the radiolysis of fluoroorganic compounds

    NASA Astrophysics Data System (ADS)

    Goldanskii, V. I.; Barkalov, I. M.

    The existence of anomally long-living radicals (life time in liquid more than 100 days at 300 K) which arise in the process of radiolysis has been discovered in liquid perfluorocarbons. The ESR spectra analysis has allowed the singling out of two types of radical: (1) the perfluoroalkyl radical in which the unpaired electron stabilization is thought to be connected with the steric isolation of the surrounding perfluoromethyl groups and (2) the perfluoroalkyl radical whose stabilization is connected with the delocalization of the unpaired electron conjugated with the double CC bond. These stable radicals may be employed in the synthesis and modification of fluoropolymers as initiators and regulators, in the dosimetry of reactor irradiation, as well as in medico-biological investigations as spin-labelled compounds.

  1. The oil body formation and breakup in the compound vortex

    NASA Astrophysics Data System (ADS)

    Chaplina, T. O.; Stepanova, E. V.

    2012-04-01

    The flows in the Ocean and Atmosphere combine different types of motion: streams, jets, wakes, vortices and waves. When flows transport solid bodies or immiscible admixtures picturesque flow patterns are revealed and indicated the type of flow. Different spiral patterns visualize vortex flow structure. In experiments is studied the transport of finite volumes of immiscible admixture introduced on the free surface of water drawn into the vortex motion in the vertical cylindrical container. The basic medium was tap water, preliminary degasified to make the visualization less difficult. The fixed volume of immiscible admixture (castor or sunflower oil) is introduced on the quiescent free surface of water inside the cylindrical container. The generation of compound vortex in the cylindrical container started after all the disturbances caused by deposition of the oil volume are damped. In compound vortex the flow oil patch with smooth boundary placed onto free surface is transformed into a set of spiral arms and separate drops contacting with the central oil volume. The droplets are separated from the central spot and slowly travel towards the container sidewall. With time, the spot is transformed into pronounced spiral arms. The most part of oil under the influence of vortex flow is gathered into the central volume contacting with the free surface. This volume is called "the oil body". On the lower frequencies of disk rotation and respectively slow flow gyration the oil body has smooth boundaries with water and air. The growth of disk rotation frequency leads to more pronounced deformation of the contact surface between liquid and air, the boundary of the oil body and water then is covered by small pimples. At the further increase of disk rotation frequency the oil body comes to the breakup, the water-oil boundary become irregular and on the lowest part of the oil body the analog of foam appears (the water-oil emulsion). The work is supported by Ministry of Education

  2. Oxidation of high-temperature intermetallics; Proceedings of the Workshop, Cleveland, OH, Sept. 22, 23, 1988

    NASA Technical Reports Server (NTRS)

    Grobstein, Toni (Editor); Doychak, Joseph (Editor)

    1989-01-01

    The present conference on the high-temperature oxidation behavior of aerospace structures-applicable intermetallic compounds discusses the influence of reactive-element additions on the oxidation of Ni3Al base alloys, the effect of Ni3Al oxidation below 850 C on fracture behavior, the oxidation of FeAl + Hf, Zr, and B, the synergistic effect of Al and Si on the oxidation resistance of Fe alloys, and pack cementation coatings of Cr-Al on Fe, Ni, and Co alloys. Also discussed are the formation of alumina on Nb- and Ti-base alloys, the oxidation behavior of titanium aluminide alloys, silicide coatings for refractory metals, the oxidation of chromium disilicide, and the oxidation behavior of nickel beryllides.

  3. An intermetallic forming steel under radiation for nuclear applications

    NASA Astrophysics Data System (ADS)

    Hofer, C.; Stergar, E.; Maloy, S. A.; Wang, Y. Q.; Hosemann, P.

    2015-03-01

    In this work we investigated the formation and stability of intermetallics formed in a maraging steel PH 13-8 Mo under proton radiation up to 2 dpa utilizing nanoindentation, microcompression testing and atom probe tomography. A comprehensive discussion analyzing the findings utilizing rate theory is introduced, comparing the aging process to radiation induced diffusion. New findings of radiation induced segregation of undersize solute atoms (Si) towards the precipitates are considered.

  4. The Electronic, Elastic, and Structural Properties of Ti-Pd Intermetallics and Associated Hydrides from First-Principles Calculations

    SciTech Connect

    Chen, Xingqiu; Fu, Chong Long; Morris, James R

    2010-01-01

    Using an ab initio density functional approach, we report on the ground-state phase stabilities, enthalpies of formation, electronic, and elastic properties of the Ti-Pd alloy system. The calculated enthalpies of formation are in excellent agreement with available calorimetric data. We found a linear dependence between the calculated enthalpies of formation of several intermetallic structures and the Pd-concentration, indicating that each of these compounds has a very limited composition range. The elastic constants for many of these Ti-Pd intermetallics were calculated and analyzed. The B2 TiPd phase is found to be mechanically unstable with respect to the transformation into the monoclinic B19 structure. A series of hydrides, Ti2PdHx (x=1, 1.5, 2, 3, 4), have been investigated in terms of electronic structure, enthalpies of hydrogen absorption, and site preference of H atoms. Our results illustrate the physical mechanism for hydrogen absorption in term of the charge transfer, and explain why TiPd2 does not form a stable hydride.

  5. Local magnetic moment formation at 119Sn Mössbauer impurity in RFe2 ( R=rare-earth metals) Laves phases compounds

    NASA Astrophysics Data System (ADS)

    de Oliveira, A. L.; de Oliveira, N. A.; Troper, A.

    2010-05-01

    The purpose of the present work is to theoretically study the local magnetic moment formation and the systematics of the magnetic hyperfine fields at a non-magnetic s-p Mössbauer 119Sn impurity diluted on R sites ( R=rare-earth metals) of the cubic Laves phases intermetallic compounds RFe2. One considers that the magnetic hyperfine field has two contributions (i) the contribution from R ions, calculated via an extended Daniel-Friedel [J. Phys. Chem. Solids 24 (1963) 1601] model and (ii) the contribution from the induced magnetic moments arising from the Fe neighboring sites. We have in this case a two-center Blandin-Campbell-like [Phys. Rev. Lett. 31 (1973) 51; J. Magn. Magn. Mater. 1 (1975) 1] problem, where a magnetic 3d-element located at a distance from the 119Sn impurity gives an extra magnetization to a polarized electron gas which is strongly charge perturbed at the 119Sn impurity site. We also include in the model, the nearest-neighbor perturbation due to the translational invariance breaking introduced by the impurity. Our self-consistent total magnetic hyperfine field calculations are in a very good agreement with recent experimental data.

  6. Volatile compounds formation in alcoholic fermentation from grapes collected at 2 maturation stages: influence of nitrogen compounds and grape variety.

    PubMed

    Martínez-Gil, Ana M; Garde-Cerdán, Teresa; Lorenzo, Cándida; Lara, José Félix; Pardo, Francisco; Salinas, M Rosario

    2012-01-01

    The aim of this work was to study the influence of nitrogen compounds on the formation of volatile compounds during the alcoholic fermentation carried out with 4 nonaromatic grape varieties collected at 2 different maturation stages. To do this, Monastrell, Merlot, Syrah, and Petit Verdot grapes were collected 1 wk before harvest and at harvest. Then, the musts were inoculated with the same Saccharomyces cerevisiae yeast strain and were fermented in the same winemaking conditions. Amino acids that showed the highest and the lowest concentration in the must were the same, regardless of the grape variety and maturation stage. Moreover, the consumption of amino acids during the fermentation increased with their concentration in the must. The formation of volatile compounds was not nitrogen composition dependent. However, the concentration of amino acids in the must from grapes collected 1 wk before harvest can be used as a parameter to estimate the concentration of esters in wines from grapes collected at harvest and therefore to have more information to know the grape oenological capacity. Application of principal components analysis (PCA) confirmed the possibility to estimate the concentration of esters in the wines with the concentration of nitrogen compounds in the must.

  7. Method for making devices having intermetallic structures and intermetallic devices made thereby

    DOEpatents

    Paul, Brian Kevin; Wilson, Richard Dean; Alman, David Eli

    2004-01-06

    A method and system for making a monolithic intermetallic structure are presented. The structure is made from lamina blanks which comprise multiple layers of metals which are patternable, or intermetallic lamina blanks that are patternable. Lamina blanks are patterned, stacked and registered, and processed to form a monolithic intermetallic structure. The advantages of a patterned monolithic intermetallic structure include physical characteristics such as melting temperature, thermal conductivity, and corrosion resistance. Applications are broad, and include among others, use as a microreactor, heat recycling device, and apparatus for producing superheated steam. Monolithic intermetallic structures may contain one or more catalysts within the internal features.

  8. Transient liquid phase bonding of intermetallics

    NASA Astrophysics Data System (ADS)

    Guan, Yimin

    The present work was undertaken to examine the applicability of transient liquid phase bonding to structural intermetallics. This research was based on an investigation of the mechanisms governing microstructural development in the joint and adjacent substrates during the joining process. The bonding systems investigated included polycrystalline NiAl/Cu/Ni, polycrystalline NiAl/Cu/superalloys (Martin-Marietta (MM)-247, Inconel (IN) 718 and Nimonic 90), single-crystal NiAl (with 1.5 at % Hf) joined to MM-247 using different filler metals (Cu foil, powder filler metal and electro-plated thin Cu film), and martensitic NiAl joined with martensitic NiTi using Cu foil and specially designed powder filler metals. In polycrystalline NiAl/Cu/Ni bonds, the mechanism of isothermal solidification is considered. Changes in the microstructure of the bond centerline due to element redistribution are discussed. The precipitation of both L1sb2 type gammasp' and B2 type beta phase at the joint centerline is investigated. The formation of martensitic L1sb0 type NiAl is also examined. The mechanical properties of the joints are investigated using shear strength and microhardness tests. In TLP bonding of polycrystalline NiAl with MM-247, both the epitaxial growth of the beta phase NiAl into the joint and the formation of non-epitaxial beta-phase layers are considered. The formation of second-phases, including the gammasp' phase, carbides, and sigma-phase intermetallics is also examined. Bond-line and adjacent substrate microstructures for the NiAl/Cu/MM-247 bonds are correlated with joint mechanical properties determined by room temperature shear testing. Single-crystal NiAl (1.5 at % Hf)/Cu/MM-247 joints are examined and compared with polycrystalline NiAl/Cu/MM247 joints. The effect of Hf on the microstructure of joints is investigated. The influence of different filler metals (i.e., wide-gap powder filler metal and electro-plated thin film filler metal) on the joining process is also

  9. N-nitrosodimethylamine (NDMA) formation from the ozonation of model compounds.

    PubMed

    Marti, Erica J; Pisarenko, Aleksey N; Peller, Julie R; Dickenson, Eric R V

    2015-04-01

    Nitrosamines are a class of toxic disinfection byproducts commonly associated with chloramination, of which several were included on the most recent U.S. EPA Contaminant Candidate List. Nitrosamine formation may be a significant barrier to ozonation in water reuse applications, particularly for direct or indirect potable reuse, since recent studies show direct formation during ozonation of natural water and treated wastewaters. Only a few studies have identified precursors which react with ozone to form N-nitrosodimethylamine (NDMA). In this study, several precursor compound solutions, prepared in ultrapure water and treated wastewater, were subjected to a 10 M excess of ozone. In parallel experiments, the precursor solutions in ultrapure water were exposed to gamma radiation to determine NDMA formation as a byproduct of reactions of precursor compounds with hydroxyl radicals. The results show six new NDMA precursor compounds that have not been previously reported in the literature, including compounds with hydrazone and carbamate moieties. Molar yields in deionized water were 61-78% for 3 precursors, 12-23% for 5 precursors and <4% for 2 precursors. Bromide concentration was important for three compounds (1,1-dimethylhydrazine, acetone dimethylhydrazone and dimethylsulfamide), but did not enhance NDMA formation for the other precursors. NDMA formation due to chloramination was minimal compared to formation due to ozonation, suggesting distinct groups of precursor compounds for these two oxidants. Hydroxyl radical reactions with the precursors will produce NDMA, but formation is much greater in the presence of molecular ozone. Also, hydroxyl radical scavenging during ozonation leads to increased NDMA formation. Molar conversion yields were higher for several precursors in wastewater as compared to deionized water, which could be due to catalyzed reactions with constituents found in wastewater or hydroxyl radical scavenging.

  10. Suppressors made from intermetallic materials

    SciTech Connect

    Klett, James W; Muth, Thomas R; Cler, Dan L

    2014-11-04

    Disclosed are several examples of apparatuses for suppressing the blast and flash produced as a projectile is expelled by gases from a firearm. In some examples, gases are diverted away from the central chamber to an expansion chamber by baffles. The gases are absorbed by the expansion chamber and desorbed slowly, thus decreasing pressure and increasing residence time of the gases. In other examples, the gases impinge against a plurality of rods before expanding through passages between the rods to decrease the pressure and increase the residence time of the gases. These and other exemplary suppressors are made from an intermetallic material composition for enhanced strength and oxidation resistance at high operational temperatures.

  11. Intermetallic Nanocrystals: Syntheses and Catalytic Applications.

    PubMed

    Yan, Yucong; Du, Jingshan S; Gilroy, Kyle D; Yang, Deren; Xia, Younan; Zhang, Hui

    2017-02-24

    At the forefront of nanochemistry, there exists a research endeavor centered around intermetallic nanocrystals, which are unique in terms of long-range atomic ordering, well-defined stoichiometry, and controlled crystal structure. In contrast to alloy nanocrystals with no elemental ordering, it is challenging to synthesize intermetallic nanocrystals with a tight control over their size and shape. Here, recent progress in the synthesis of intermetallic nanocrystals with controllable sizes and well-defined shapes is highlighted. A simple analysis and some insights key to the selection of experimental conditions for generating intermetallic nanocrystals are presented, followed by examples to highlight the viable use of intermetallic nanocrystals as electrocatalysts or catalysts for various reactions, with a focus on the enhanced performance relative to their alloy counterparts that lack elemental ordering. Within the conclusion, perspectives on future developments in the context of synthetic control, structure-property relationships, and applications are discussed.

  12. Forming metal-intermetallic or metal-ceramic composites by self-propagating high-temperature reactions

    DOEpatents

    Rawers, James C.; Alman, David E.; Petty, Jr., Arthur V.

    1996-01-01

    Industrial applications of composites often require that the final product have a complex shape. In this invention intermetallic or ceramic phases are formed from sheets of unreacted elemental metals. The process described in this invention allows the final product shape be formed prior to the formation of the composite. This saves energy and allows formation of shaped articles of metal-intermetallic composites composed of brittle materials that cannot be deformed without breaking.

  13. Production of antibacterial compounds and biofilm formation by Roseobacter species are influenced by culture conditions.

    PubMed

    Bruhn, Jesper Bartholin; Gram, Lone; Belas, Robert

    2007-01-01

    Bacterial communities associated with marine algae are often dominated by members of the Roseobacter clade, and in the present study, we describe Roseobacter phenotypes that may provide this group of bacteria with selective advantages when colonizing this niche. Nine of 14 members of the Roseobacter clade, of which half were isolated from cultures of the dinoflagellate Pfiesteria piscicida, produced antibacterial compounds. Many non-Roseobacter marine bacteria were inhibited by sterile filtered supernatants of Silicibacter sp. TM1040 and Phaeobacter (formerly Roseobacter) strain 27-4, which had the highest production of antibacterial compound. In contrast, Roseobacter strains were susceptible only when exposed to concentrated compound. The production of antibacterial compound was influenced by the growth conditions, as production was most pronounced when bacteria were grown in liquid medium under static conditions. Under these conditions, Silicibacter sp. TM1040 cells attached to one another, forming rosettes, as has previously been reported for Phaeobacter 27-4. A spontaneous Phaeobacter 27-4 mutant unable to form rosettes was also defective in biofilm formation and the production of antibacterial compound, indicating a possible link between these phenotypes. Rosette formation was observed in 8 of 14 Roseobacter clade strains examined and was very pronounced under static growth in 5 of these strains. Attachment to surfaces and biofilm formation at the air-liquid interface by these five strains was greatly facilitated by growth conditions that favored rosette formation, and rosette-forming strains were 13 to 30 times more efficient in attaching to glass compared to strains under conditions where rosette formation was not pronounced. We hypothesize that the ability to produce antibacterial compounds that principally inhibit non-Roseobacter species, combined with an enhancement in biofilm formation, may give members of the Roseobacter clade a selective advantage and

  14. Relationship between virgin olive oil phenolic compounds and acrylamide formation in fried crisps.

    PubMed

    Napolitano, Aurora; Morales, Francisco; Sacchi, Raffaele; Fogliano, Vincenzo

    2008-03-26

    In this paper the relationship between virgin olive oil (VOO) phenol compounds and the formation of acrylamide in potato crisps was investigated. The phenol compositions of 20 VOO samples were screened by LC-MS, and 4 oils, characterized by different phenol compound patterns, were selected for frying experiments. Slices of potatoes were fried at 180 degrees C for 5, 10, and 15 min, and acrylamide content was determined by LC-MS. Results demonstrated that VOO phenolic compounds are not degraded during frying, and crisp color was not significantly different among the four VOOs. Acrylamide concentration in crisps increased during frying time, but the formation was faster in the oil having the lowest concentration of phenolic compounds. Moreover, the VOO having the highest concentration of ortho-diphenolic compounds is able to efficiently inhibit acrylamide formation in crisps from mild to moderate frying conditions. It was concluded that the use of ortho-diphenolic-rich VOOs can be proposed as a reliable mitigation strategy to reduce acrylamide formation in domestic deep-frying.

  15. Formation mechanisms of trichloromethyl-containing compounds in the terrestrial environment: a critical review.

    PubMed

    Breider, Florian; Albers, Christian Nyrop

    2015-01-01

    Natural trichloromethyl compounds present in the terrestrial environment are important contributors to chlorine in the lower atmosphere and may be also a cause for concern when high concentrations are detected in soils and groundwater. During the last decade our knowledge of the mechanisms involved in the formation of these compounds has grown. This critical review summarizes our current understanding and uncertainties on the mechanisms leading to the formation of natural trichloromethyl compounds. The objective of the review is to gather information regarding the natural processes that lead to the formation of trichloromethyl compounds and then to compare these mechanisms with the much more comprehensive literature on the reactions occurring during chemical chlorination of organic material. It turns out that the reaction mechanisms during chemical chlorination are likely to be similar to those occurring naturally and that significant knowledge may therefore be transferred between the scientific disciplines of chemical chlorination and natural organohalogens. There is however still a need for additional research before we understand fully the mechanisms occurring during the formation of natural trichloromethyl compounds and open questions and future research needs are identified in the last part of the review.

  16. Formation of Haloacetonitriles, Haloacetamides, and Nitrogenous Heterocyclic Byproducts by Chloramination of Phenolic Compounds.

    PubMed

    Nihemaiti, Maolida; Le Roux, Julien; Hoppe-Jones, Christiane; Reckhow, David A; Croué, Jean-Philippe

    2017-01-03

    The potential formation of nitrogenous disinfection byproducts (N-DBPs) was investigated from the chloramination of nitrogenous and non-nitrogenous aromatic compounds. All molecules led to the formation of known N-DBPs (e.g., dichloroacetonitrile, dichloroacetamide) with various production yields. Resorcinol, a major precursor of chloroform, also formed di/trichloroacetonitrile, di/trichloroacetamide, and haloacetic acids, indicating that it is a precursor of both N-DBPs and carbonaceous DBPs (C-DBPs) upon chloramination. More detailed experiments were conducted on resorcinol to understand N-DBPs formation mechanisms and to identify reaction intermediates. Based on the accurate mass from high resolution Quadrupole Time-of-Flight GC-MS (GC-QTOF) and fragmentation patterns from electronic impact and positive chemical ionization modes, several products were tentatively identified as nitrogenous heterocyclic compounds (e.g., 3-chloro-5-hydroxy-1H-pyrrole-2-one with dichloromethyl group, 3-chloro-2,5-pyrroledione). These products were structurally similar to the heterocyclic compounds formed during chlorination, such as the highly mutagenic MX (3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone) or halogenated pyrroles. To our knowledge, this is the first time that the formation of halogenated nitrogenous heterocyclic compounds is reported from chloramination process. The formation of these nitrogenous byproducts during chloramination might be of concern considering their potential toxicity.

  17. Proximal Pocket Hydrogen Bonds Significantly Influence the Mechanism of Chloroperoxidase Compound I Formation.

    PubMed

    Pardillo, Armando D; Morozov, Alexander N; Chatfield, David C

    2015-10-01

    The influence of backbone hydrogen bonds to the sulfur atom of the proximal thiolate (NH···S hydrogen bonds) on the formation of compound I in chloroperoxidase is investigated with DFT calculations. Reaction profiles for the transformation of the ferric resting state into compound I in the presence of a peroxide substrate are calculated for a model system incorporating the heme and key proximal and distal amino acid residues. We find that NH···S hydrogen bonds (1) reduce the barrier for the formation of compound 0 by 7.6 kcal/mol, (2) increase the stability of compound 0 by 5.2 kcal/mol, (3) reduce the stability of compound I relative to compound 0 by 6.2 kcal/mol, and (4) reduce the stability of protonated compound 0, favoring a hybrid homo-heterolytic relative to a classic heterolytic mechanism for O-O bond scission. In general, the influence of the NH···S hydrogen bonds can be traced to a reduction in the pKa of the heme-bound substrate. We find that the hydrogen bond networks on the proximal and distal sides of the heme function together to modulate the mechanism of reaction. These results confirm and extend long-standing theories that the NH···S hydrogen bonds in heme thiolate proteins influence reactivity by tuning the thiolate "push" effect.

  18. The preparation of the Ti-Al alloys based on intermetallic phases

    NASA Astrophysics Data System (ADS)

    Kosova, N.; Sachkov, V.; Kurzina, I.; Pichugina, A.; Vladimirov, A.; Kazantseva, L.; Sachkova, A.

    2016-01-01

    This article deals with a method of obtaining materials in the Ti-Al system. Research was carried out in accordance with the phase diagram of the system state. It was established, that both single-phase and multiphase systems, containing finely dispersed intermetallic compositions of phases Ti3Al, TiAl and TiAl3, are formed. Additionally, it was found that the pure finely dispersed (coherent-scattering region (CSR) up to 100 nm) intermetallic compound TiAl3 is formed at molar ratio of Ti:Al = 1:3. Experimentally proved the possibility of produce the complex composition of alloys and intermetallic compounds and products based on them.

  19. Rare-earth transition-metal intermetallics: Structure-bonding-property relationships

    SciTech Connect

    Han, M. K.

    2006-01-01

    The explorations of rare-earth, transition metal intermetallics have resulted in the synthesis and characterization, and electronic structure investigation, as well as understanding the structure-bonding property relationships. The work has presented the following results: (1) Understanding the relationship between compositions and properties in LaFe13-xSix system: A detailed structural and theoretical investigation provided the understanding of the role of a third element on stabilizing the structure and controlling the transformation of cubic NaZn{sub 13}-type structures to the tetragonal derivative, as well as the relationship between the structures and properties. (2) Synthesis of new ternary rare-earth iron silicides Re2-xFe4Si14-y and proposed superstructure: This compound offers complex structural challenges such as fractional occupancies and their ordering in superstructure. (3) Electronic structure calculation of FeSi2: This shows that the metal-semiconductor phase transition depends on the structure. The mechanism of band gap opening is described in terms of bonding and structural distortion. This result shows that the electronic structure calculations are an essential tool for understanding the relationship between structure and chemical bonding in these compounds. (4) Synthesis of new ternary rare-earth Zinc aluminides Tb3Zn3.6Al7.4: Partially ordered structure of Tb3Zn3.6Al7.4 compound provides new insights into the formation, composition and structure of rare-earth transition-metal intermetallics. Electronic structure calculations attribute the observed composition to optimizing metal-metal bonding in the electronegative (Zn, Al) framework, while the specific ordering is strongly influenced by specific orbital interactions. (5) Synthesis of new structure type of Zn39(CrxAl1-x)81

  20. Rare-Earth Transition-Metal Intermetallics: Structure-bonding-Property Relationships

    SciTech Connect

    Han, Mi-Kyung

    2006-01-01

    Our explorations of rare-earth, transition metal intermetallics have resulted in the synthesis and characterization, and electronic structure investigation, as well as understanding the structure-bonding-property relationships. Our work has presented the following results: (1) Understanding the relationship between compositions and properties in LaFe13-xSix system: A detailed structural and theoretical investigation provided the understanding of the role of a third element on stabilizing the structure and controlling the transformation of cubic NaZn13-type structures to the tetragonal derivative, as well as the relationship between the structures and properties. (2) Synthesis of new ternary rare-earth iron silicides RE2-xFe4Si14-y and proposed superstructure: This compound offers complex structural challenges such as fractional occupancies and their ordering in superstructure. (3) Electronic structure calculation of FeSi2: This shows that the metal-semiconductor phase transition depends on the structure. The mechanism of band gap opening is described in terms of bonding and structural distortion. This result shows that the electronic structure calculations are an essential tool for understanding the relationship between structure and chemical bonding in these compounds. (4) Synthesis of new ternary rare-earth Zinc aluminides Tb3Zn3.6Al7.4: Partially ordered structure of Tb3.6Zn13-xAl7.4 compound provides new insights into the formation, composition and structure of rare-earth transition-metal intermetallics. Electronic structure calculations attribute the observed composition to optimizing metal-metal bonding in the electronegative (Zn, Al) framework, while the specific ordering is strongly influenced by specific orbital interactions. (5) Synthesis of new structure type of Zn39(CrxAl1-x

  1. Electron microscopy of severely deformed L12 intermetallics

    NASA Astrophysics Data System (ADS)

    Geist, D.; Gammer, C.; Mangler, C.; Rentenberger, C.; Karnthaler, H. P.

    2010-12-01

    Severe plastic deformation (SPD) can be used to make bulk, nanostructured materials. Three L12 long-range ordered (LRO) intermetallic compounds were studied by TEM methods. The superlattice glide dislocations can dissociate according to two schemes: antiphase boundary (APB) coupled unit dislocations or superlattice intrinsic stacking fault (SISF) coupled super Shockley partials; both of them are analysed by weak-beam TEM methods. The nanostructures resulting from SPD carried out by high pressure torsion (HPT) are strongly affected by the different dissociation schemes of the dislocations. APB-dissociated superlattice dislocations and especially the APB tubes they form lead to the destruction of the LRO by HPT deformation as observed in Cu3Au and Ni3Al, whereas in Zr3Al heavily deformed (∼100,000% shear strain) at low temperatures the order is not destroyed since the deformation occurs by SISF-dissociated dislocations. In addition to the effects on the LRO the different dissociation schemes of the dislocations have a strong impact on the refinement and destruction of the crystalline structure by SPD. They seem to be decisive for the dynamic recovery considered as the limiting factor for the final grain sizes and the possibility of reaching amorphisation. Finally, the correlation between the reduction of the LRO and the structural refinement occurring during SPD is different in the three different alloys: In Cu3Au, the LRO is already strongly reduced before the structural refinement reaches saturation, in Ni3Al both are occurring simultaneously, whereas in Zr3Al, the formation of the nanograins does not seem to be connected with disordering.

  2. Microplasticity and fatigue in a damage tolerant niobium aluminide intermetallic

    SciTech Connect

    Soboyejo, W.O.; DiPasquale, J.; Srivatsan, T.S.; Konitzer, D.

    1997-12-31

    In this paper, the micromechanisms of microplasticity and fatigue are elucidated for a damage tolerant niobium aluminide intermetallic deformed to failure under both monotonic and cyclic loading. Localized microplasticity is shown to occur by the formation of slip bands at stresses as low as 9% of the bulk yield stress. Formation and presence of slip bands is also observed upon application of the first cycle of fatigue load. The deformation and cracking phenomena are discussed in light of classical fatigue crack initiation and propagation models. The implications of microplasticity are elucidated for both fatigue crack initiation and crack growth.

  3. Bacterial ethane formation from reduced, ethylated sulfur compounds in anoxic sediments

    USGS Publications Warehouse

    Oremland, R.S.; Whiticar, Michael J.; Strohmaier, F.E.; Kiene, R.P.

    1988-01-01

    Trace levels of ethane were produced biologically in anoxic sediment slurries from five chemically different aquatic environments. Gases from these locations displayed biogenic characteristics, having 12C-enriched values of ??13CH4 (-62 to -86%.), ??13C2H6 (-35 to -55%.) and high ratios (720 to 140,000) of CH4 [C2H6 + C3H8]. Endogenous production of ethane by slurries was inhibited by autoclaving or by addition of the inhibitor of methanogenic bacteria, 2-bromoethanesulfonic acid (BES). Ethane formation was stimulated markedly by ethanethiol (ESH), and, to a lesser extent, by diethylsulfide (DES). Formation of methane and ethane in ESH- or DES-amended slurries was blocked by BES. Experiments showed that ethionine (or an analogous compound) could be a precursor of ESH. Ethylamine or ethanol additions to slurries caused only a minor stimulation of ethane formation. Similarly, propanethiol additions resulted in only a minor enhancement of propane formation. Cell suspensions of a methyltrophic methanogen produced traces of ethane when incubated in the presence of DES, although the organism did not grow on this compound. These results indicate that methanogenic bacteria produce ethane from the traces of ethylated sulfur compounds present in recent sediments. Preliminary estimates of stable carbon isotope fractionation associated with sediment methane formation from dimethylsulfide was about 40%., while ethane formation from DES and ESH was only 4. 6 and 6.5%., respectively. ?? 1988.

  4. Structure and magnetism of new rare-earth-free intermetallic compounds: Fe3+xCo3-xTi2 (0 ≤ x ≤ 3)

    SciTech Connect

    Balasubramanian, Balamurugan; Das, Bhaskar; Nguyen, Manh Cuong; Xu, Xiaoshan; Zhang, Jie; Zhang, Xiaozhe; Liu, Yaohua; Huq, Ashfia; Valloppilly, Shah R.; Jin, Yunlong; Wang, Cai -Zhuang; Ho, Kai -Ming; Sellmyer, David J.

    2016-11-28

    Here, we report the fabrication of a set of new rare-earth-free magnetic compounds, which form the Fe3Co3Ti2-type hexagonal structure with P-6m2 symmetry. Neutron powder diffraction shows a significant Fe/Co anti-site mixing in the Fe3Co3Ti2 structure, which has a strong effect on the magnetocrystalline anisotropy as revealed by first-principle calculations. Increasing substitution of Fe atoms for Co in the Fe3Co3Ti2 lattice leads to the formation of Fe4Co2Ti2, Fe5CoTi, and Fe6Ti2 with significantly improved permanent-magnet properties. A high magnetic anisotropy (13.0 Mergs/cm3) and saturation magnetic polarization (11.4 kG) are achieved at 10 K by altering the atomic arrangements and decreasing Fe/Co occupancy disorder.

  5. A Connectionist Model of Stimulus Class Formation with a Yes/No Procedure and Compound Stimuli

    ERIC Educational Resources Information Center

    Tovar, Angel E.; Chavez, Alvaro Torres

    2012-01-01

    We analyzed stimulus class formation in a human study and in a connectionist model (CM) with a yes/no procedure, using compound stimuli. In the human study, the participants were six female undergraduate students; the CM was a feed-forward back-propagation network. Two 3-member stimulus classes were trained with a similar procedure in both the…

  6. Environmental Effects in Advanced Intermetallics

    SciTech Connect

    Liu, C.T.

    1998-11-24

    This paper provides a comprehensive review of environmental embrittlement in iron and nickel aluminizes. The embrittlement involves the interaction of these intermetallics with moisture in air and generation of atomic hydrogen, resulting in hydrogen-induced embrittlement at ambient temperatures. Environmental embrittlement promotes brittle grain-boundary fracture in Ni{sub 3}Al alloys but brittle cleavage fracture in Fe{sub 3}Al-FeAl alloys. The embrittlement strongly depends on strain rate, with tensile-ductility increase with increasing strain rate. It has been demonstrated that environmental embrittlement can be alleviated by alloying additions, surface modifications, and control of grain size and shape. Boron tends to segregate strongly to grain boundaries and is most effective in suppressing environmental embrittlement in Ni{sub 3}Al alloys. The mechanistic understanding of alloy effects and environmental embrittlement has led to the development of nickel and iron aluminide alloys with improved properties for structural use at elevated temperatures in hostile environments.

  7. Monitoring the apple polyphenol oxidase-modulated adduct formation of phenolic and amino compounds.

    PubMed

    Reinkensmeier, Annika; Steinbrenner, Katrin; Homann, Thomas; Bußler, Sara; Rohn, Sascha; Rawel, Hashadrai M

    2016-03-01

    Minimally processed fruit products such as smoothies are increasingly coming into demand. However, they are often combined with dairy ingredients. In this combination, phenolic compounds, polyphenoloxidases, and amino compounds could interact. In this work, a model approach is presented where apple serves as a source for a high polyphenoloxidase activity for modulating the reactions. The polyphenoloxidase activity ranged from 128 to 333nakt/mL in different apple varieties. From these, 'Braeburn' was found to provide the highest enzymatic activity. The formation and stability of resulting chromogenic conjugates was investigated. The results show that such adducts are not stable and possible degradation mechanisms leading to follow-up products formed are proposed. Finally, apple extracts were used to modify proteins and their functional properties characterized. There were retaining antioxidant properties inherent to phenolic compounds after adduct formation. Consequently, such interactions may also be utilized to improve the textural quality of food products.

  8. Negative thermal expansion induced by intermetallic charge transfer.

    PubMed

    Azuma, Masaki; Oka, Kengo; Nabetani, Koichiro

    2015-06-01

    Suppression of thermal expansion is of great importance for industry. Negative thermal expansion (NTE) materials which shrink on heating and expand on cooling are therefore attracting keen attention. Here we provide a brief overview of NTE induced by intermetallic charge transfer in A-site ordered double perovskites SaCu3Fe4O12 and LaCu3Fe4-x Mn x O12, as well as in Bi or Ni substituted BiNiO3. The last compound shows a colossal dilatometric linear thermal expansion coefficient exceeding -70 × 10(-6) K(-1) near room temperature, in the temperature range which can be controlled by substitution.

  9. Processing - Property Relationship in Advanced Intermetallics

    DTIC Science & Technology

    1994-07-01

    AD-A285 262 - IlE I !!III Illl iIII c.,. Processing- Property Relationship I in Advanced Intermetallics Final Report For Period March 4,1991 through...through 03-03-94 4. TITLE AND SUBTITLE 5. FUNDING NUMBERS Processing- Property Relationship in Advanced Intermetallics; 4. AUTHOR(S) D.A. Hardwick and P.L...2 M echanical Properties ......................................................................... 9 3 C

  10. Electronic packing frustration in complex intermetallic structures: the role of chemical pressure in Ca2Ag7.

    PubMed

    Fredrickson, Daniel C

    2011-07-06

    The assignment of distinct roles to electronics and sterics has a long history in our rationalization of chemical phenomena. Exploratory synthesis in the field of intermetallic compounds challenges this dichotomy with a growing list of phases whose structural chemistry points to an interplay between atomic size effects and orbital interactions. In this paper, we begin with a simple model for how this interdependence may arise in the dense atomic packing of intermetallics: correlations between interatomic distances lead to the inability of a phase to optimize bonds without simultaneously shortening electronically under-supported contacts, a conflict we term electronic packing frustration (EPF). An anticipated consequence of this frustration is the emergence of chemical pressures (CPs) acting on the affected atoms. We develop a theoretical method based on DFT-calibrated μ(2)-Hückel calculations for probing these CP effects. Applying this method to the Ca(2)Ag(7) structure, a variant of the CaCu(5) type with defect planes, reveals its formation is EPF-driven. The defect planes resolve severe CPs surrounding the Ca atoms in a hypothetical CaCu(5)-type CaAg(5) phase. CP analysis also points to a rationale for these results in terms of a CP analogue of the pressure-distance paradox and predicts that the impetus for defect plane insertion is tunable via variations in the electron count.

  11. Effect of select organic compounds on perchlorate formation at boron-doped diamond film anodes.

    PubMed

    Donaghue, Adrienne; Chaplin, Brian P

    2013-01-01

    Rates of ClO4(-) formation from ClO3(-) oxidation were investigated in batch experiments as a function of organic compounds (p-nitrophenol, p-benzoquinone, p-methoxyphenol, and oxalic acid) and current density using boron-doped diamond film anodes. Excluding organics, ClO4(-) formation rates ranged from 359 to 687 μmoles m(-2) min(-1) for current densities of 1-10 mA cm(-2). The presence of p-substituted phenols inhibited ClO4(-) formation rates between 13.0 and 99.6%. Results from a reactive-transport model of the diffuse layer adjacent to the anode surface indicate that competition between organics and ClO3(•) for OH(•) within a reaction zone (0.02-0.96 μm) adjacent to the anode controls ClO4(-) formation. Under kinetic-limited conditions (1.0 mA cm(-2)), organics reach the anode surface and substrates with higher OH(•) reaction rates demonstrate greater inhibition of perchlorate formation (IPF). At higher current densities (10 mA cm(-2)), organic compound oxidation becomes mass transfer-limited and compounds degrade a small distance from the anode surface (∼ 0.26 μm for p-methoxyphenol). Therefore, OH(•) scavenging does not occur at the anode surface and IPF values decrease. Results provide evidence for the existence of desorbed OH(•) near the anode surface and highlight the importance of controlling reactor operating conditions to limit ClO4(-) production during anodic treatment of organic compounds.

  12. Catalytic asymmetric carbon-carbon bond formation via allylic alkylations with organolithium compounds.

    PubMed

    Pérez, Manuel; Fañanás-Mastral, Martín; Bos, Pieter H; Rudolph, Alena; Harutyunyan, Syuzanna R; Feringa, Ben L

    2011-05-01

    Carbon-carbon bond formation is the basis for the biogenesis of nature's essential molecules. Consequently, it lies at the heart of the chemical sciences. Chiral catalysts have been developed for asymmetric C-C bond formation to yield single enantiomers from several organometallic reagents. Remarkably, for extremely reactive organolithium compounds, which are among the most broadly used reagents in chemical synthesis, a general catalytic methodology for enantioselective C-C formation has proven elusive, until now. Here, we report a copper-based chiral catalytic system that allows carbon-carbon bond formation via allylic alkylation with alkyllithium reagents, with extremely high enantioselectivities and able to tolerate several functional groups. We have found that both the solvent used and the structure of the active chiral catalyst are the most critical factors in achieving successful asymmetric catalysis with alkyllithium reagents. The active form of the chiral catalyst has been identified through spectroscopic studies as a diphosphine copper monoalkyl species.

  13. Exo-Melt{trademark} process for intermetallic powders

    SciTech Connect

    Sikka, V.K.; Deevi, S.C.

    1996-06-01

    The methods of powder production for intermetallics are reviewed. An innovative method known as Exo-Melt{trademark} is described for producing molten aluminides for gas- and water-atomization processes that require a molten metal stream. The Exo-Melt{trademark} process is based on the effective utilization of the heats of formation of aluminides from their constituent elements. The Exo-Melt{trademark} process principles are discussed along with a description of a furnace-loading sequence that uses the principles for practical applications. The benefits of the Exo-Melt{trademark} process are compared with the problems associated with the conventional melting process.

  14. Magnetic Structures of Heterometallic M(II)-M(III) Formate Compounds.

    PubMed

    Mazzuca, Lidia; Cañadillas-Delgado, Laura; Rodríguez-Velamazán, J Alberto; Fabelo, Oscar; Scarrozza, Marco; Stroppa, Alessandro; Picozzi, Silvia; Zhao, Jiong-Peng; Bu, Xian-He; Rodríguez-Carvajal, Juan

    2017-01-03

    A study of the magnetic structure of the [NH2(CH3)2]n[Fe(III)M(II)(HCOO)6]n niccolite-like compounds, with M(II) = Co(II) (2) and Mn(II) (3) ions, has been carried out using neutron diffraction and compared with the previously reported Fe(II)-containing compound (1). The inclusion of two different metallic atoms into the niccolite-like structure framework leads to the formation of isostructural compounds with very different magnetic behaviors due to the compensation or not of the different spins involved in each lattice. Below TN, the magnetic order in these compounds varies from ferrimagnetic behavior for 1 and 2 to an antiferromagnetic behavior with a weak spin canting for 3. Structure refinements of 2 and 3 at low temperature (45 K) have been carried out combining synchrotron X-ray and high-resolution neutron diffraction in a multipattern approach. The magnetic structures have been determined from the difference patterns between the neutron data in the paramagnetic and the magnetically ordered regions. These difference patterns have been analyzed using a simulated annealing protocol and symmetry analysis techniques. The obtained magnetic structures have been further rationalized by means of ab initio DFT calculations. The direction of the magnetic moment of each compound has been determined. The easy axis of the M(II) for compound 1 (Fe(II)) is along the c axis; for compound 2 (Co(II)), the moments are mainly within the ab plane; finally, for compound 3 (Mn(II)), the calculations show that the moments have components both in the ab plane and along the c axis.

  15. Determining heats of detonation of non-aromatic energetic compounds without considering their heats of formation.

    PubMed

    Keshavarz, Mohammad Hossein

    2007-04-02

    A new procedure is introduced for calculating heats of detonation of non-aromatic energetic compounds through ratios of oxygen to carbon and hydrogen to oxygen as well as the contribution of some structural parameters. There is no need to use heats of formation of non-aromatic energetic compounds that are usually needed by the other methods. Moreover, this much simple method does not use any experimental and computed data of energetic materials. Predicted heats of detonation for 28 non-aromatic energetic compounds have a root mean square (rms) of deviation of 0.54 kJ/g from experiment, which show good agreement with respect to measured values. The new method is the simplest procedure for predicting heats of detonation and provides reliable results which are comparable with the other methods.

  16. Dislocation sources in ordered intermetallics

    SciTech Connect

    Yoo, M.H.; Appel, F.; Wagner, R.; Mecking, H.

    1996-09-01

    An overview on the current understanding of dislocation sources and multiplication mechanisms is made for ordered intermetallic alloys of the L1{sub 2}, B2, and D0{sub 19} structures. In L1{sub 2} alloys, a large disparity of edge/screw segments in their relative mobility reduces the efficiency of a Frank-Read Type multiplication mechanism. In Fe-40%Al of the B2 structure, a variety of dislocation sources are available for <111> slip, including ones resulting from condensation of thermal vacancies. In NiAl with the relatively high APB energy, <100> dislocations may result from the dislocation decomposition reactions, the prismatic punching out from inclusion particles, and/or steps and coated layers of the surface. Internal interfaces often provide sites for dislocation multiplication, e.g., grain boundaries, sub-boundaries in Ni{sub 3}Ga, NiAl and Ti{sub 3}Al, and antiphase domain boundaries in Ti{sub 3}Al. As for the crack tip as a dislocation source, extended SISFs trailed by super-Shockley partials emanating form the cracks in Ni{sub 3}Al and Co{sub 3}Ti are discussed in view of a possible toughening mechanism.

  17. Advanced ordered intermetallic alloy deployment

    SciTech Connect

    Liu, C.T.; Maziasz, P.J.; Easton, D.S.

    1997-04-01

    The need for high-strength, high-temperature, and light-weight materials for structural applications has generated a great deal of interest in ordered intermetallic alloys, particularly in {gamma}-based titanium aluminides {gamma}-based TiAl alloys offer an attractive mix of low density ({approximately}4g/cm{sup 3}), good creep resistance, and high-temperature strength and oxidation resistance. For rotating or high-speed components. TiAl also has a high damping coefficient which minimizes vibrations and noise. These alloys generally contain two phases. {alpha}{sub 2} (DO{sub 19} structure) and {gamma} (L 1{sub 0}), at temperatures below 1120{degrees}C, the euticoid temperature. The mechanical properties of TiAl-based alloys are sensitive to both alloy compositions and microstructure. Depending on heat-treatment and thermomechanical processing, microstructures with near equiaxed {gamma}, a duplex structure (a mix of the {gamma} and {alpha}{sub 2} phases) can be developed in TiAl alloys containing 45 to 50 at. % Al. The major concern for structural use of TiAl alloys is their low ductility and poor fracture resistance at ambient temperatures. The purpose of this project is to improve the fracture toughness of TiAl-based alloys by controlling alloy composition, microstructure and thermomechanical treatment. This work is expected to lead to the development of TiAl alloys with significantly improved fracture toughness and tensile ductility for structural use.

  18. Natural abiotic formation of oxalic acid in soils: results from aromatic model compounds and soil samples.

    PubMed

    Studenroth, Sabine; Huber, Stefan G; Kotte, Karsten; Schöler, Heinz F

    2013-02-05

    Oxalic acid is the smallest dicarboxylic acid and plays an important role in soil processes (e.g., mineral weathering and metal detoxification in plants). We have first proven its abiotic formation in soils and investigated natural abiotic degradation processes based on the oxidation of soil organic matter, enhanced by Fe(3+) and H(2)O(2) as hydroxyl radical suppliers. Experiments with the model compound catechol and further hydroxylated benzenes were performed to examine a common degradation pathway and to presume a general formation mechanism of oxalic acid. Two soil samples were tested for the release of oxalic acid and the potential effects of various soil parameters on oxalic acid formation. Additionally, the soil samples were treated with different soil sterilization methods to prove the oxalic acid formation under abiotic soil conditions. Different series of model experiments were conducted to determine a range of factors including Fe(3+), H(2)O(2), reaction time, pH, and chloride concentration on oxalic acid formation. Under certain conditions, catechol is degraded up to 65.6% to oxalic acid referring to carbon. In serial experiments with two soil samples, oxalic acid was produced, and the obtained results are suggestive of an abiotic degradation process. In conclusion, Fenton-like conditions with low Fe(3+) concentrations and an excess of H(2)O(2) as well as acidic conditions were required for an optimal oxalic acid formation. The presence of chloride reduced oxalic acid formation.

  19. In situ examination of moving crack tips in ordered intermetallics.

    SciTech Connect

    Heuer, J.; Lam, N. Q.; Okamoto, P. R.; Stubbins, J. F.

    1999-01-25

    Recent studies have shown that high stress concentrations at moving crack tips in the intermetallic compound NiTi can induce a crystalline-to-amorphous (C-A) transformation of the crack tip region. This stress-induced C-A transformation has a temperature dependence and crystallization behavior similar to those of ion irradiation-induced C-A transformation of NiTi. The present study examines if these similarities between stress- and irradiation-induced amorphization hold true for two other intermetallic compounds, CuTi and Ni{sub 3}Ti. In situ straining was performed in an intermediate-voltage transmission electron microscope. The presence or absence of an amorphous phase was determined by dark field imaging and selected area diffraction of crack tip regions. Crack tips in both CuTi and Ni{sub 3}Ti were found to remain crystalline upon fracture. The observed absence of stress-induced amorphization in Ni{sub 3}Ti is consistent with its known absence during irradiation, but the absence in CuTi differs from its known irradiation-induced amorphization behavior. Reasons for the similarity and difference are discussed.

  20. Metabolic Impact of Redox Cofactor Perturbations on the Formation of Aroma Compounds in Saccharomyces cerevisiae

    PubMed Central

    Sanchez, Isabelle; Dequin, Sylvie; Camarasa, Carole

    2015-01-01

    Redox homeostasis is a fundamental requirement for the maintenance of metabolism, energy generation, and growth in Saccharomyces cerevisiae. The redox cofactors NADH and NADPH are among the most highly connected metabolites in metabolic networks. Changes in their concentrations may induce widespread changes in metabolism. Redox imbalances were achieved with a dedicated biological tool overexpressing native NADH-dependent or engineered NADPH-dependent 2,3-butanediol dehydrogenase, in the presence of acetoin. We report that targeted perturbation of the balance of cofactors (NAD+/NADH or, to a lesser extent, NADP+/NADPH) significantly affected the production of volatile compounds. In most cases, variations in the redox state of yeasts modified the formation of all compounds from the same biochemical pathway (isobutanol, isoamyl alcohol, and their derivatives) or chemical class (ethyl esters), irrespective of the cofactors. These coordinated responses were found to be closely linked to the impact of redox status on the availability of intermediates of central carbon metabolism. This was the case for α-keto acids and acetyl coenzyme A (acetyl-CoA), which are precursors for the synthesis of many volatile compounds. We also demonstrated that changes in the availability of NADH selectively affected the synthesis of some volatile molecules (e.g., methionol, phenylethanol, and propanoic acid), reflecting the specific cofactor requirements of the dehydrogenases involved in their formation. Our findings indicate that both the availability of precursors from central carbon metabolism and the accessibility of reduced cofactors contribute to cell redox status modulation of volatile compound formation. PMID:26475113

  1. Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate

    NASA Technical Reports Server (NTRS)

    McCollom, T. M.; Simoneit, B. R.

    1999-01-01

    The formation of organic compounds during the decomposition of iron oxalate dihydrate (IOD) was investigated as a possible analog for abiotic organic synthesis in geological systems. After heating at 330 degrees C for 2-4 days, IOD decomposed to a mixture of the minerals siderite and magnetite plus gas and non-volatile organic compounds. The organic products included an extremely large variety of compounds, making identification of individual reaction products difficult. However, the non-volatile products were dominated by several homologous series of alkylated cyclic compounds mostly containing a single aromatic ring, including alkylphenols, alkylbenzenes, alkyltetrahydronaphthols, and alkyltetrahydronaphthalenes. Traces of n-alkanols, n-alkanoic acids, n-alkanones, and n-alkanes were also identified. Carbon in the gas phase was predominantly CO2 (+CO?), with lesser amounts of light hydrocarbons to > C6 including all possible branched and normal isomers of the alkanes and alkenes. The organic products were apparently the result of two concurrent reaction processes: (1) condensation of the two-carbon units present in the initial oxalate moiety, and (2) Fischer-Tropsch-type synthesis from CO2 or CO generated during the experiment. Compounds produced by the former process may not be characteristic of synthesis from the single-carbon precursors which predominate in geologic systems, suggesting iron oxalate decomposition may not provide a particularly suitable analog for investigation of abiotic organic synthesis. When water was included in the reaction vessels, CO2 and traces of methane and light hydrocarbon gases were the only carbon products observed (other than siderite), suggesting that the presence of water allowed the system to proceed rapidly towards equilibrium and precluded the formation of metastable organic intermediates.

  2. Formation of bioorganic compounds in simulated planetary atmospheres by high energy particles or photons.

    PubMed

    Kobayashi, K; Masuda, H; Ushio, K I; Ohashi, A; Yamanashi, H; Kaneko, T; Takahashi, J I; Hosokawa, T; Hashimoto, H; Saito, T

    2001-01-01

    Various types of organic compounds have been detected in Jupiter, Titan, and cometary coma. It is probable that organic compounds were formed in primitive Earth and Mars atmospheres. Cosmic rays and solar UV are believed to be two major energy sources for organic formation in space. We examined energetics of organic formation in simulated planetary atmospheres. Gas mixtures including a C-source (carbon monoxide or methane) and a N-source (nitrogen or ammonia) was irradiated with the followings: High energy protons or electrons from accelerators, gamma-rays from 60Co, UV light from a deuterium lamp, and soft X-rays or UV light from an electron synchrotron. Amino acids were detected in the products of particles, gamma-rays and soft X-rays irradiation from each gas mixture examined. UV light gave, however, no amino acid precursors in the gas mixture of carbon monoxide, nitrogen and nitrogen. It gave only a trace of them in the gas mixture of carbon monoxide, ammonia and water or that of methane, nitrogen and water. Yield of amino acid precursors by photons greatly depended on their wavelength. These results suggest that nitrogen-containing organic compounds like amino acid precursors were formed chiefly with high energy particles, not UV photons, in Titan or primitive Earth/Mars atmospheres where ammonia is not available as a predominant N-source.

  3. Formation and emission of volatile polonium compound by microbial activity and polonium methylation with methylcobalamin.

    PubMed

    Momoshima, N; Song, L X; Osaki, S; Maeda, Y

    2001-07-15

    We observed biologically mediated emission of Po from culture solution inoculated sea sediment extract and incubated under natural light/dark cycle condition or dark condition the emitted Po compound would be lipophilic because of effective collection in organic solvent. Sterilization of the culture medium with antibiotics or CuSO4 completely suppressed growth of microorganisms and resulted in no emission of Po, indicating biological activity of microorganisms is responsible for formation and emission of volatile Po compound. Po emission also occurred when seawater was used as a culture medium. Our finding indicates a possibility of biotic source for atmospheric Po in the environment, which has been believed to be originated from abiotic sources. We compared emission behavior of Po and S in the culture experiments, the elements belong to XVI group in the Periodical Table, and consider that their emission mechanisms involved would be different though the emission of both elements is supported by biological activity of microorganisms. One of the chemical forms of S emitted was confirmed to be dimethyl sulfide (DMS) but that of Po is not known. Methylation experiments of Po with methylcobalamin demonstrated a formation and emission of volatile Po compound. The methylation of Po with methylcobalamin might be related to the observed Po emission in the culture experiments.

  4. Ammoxidation of Lignocellulosic Materials: Formation of Nonheterocyclic Nitrogenous Compounds from Monosaccharides

    PubMed Central

    2013-01-01

    Ammoxidized technical lignins are valuable soil-improving materials that share many similarities with native terrestrial humic substances. In contrast to lignins, the chemical fate of carbohydrates as typical minor constituents of technical lignins during the ammoxidation processes has not been thoroughly investigated. Recently, we reported the formation of N-heterocyclic, ecotoxic compounds (OECD test 201) from both monosaccharides (d-glucose, d-xylose) and polysaccharides (cellulose, xylan) under ammoxidation conditions and showed that monosaccharides are a source more critical than polysaccharides in this respect. GC/MS-derivatization analysis of the crude product mixtures revealed that ammoxidation of carbohydrates which resembles the conditions encountered in nonenzymatical browning of foodstuff affords also a multitude of nonheterocyclic nitrogenous compounds such as aminosugars, glycosylamines, ammonium salts of aldonic, deoxyaldonic, oxalic and carbaminic acids, urea, acetamide, α-hydroxyamides, and even minor amounts of α-amino acids. d-Glucose and d-xylose afforded largely similar product patterns which differed from each other only for those products that were formed under preservation of the chain integrity and stereoconfiguration of the respective monosaccharide. The kinetics and reaction pathways involved in the formation of the different classes of nitrogenous compounds under ammoxidation conditions are discussed. PMID:23967905

  5. Ammoxidation of lignocellulosic materials: formation of nonheterocyclic nitrogenous compounds from monosaccharides.

    PubMed

    Klinger, Karl Michael; Liebner, Falk; Hosoya, Takashi; Potthast, Antje; Rosenau, Thomas

    2013-09-25

    Ammoxidized technical lignins are valuable soil-improving materials that share many similarities with native terrestrial humic substances. In contrast to lignins, the chemical fate of carbohydrates as typical minor constituents of technical lignins during the ammoxidation processes has not been thoroughly investigated. Recently, we reported the formation of N-heterocyclic, ecotoxic compounds (OECD test 201) from both monosaccharides (D-glucose, D-xylose) and polysaccharides (cellulose, xylan) under ammoxidation conditions and showed that monosaccharides are a source more critical than polysaccharides in this respect. GC/MS-derivatization analysis of the crude product mixtures revealed that ammoxidation of carbohydrates which resembles the conditions encountered in nonenzymatical browning of foodstuff affords also a multitude of nonheterocyclic nitrogenous compounds such as aminosugars, glycosylamines, ammonium salts of aldonic, deoxyaldonic, oxalic and carbaminic acids, urea, acetamide, α-hydroxyamides, and even minor amounts of α-amino acids. D-glucose and D-xylose afforded largely similar product patterns which differed from each other only for those products that were formed under preservation of the chain integrity and stereoconfiguration of the respective monosaccharide. The kinetics and reaction pathways involved in the formation of the different classes of nitrogenous compounds under ammoxidation conditions are discussed.

  6. Influence of Sintering Time on the Structure Formation of Al-ZrW2O8 Pseudo Alloys

    NASA Astrophysics Data System (ADS)

    Shadrin, V. S.; Kulkov, S. N.

    2017-02-01

    Al – ZrW2O8 pseudo alloys were synthesized by free sintering of Al – ZrW2O8 powder mixture. Influence of sintering time on the structure formation of the pseudo alloys obtained was investigated. It has been shown that during sintering process zirconium tungstate decomposes into constituent oxides and re-synthesis of zirconium tungstate proceeds through intermediate stage – formation of WAl12 and ZrAl3 intermetallic compounds.

  7. Effect of different cooking methods on lipid oxidation and formation of volatile compounds in foal meat.

    PubMed

    Domínguez, Rubén; Gómez, María; Fonseca, Sonia; Lorenzo, José M

    2014-06-01

    The influence of four different cooking methods (roasting, grilling, microwaving and frying) on cooking loss, lipid oxidation and volatile profile of foal meat was studied. Cooking loss were significantly (P<0.001) affected by thermal treatment, being higher (32.5%) after microwaving and lower after grilling (22.5%) and frying (23.8%). As expected, all the cooking methods increased TBARs content, since high temperature during cooking causes increased oxidation in foal steaks, this increase was significantly (P<0.001) higher when foal steaks were microwaved or roasted. The four different cooking methods led to increased total volatile compounds (between 366.7 and 633.1AU×10(6)/g dry matter) compared to raw steaks (216.4AU×10(6)/g dry matter). The roasted steaks showed the highest volatile content, indicating that increased cooking temperature increases the formation of volatile compounds. Aldehydes were the most abundant compounds in cooked samples, with amounts of 217.2, 364.5, 283.5 and 409.1AU×10(6)/g dry matter in grilled, microwaved, fried and roasted samples, respectively, whereas esters were the most abundant compounds in raw samples, with mean amounts of 98.8AU×10(6)/g dry matter.

  8. Formation, transformation and superhydrophobicity of compound surfactant-assisted aligned ZnO nanoplatelets

    NASA Astrophysics Data System (ADS)

    Xue, Mingshan; Xu, Tao; Xie, Xiaolin; Ou, Junfei; Wang, Fajun; Li, Wen

    2015-11-01

    Synthesis and understanding of hierarchically nanostructured materials are significant for exploring peculiar functional properties and underlying applications. In this study, the self-assembly formation and detailed transformation process of ZnO nanoplatelets grown by hydrothermal methods with the addition of compound surfactants (CTAB and Tween-20) have been investigated. The initial growth of ZnO nanoplatelets as well as the subsequent formation of bilayer nanorod arrays and divergent nanocone arrays on the surface and side face of these nanoplatelets were found. Compared with the formation of bulk/block crystals without the case of surfactants, the addition of compound surfactants into zinc nitrate solution is responsible for the self-assembly processes of ZnO because of the effective role of CTAB in decreasing the degree of crystallinity and the positive effect of Tween-20 on decreasing the particle size owing to the space hindered effect. As-formed hierarchically micro-nanostructured ZnO exhibits superhydrophobicity without any chemical modification, which can make water droplets suspend on the air film trapped between the nanoplatelet and nanoplatelet as well as between nanocone and nanocone.

  9. Determination of volatile organic compound emissions and ozone formation from spraying solvent-based pesticides.

    PubMed

    Kumar, Anuj; Howard, Cody J; Derrick, Doniche; Malkina, Irina L; Mitloehner, Frank M; Kleeman, Michael J; Alaimo, Christopher P; Flocchini, Robert G; Green, Peter G

    2011-01-01

    Large-scale agricultural activities have come under scrutiny for possible contributions to the emission of ozone precursors. The San Joaquin Valley (SJV) of California is an area with intense agricultural activity that exceeds the federal ozone standards for more than 30 to 40 d yr(-1) and the more stringent state standards for more than 100 d yr(-1). Pesticides are used widely in both agricultural and residential subregions of the SJV, but the largest use, by weight of "active ingredient," is in agriculture. The objective of the study was to determine the role of pesticide application on airborne volatile organic compounds (VOC) concentrations and ozone formation in the SJV. The ozone formation from the pesticide formulation sprayed on commercial orchards was studied using two transportable smog chambers at four application sites during the summers of 2007 and 2008. In addition to the direct measurements of ozone formation, airborne VOC concentrations were measured before and after pesticide spraying using canister and sorbent tube sampling techniques. Soil VOC concentrations were also measured to understand the distribution of VOCs between different environmental compartments. Numerous VOCs were detected in the air and soil samples throughout the experiment but higher molecular weight aromatic hydrocarbons were the primary compounds observed in elevated concentrations immediately after pesticide spraying. Measurements indicate that the ozone concentration formed by VOC downwind of the orchard may increase up to 15 ppb after pesticide application, with a return back to prespray levels after 1 to 2 d.

  10. Compound-specific sulfur isotope analysis of thiadiamondoids of oils from the Smackover Formation, USA

    NASA Astrophysics Data System (ADS)

    Gvirtzman, Zvi; Said-Ahmad, Ward; Ellis, Geoffrey S.; Hill, Ronald J.; Moldowan, J. Michael; Wei, Zhibin; Amrani, Alon

    2015-10-01

    Thiadiamondoids (TDs) are diamond-like compounds with a sulfide bond located within the cage structure. These compounds were suggested as a molecular proxy for the occurrence and extent of thermochemical sulfate reduction (TSR). Compound-specific sulfur-isotope analysis of TDs may create a multi-parameter system, based on molecular and δ34S values that may be sensitive over a wider range of TSR and thermal maturation stages. In this study, we analyzed a suite of 12 Upper Jurassic oil and condensate samples generated from source rocks in the Smackover Formation to perform a systematic study of the sulfur isotope distribution in thiadiamondoids (one and two cages). For comparison we measured the δ34S composition of benzothiophenes (BTs) and dibenzothiophenes (DBTs). We also conducted pyrolysis experiments with petroleum and model compounds to have an insight into the formation mechanisms of TDs. The δ34S of the TDs varied significantly (ca 30‰) between the different oils depending on the degree of TSR alteration. The results showed that within the same oil, the one-cage TDs were relatively uniform, with 34S enriched values similar to those of the coexisting BTs. The two-cage TDs had more variable δ34S values that range from the δ34S values of BTs to those of the DBTs, but with general 34S depletion relative to one cage TDs. Hydrous pyrolysis experiments (360 °C, 40 h) with either CaSO4 or elemental S (equivalent S molar concentrations) and adamantane as a model compound demonstrate the formation of one cage TDs in relatively low yields (<0.2%). Higher concentrations of TDs were observed in the elemental sulfur experiments, most likely because of the higher rates of reaction with adamantane under these experimental conditions. These results show that the formation of TDs is not exclusive to TSR reactions, and that they can also form by reaction with reduced S species apart from sulfate reduction, though at low yields. Oxygenated compounds, most notably 2

  11. Compound-specific sulfur isotope analysis of thiadiamondoids of oils from the Smackover Formation, USA

    USGS Publications Warehouse

    Zvi Gvirtzman,; Ward Said-Ahmad,; Ellis, Geoffrey S.; Ronald J. Hill,; J. Michael Moldowan,; Zhibin Wei,; Alon Amrani,

    2015-01-01

    Thiadiamondoids (TDs) are diamond-like compounds with a sulfide bond located within the cage structure. These compounds were suggested as a molecular proxy for the occurrence and extent of thermochemical sulfate reduction (TSR). Compound-specific sulfur-isotope analysis of TDs may create a multi-parameter system, based on molecular and δ34S values that may be sensitive over a wider range of TSR and thermal maturation stages. In this study, we analyzed a suite of 12 Upper Jurassic oil and condensate samples generated from source rocks in the Smackover Formation to perform a systematic study of the sulfur isotope distribution in thiadiamondoids (one and two cages). For comparison we measured the δ34S composition of benzothiophenes (BTs) and dibenzothiophenes (DBTs). We also conducted pyrolysis experiments with petroleum and model compounds to have an insight into the formation mechanisms of TDs. The δ34S of the TDs varied significantly (ca 30‰) between the different oils depending on the degree of TSR alteration. The results showed that within the same oil, the one-cage TDs were relatively uniform, with 34S enriched values similar to those of the coexisting BTs. The two-cage TDs had more variable δ34S values that range from the δ34S values of BTs to those of the DBTs, but with general 34S depletion relative to one cage TDs. Hydrous pyrolysis experiments (360 °C, 40 h) with either CaSO4 or elemental S (equivalent S molar concentrations) and adamantane as a model compound demonstrate the formation of one cage TDs in relatively low yields (<0.2%). Higher concentrations of TDs were observed in the elemental sulfur experiments, most likely because of the higher rates of reaction with adamantane under these experimental conditions. These results show that the formation of TDs is not exclusive to TSR reactions, and that they can also form by reaction with reduced S species apart from sulfate reduction, though at low yields. Oxygenated compounds, most notably 2

  12. Salt lakes of Western Australia - Natural abiotic formation of volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Krause, T.; Studenroth, S.; Mulder, I.; Tubbesing, C.; Kotte, K.; Ofner, J.; Junkermann, W.; Schöler, H. F.

    2012-04-01

    Western Australia is a semi-/arid region that is heavily influenced by global climate change and agricultural land use. The area is known for its many ephemeral saline and hypersaline lakes with a wide range of hydrogeochemical parameters that have gradually changed over the last fifty years. Historically, the region was covered by eucalyptus trees and shrubs, but was cleared mainly within 10 years after WWII to make room for wheat and live stock. After the clearance of the deep rooted native plants the groundwater started to rise, bringing increased amounts of dissolved salts and minerals to the surface and discharging them into streams and lakes. Thus most of Western Australia is influenced by secondary salinisation (soil salting) [1]. Another problem is that the discharged minerals affect the pH of ground and surface water, which ranges from acidic to slightly basic. During the 2011 campaign surface water was measured with a pH between 2.5 and 7.1. Another phenomenon in Western Australia is the decrease of rainfall over the last decades assumed to be linked to the secondary salinisation. The rising saline and mineral rich groundwater increases the biotical and abiotical activity of the salt lakes. Halogenated and non-halogenated volatile organic compounds emitted from those lakes undergo fast oxidation and chemical reactions to form small particles modifying cloud microphysics and thus suppressing rain events [2]. Our objective is to gain a better understanding of this extreme environment with its hypersaline acidic lakes with regard to the potential abiotic formation of volatile organic compounds and its impact on the local climate. In spring 2011 fifty-three sediment samples from ten salt lakes in the Lake King region where taken, freeze-dried and ground. In order to simulate the abiotic formation of volatile organic compounds the soil samples were resuspended with water in gas-tight headspace vials. The headspace was measured using a purge and trap GC

  13. A comparative first-principles study on electronic structures and mechanical properties of ternary intermetallic compounds Al8Cr4Y and Al8Cu4Y: Pressure and tension effects

    NASA Astrophysics Data System (ADS)

    Yang, Wenchao; Pang, Mingjun; Tan, Yong; Zhan, Yongzhong

    2016-11-01

    An investigation into the bulk properties, elastic properties and Debye temperature under pressure, and deformation mode under tension of Al8Cu4Y and Al8Cr4Y compounds was investigated by using first principles calculations based on density functional theory. The calculated lattice constants for the ternary compounds (Al8Cu4Y and Al8Cr4Y) are in good agreement with the experimental data. It can be seen from interatomic distances that the bonding between Al1 atom and Cr, Y, and Al2 atoms in Al8Cr4Y are stronger than Al8Cu4Y. The results of cohesive energy show that Al8Cr4Y should be easier to be formed and much stronger chemical bonds than Al8Cu4Y. The bulk modulus B, shear modulus G, Young's modulus E and Poisson's ratio ν can be obtained by using the Voigt-Reuss-Hill averaging scheme. From the results of elastic properties, Al8Cr4Y has the stronger mechanical behavior than Al8Cu4Y. Our calculations also show that pressure has a greater effect on mechanical behavior for both compounds. The ideal tensile strength are obtained by stress-strain relationships under [001](001) uniaxial tensile deformation, which are 15.4 and 23.4 GPa for Al8Cu4Y and Al8Cr4Y, respectively. The total and partial density of states and electron charge density under uniaxial tensile deformations for Al8Cu4Y and Al8Cr4Y compounds are also calculated and discussed in this work.

  14. Formation Energy of Disordered Alloys form the Energetics of Ordered Compounds

    NASA Technical Reports Server (NTRS)

    Amador, Carlos; Bozzolo, Guillermo

    1994-01-01

    The cluster expansion technique is used in combination with first-principles calculations of the total energy of ordered compounds to study the energetics of the disordered phase for a number of alloy systems. The effect of short-range order, as seen in the energy differences between an alloy with the configuration corresponding to finite temperature and the perfectly random one is studied. The role of relaxation due to large size mismatch is discussed in terms of an effective cluster volume approximation. Very good agreement with measured energies of formation is obtained when short-range order and relaxation effects are taken into account.

  15. Spark plasma sintering of titanium aluminide intermetallics and its composites

    NASA Astrophysics Data System (ADS)

    Aldoshan, Abdelhakim Ahmed

    Titanium aluminide intermetallics are a distinct class of engineering materials having unique properties over conventional titanium alloys. gamma-TiAl compound possesses competitive physical and mechanical properties at elevated temperature applications compared to Ni-based superalloys. gamma-TiAl composite materials exhibit high melting point, low density, high strength and excellent corrosion resistance. Spark plasma sintering (SPS) is one of the powder metallurgy techniques where powder mixture undergoes simultaneous application of uniaxial pressure and pulsed direct current. Unlike other sintering techniques such as hot iso-static pressing and hot pressing, SPS compacts the materials in shorter time (< 10 min) with a lower temperature and leads to highly dense products. Reactive synthesis of titanium aluminide intermetallics is carried out using SPS. Reactive sintering takes place between liquid aluminum and solid titanium. In this work, reactive sintering through SPS was used to fabricate fully densified gamma-TiAl and titanium aluminide composites starting from elemental powders at different sintering temperatures. It was observed that sintering temperature played significant role in the densification of titanium aluminide composites. gamma-TiAl was the predominate phase at different temperatures. The effect of increasing sintering temperature on microhardness, microstructure, yield strength and wear behavior of titanium aluminide was studied. Addition of graphene nanoplatelets to titanium aluminide matrix resulted in change in microhardness. In Ti-Al-graphene composites, a noticeable decrease in coefficient of friction was observed due to the influence of self-lubrication caused by graphene.

  16. Formation mechanisms of water-soluble organic compounds in atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Huang, Xiaofeng

    Water-soluble organic compounds (WSOCs) are abundant in atmospheric aerosols, typically accounting for 20˜80% of particulate organic matter mass. Due to their affinity for water, WSOCs play an active role in aerosol-water interaction, and thus influence hygroscopic properties of aerosols, which in turn affect cloud formation processes and earth's radiation balance. Despite their abundance and significance, the sources of WSOCs are not well understood. Some primary sources (e.g., biomass burning) are known to emit WSOCs. It is also known from smog chamber experiments that photochemical oxidation of volatile organic compounds lead to less volatile oxygenated compounds that reside in the aerosol phase and are water-soluble because of the presence of polar functional groups. More recent work points to in-cloud/fog processes as a potentially important source for WSOCs. Work in this thesis aims to improve our understanding of the sources and formation mechanisms of WSOCs in atmospheric aerosols. Multiple approaches have been taken, including field measurements and controlled laboratory experiments. The thesis consists of the following four parts: (1) The formation mechanism of the most abundant WSOC species, oxalate, was investigated by synthesizing field measurement data obtained by our group and those available in the literature. Our measurements of aerosol sulfate and oxalate across a wide geographical span in the East Asia region, up to Beijing in the north and down to Hong Kong in the south, indicated that the two species were highly correlated. This good correlation was also found in measurements made elsewhere in the world by other researchers. Through a detailed analysis of factors influencing ambient oxalate, it can be argued that a common dominant formation pathway, likely in-cloud processing, explains the close tracking of the two chemically distinct species. This result also highlights the potential importance of in-cloud processing as a pathway leading to

  17. Computational Simulation of Equivalence Class Formation Using the go/no-go Procedure with Compound Stimuli.

    PubMed

    Vernucio, Renato Roberto; Debert, Paula

    Research about equivalence has commonly utilized human participants as experimental subjects. More recently, computational models have been capable of reproducing performances observed in experiments with humans. The computational model often utilized is called RELNET, and it simulates training and testing trials of conditional relations using the matching-to-sample procedure (MTS). The differentiation between sample stimulus and comparison stimuli, indispensable in MTS, implies operational difficulties for simulations. For this reason, new studies seek to utilize alternative procedures to MTS, which do not differentiate the functions of the antecedent stimuli. This work evaluated the possibility of developing a new computational model to simulate equivalence class formation using the go/no-go procedure with compound stimuli. In Experiment 1, artificial neural networks were utilized to simulate training of the AB and BC relations as well as the testing of the AC relation. The results showed that four out of six runs demonstrated equivalence class formation. Experiment 2 evaluated whether the additional class training performed in Experiment 1, which was analogous to the simulation of pre-experimental experience of human participants, would be essential for simulating the establishment of equivalence classes. It was found that it was not possible to simulate equivalence class formation without the additional class training. Altogether, the experiments show that it is possible to simulate equivalence class formation using the go/no-go procedure with compound stimuli and that it is necessary to conduct additional class training. The model developed is, therefore, an alternative to RELNET for the study of equivalence relations using computational simulations.

  18. Polar intermetallic compounds as catalysts for hydrogenation reactions: synthesis, structures, bonding, and catalytic properties of Ca(1-x)Sr(x)Ni4Sn2 (x=0.0, 0.5, 1.0) and catalytic properties of Ni3Sn and Ni3Sn2.

    PubMed

    Hlukhyy, Viktor; Raif, Fabian; Claus, Peter; Fässler, Thomas F

    2008-01-01

    The potential of polar intermetallic compounds to catalyze hydrogenation reactions was evaluated. The novel compounds CaNi4Sn2, SrNi4Sn2, and Ca(0.5)Sr(0.5)Ni(4)Sn(2) were tested as unsupported alloys in the liquid-phase hydrogenation of citral. Depending on the reaction conditions, conversions of up to 21.0 % (253 K and 9.0 MPa hydrogen pressure) were reached. The binary compounds Ni3Sn and Ni3Sn2 were also tested in citral hydrogenation under the same conditions. These materials gave conversions of up to 37.5 %. The product mixtures contained mainly geraniol, nerol, citronellal, and citronellol. The isotypic stannides CaNi4Sn2, Ca(0.5)Sr(0.5)Ni4Sn2, and SrNi4Sn2 were obtained by melting mixtures of the elements in an arc-furnace under an argon atmosphere. Single crystals were synthesized in tantalum ampoules using special temperature modes. The novel structures were established by single-crystal X-ray diffraction. They crystallize in the tetragonal space group I4/mcm with parameters: a=7.6991(7), c=7.8150(8) A, wR2=0.034, 162 F(2) values, 14 variable parameters for CaNi4Sn2; a=7.7936(2), c=7.7816(3) A, wR2=0.052, 193 F(2) values, 15 variable parameters for Ca(0.5)Sr(0.5)Ni4Sn2; and a=7.8916(4), c=7.7485(5) A, wR2=0.071, 208 F(2) values, 14 variable parameters for SrNi4Sn2. The Ca(1-x)Sr(x)Ni(4)Sn(2) (x=0.0, 0.5, 1.0) structures can be represented as a stuffed variant of the CuAl2 type by the formal insertion of one-dimensional infinite Ni-cluster chains [Ni4] into the Ca(Sr)Sn2 substructure. The Ni and Sn atoms form a three-dimensional infinite [Ni4Sn2] network in which the Ca or Sr atoms fill distorted octagonal channels. The densities of states obtained from TB-LMTO-ASA calculations show metallic character for both compounds.

  19. Wet chemical synthesis of intermetallic Pt3Zn nanocrystals via weak reduction reaction together with UPD process and their excellent electrocatalytic performances.

    PubMed

    Chen, Qiaoli; Zhang, Jiawei; Jia, Yanyan; Jiang, Zhiyuan; Xie, Zhaoxiong; Zheng, Lansun

    2014-06-21

    Platinum based alloy nanocrystals are promising catalysts for a variety of important practical process. However, it remains a great challenge to synthesize platinum-based intermetallic compound nanocrystals with well-defined surface structures. In this communication, taking the synthesis of concave cubic intermetallic Pt3Zn nanocrystals with {hk0} facets as an example, we proposed a new synthesis strategy for intermetallic compounds by reduction of noble metal precursors via a slow reduction process and reduction of transition metal ions via an underpotential deposition (UPD) process in wet chemical synthesis. The as-prepared intermetallic Pt3Zn nanocrystals exhibited superior CO poisoning tolerance and high electro-catalytic activity in both methanol and formic acid oxidation reactions in comparison with solid solution Pt3Zn nanocrystals and Pt/C.

  20. Surfaces of Intermetallics: Quasicrystals and Beyond

    SciTech Connect

    Yuen, Chad

    2012-01-01

    The goal of this work is to characterize surfaces of intermetallics, including quasicrystals. In this work, surface characterization is primarily focused on composition and structure using X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM) performed under ultrahigh vacuum (UHV) conditions.

  1. The synthesis and formation process of a new cubic conductive Cu7O(8-y)(NO3) compound

    NASA Astrophysics Data System (ADS)

    Yazawa, Ichiro; Sugise, Ryoji; Terada, Norio; Jo, Masatoshi; Oka, Kunihiko

    1990-08-01

    The synthesis and formation process of a new cubic conductive Cu7O(8-y)(NO3) compound was studied. This material was formed as an intermediate compound in the decomposition process of copper nitrate by a firing process in oxygen flowing gas. It has a CuO2 plane in its lattice structure and is a parent material of the new metallic copper oxide compounds.

  2. Organic nitrate aerosol formation via NO3 + biogenic volatile organic compounds in the southeastern United States

    NASA Astrophysics Data System (ADS)

    Ayres, B. R.; Allen, H. M.; Draper, D. C.; Brown, S. S.; Wild, R. J.; Jimenez, J. L.; Day, D. A.; Campuzano-Jost, P.; Hu, W.; de Gouw, J.; Koss, A.; Cohen, R. C.; Duffey, K. C.; Romer, P.; Baumann, K.; Edgerton, E.; Takahama, S.; Thornton, J. A.; Lee, B. H.; Lopez-Hilfiker, F. D.; Mohr, C.; Wennberg, P. O.; Nguyen, T. B.; Teng, A.; Goldstein, A. H.; Olson, K.; Fry, J. L.

    2015-12-01

    Gas- and aerosol-phase measurements of oxidants, biogenic volatile organic compounds (BVOCs) and organic nitrates made during the Southern Oxidant and Aerosol Study (SOAS campaign, Summer 2013) in central Alabama show that a nitrate radical (NO3) reaction with monoterpenes leads to significant secondary aerosol formation. Cumulative losses of NO3 to terpenes are correlated with increase in gas- and aerosol-organic nitrate concentrations made during the campaign. Correlation of NO3 radical consumption to organic nitrate aerosol formation as measured by aerosol mass spectrometry and thermal dissociation laser-induced fluorescence suggests a molar yield of aerosol-phase monoterpene nitrates of 23-44 %. Compounds observed via chemical ionization mass spectrometry (CIMS) are correlated to predicted nitrate loss to BVOCs and show C10H17NO5, likely a hydroperoxy nitrate, is a major nitrate-oxidized terpene product being incorporated into aerosols. The comparable isoprene product C5H9NO5 was observed to contribute less than 1 % of the total organic nitrate in the aerosol phase and correlations show that it is principally a gas-phase product from nitrate oxidation of isoprene. Organic nitrates comprise between 30 and 45 % of the NOy budget during SOAS. Inorganic nitrates were also monitored and showed that during incidents of increased coarse-mode mineral dust, HNO3 uptake produced nitrate aerosol mass loading at a rate comparable to that of organic nitrate produced via NO3 + BVOCs.

  3. Volatile and intermediate volatility organic compounds in suburban Paris: variability, origin and importance for SOA formation

    NASA Astrophysics Data System (ADS)

    Ait-Helal, W.; Borbon, A.; Sauvage, S.; de Gouw, J. A.; Colomb, A.; Gros, V.; Freutel, F.; Crippa, M.; Afif, C.; Baltensperger, U.; Beekmann, M.; Doussin, J.-F.; Durand-Jolibois, R.; Fronval, I.; Grand, N.; Leonardis, T.; Lopez, M.; Michoud, V.; Miet, K.; Perrier, S.; Prévôt, A. S. H.; Schneider, J.; Siour, G.; Zapf, P.; Locoge, N.

    2014-10-01

    Measurements of gaseous and particulate organic carbon were performed during the MEGAPOLI experiments, in July 2009 and January-February 2010, at the SIRTA observatory in suburban Paris. Measurements comprise primary and secondary volatile organic compounds (VOCs), of both anthropogenic and biogenic origins, including C12-C16 n-alkanes of intermediate volatility (IVOCs), suspected to be efficient precursors of secondary organic aerosol (SOA). The time series of gaseous carbon are generally consistent with times series of particulate organic carbon at regional scale, and are clearly affected by meteorology and air mass origin. Concentration levels of anthropogenic VOCs in urban and suburban Paris were surprisingly low (2-963 ppt) compared to other megacities worldwide and to rural continental sites. Urban enhancement ratios of anthropogenic VOC pairs agree well between the urban and suburban Paris sites, showing the regional extent of anthropogenic sources of similar composition. Contrary to other primary anthropogenic VOCs (aromatics and alkanes), IVOCs showed lower concentrations in winter (< 5 ppt) compared to summer (13-27 ppt), which cannot be explained by the gas-particle partitioning theory. Higher concentrations of most oxygenated VOCs in winter (18-5984 ppt) suggest their dominant primary anthropogenic origin. The respective role of primary anthropogenic gaseous compounds in regional SOA formation was investigated by estimating the SOA mass concentration expected from the anthropogenic VOCs and IVOCs (I / VOCs) measured at SIRTA. From an integrated approach based on emission ratios and SOA yields, 38 % of the SOA measured at SIRTA is explained by the measured concentrations of I / VOCs, with a 2% contribution by C12-C16 n-alkane IVOCs. From the results of an alternative time-resolved approach, the average IVOC contribution to SOA formation is estimated to be 7%, which is half of the average contribution of the traditional aromatic compounds (15%). Both

  4. Formation risk of toxic and other unwanted compounds in pressure-assisted thermally processed foods.

    PubMed

    Bravo, K Segovia; Ramírez, R; Durst, R; Escobedo-Avellaneda, Z J; Welti-Chanes, J; Sanz, P D; Torres, J A

    2012-01-01

    Consumers demand, in addition to excellent eating quality, high standards of microbial and chemical safety in shelf-stable foods. This requires improving conventional processing technologies and developing new alternatives such as pressure-assisted thermal processing (PATP). Studies in PATP foods on the kinetics of chemical reactions at temperatures (approximately 100 to 120 °C) inactivating bacterial spores in low-acid foods are severely lacking. This review focuses on a specific chemical safety risk in PATP foods: models predicting if the activation volume value (V(a) ) of a chemical reaction is positive or negative, and indicating if the reaction rate constant will decrease or increase with pressure, respectively, are not available. Therefore, the pressure effect on reactions producing toxic compounds must be determined experimentally. A recent model solution study showed that acrylamide formation, a potential risk in PATP foods, is actually inhibited by pressure (that is, its V(a) value must be positive). This favorable finding was not predictable and still needs to be confirmed in food systems. Similar studies are required for other reactions producing toxic compounds including polycyclic aromatic hydrocarbons, heterocyclic amines, N-nitroso compounds, and hormone like-peptides. Studies on PATP inactivation of prions, and screening methods to detect the presence of other toxicity risks of PATP foods, are also reviewed.

  5. Wet chemical synthesis of intermetallic Pt3Zn nanocrystals via weak reduction reaction together with UPD process and their excellent electrocatalytic performances

    NASA Astrophysics Data System (ADS)

    Chen, Qiaoli; Zhang, Jiawei; Jia, Yanyan; Jiang, Zhiyuan; Xie, Zhaoxiong; Zheng, Lansun

    2014-05-01

    Platinum based alloy nanocrystals are promising catalysts for a variety of important practical process. However, it remains a great challenge to synthesize platinum-based intermetallic compound nanocrystals with well-defined surface structures. In this communication, taking the synthesis of concave cubic intermetallic Pt3Zn nanocrystals with {hk0} facets as an example, we proposed a new synthesis strategy for intermetallic compounds by reduction of noble metal precursors via a slow reduction process and reduction of transition metal ions via an underpotential deposition (UPD) process in wet chemical synthesis. The as-prepared intermetallic Pt3Zn nanocrystals exhibited superior CO poisoning tolerance and high electro-catalytic activity in both methanol and formic acid oxidation reactions in comparison with solid solution Pt3Zn nanocrystals and Pt/C.Platinum based alloy nanocrystals are promising catalysts for a variety of important practical process. However, it remains a great challenge to synthesize platinum-based intermetallic compound nanocrystals with well-defined surface structures. In this communication, taking the synthesis of concave cubic intermetallic Pt3Zn nanocrystals with {hk0} facets as an example, we proposed a new synthesis strategy for intermetallic compounds by reduction of noble metal precursors via a slow reduction process and reduction of transition metal ions via an underpotential deposition (UPD) process in wet chemical synthesis. The as-prepared intermetallic Pt3Zn nanocrystals exhibited superior CO poisoning tolerance and high electro-catalytic activity in both methanol and formic acid oxidation reactions in comparison with solid solution Pt3Zn nanocrystals and Pt/C. Electronic supplementary information (ESI) available: Additional characterization data. See DOI: 10.1039/c4nr00313f

  6. Optimization of an Escherichia coli formate dehydrogenase assay for selenium compounds.

    PubMed

    Tschursin, E; Wolf, W R; Lacroix, D; Veillon, C; Patterson, K Y

    1994-12-01

    A microbiological assay to detect different chemical compounds of selenium for potential future use in the study of the distribution of these chemical forms in foods is being developed. This assay is based on the detection, by infrared analysis, of CO2 in a culture of Escherichia coli when the bacteria are grown in the presence of various selenium compounds. The CO2 production is the result of selenium-dependent formate dehydrogenase activity, which catalyzes oxidation of formic acid produced during glucose metabolism. Smooth response curves were generated over several orders of magnitude for selenocystine, selenite, and selenomethionine. The assay detects selenium concentrations (above background) as low as 1.5 nM for selenocystine and selenite and 4 nM for selenomethionine in minimal medium. Detection of selenomethionine was enhanced (to a sensitivity of 1.5 nM) by the addition of methionine to minimal medium and was enhanced even further (to a sensitivity of 0.8 nM) by the addition of a defined mixture of amino acids. Selenomethionine could be assayed in the presence of an amino acid concentration which is proportional to the amino acid/elemental selenium ratio found in a wheat gluten reference material (NIST SRM 8418). This implies that the assay can detect selenium compounds in a variety of foods at low concentrations, avoiding the background CO2 production caused by high concentrations of non-selenium-containing amino acids. The observation that methionine enhanced selenomethionine availability for formate dehydrogenase synthesis supports studies in animals demonstrating that methionine controls selenomethionine incorporation into selenoenzymes.(ABSTRACT TRUNCATED AT 250 WORDS)

  7. Optimization of an Escherichia coli formate dehydrogenase assay for selenium compounds.

    PubMed Central

    Tschursin, E; Wolf, W R; Lacroix, D; Veillon, C; Patterson, K Y

    1994-01-01

    A microbiological assay to detect different chemical compounds of selenium for potential future use in the study of the distribution of these chemical forms in foods is being developed. This assay is based on the detection, by infrared analysis, of CO2 in a culture of Escherichia coli when the bacteria are grown in the presence of various selenium compounds. The CO2 production is the result of selenium-dependent formate dehydrogenase activity, which catalyzes oxidation of formic acid produced during glucose metabolism. Smooth response curves were generated over several orders of magnitude for selenocystine, selenite, and selenomethionine. The assay detects selenium concentrations (above background) as low as 1.5 nM for selenocystine and selenite and 4 nM for selenomethionine in minimal medium. Detection of selenomethionine was enhanced (to a sensitivity of 1.5 nM) by the addition of methionine to minimal medium and was enhanced even further (to a sensitivity of 0.8 nM) by the addition of a defined mixture of amino acids. Selenomethionine could be assayed in the presence of an amino acid concentration which is proportional to the amino acid/elemental selenium ratio found in a wheat gluten reference material (NIST SRM 8418). This implies that the assay can detect selenium compounds in a variety of foods at low concentrations, avoiding the background CO2 production caused by high concentrations of non-selenium-containing amino acids. The observation that methionine enhanced selenomethionine availability for formate dehydrogenase synthesis supports studies in animals demonstrating that methionine controls selenomethionine incorporation into selenoenzymes.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7811071

  8. 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.

  9. Natural compounds containing a catechol group enhance the formation of Nε-(carboxymethyl)lysine of the Maillard reaction.

    PubMed

    Fujiwara, Yukio; Kiyota, Naoko; Tsurushima, Keiichiro; Yoshitomi, Makiko; Mera, Katsumi; Sakashita, Naomi; Takeya, Motohiro; Ikeda, Tsuyoshi; Araki, Tomohiro; Nohara, Toshihiro; Nagai, Ryoji

    2011-04-01

    Inhibition of advanced glycation end-product (AGE) formation is a potential strategy for the prevention of clinical diabetes complications. Screening for new AGE inhibitors revealed several natural compounds that inhibited the formation of N(ε)-(carboxymethyl)lysine (CML), a major antigenic AGE structure, whereas natural compounds containing a catechol group, such as gallic acid and epicatechin, significantly enhanced CML formation. A similar enhancing effect was also observed by culturing THP-1 macrophages in the presence of catechol compounds. Although 4-methylcatechol significantly enhanced CML formation from glycated HSA (gHSA), a model for Amadori proteins, analogues of catechol such as 5-methylresorcinol and methylhydroquinone showed no enhancing effect. Even though 1mM 4-methylcatechol, epicatechin, and gallic acid significantly enhanced CML formation from gHSA, it was significantly inhibited by decreasing their concentration. The enhancing effect of 1mM catechol compounds was inhibited in the presence of the glutathione peroxidase system, thus demonstrating that hydrogen peroxide generated from catechol compounds plays an important role in the enhancement of CML formation. Furthermore, administration of 500mg/kg/day epicatechin to STZ-induced diabetic mice for 45days enhanced CML accumulation at the surface area of gastric epithelial cells in the stomach. This study provides the first evidence that high amounts of catechol-containing structures enhance oxidative stress, thus leading to enhanced CML formation, and this phenomenon may explain the paradoxical effect that some flavonoids have on redox status.

  10. Incremental Reactivity Effects of Anthropogenic and Biogenic Volatile Organic Compounds on Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Kacarab, M.; Li, L.; Carter, W. P. L.; Cocker, D. R., III

    2015-12-01

    Two surrogate reactive organic gas (ROG) mixtures were developed to create a controlled reactivity environment simulating different urban atmospheres with varying levels of anthropogenic (e.g. Los Angeles reactivity) and biogenic (e.g. Atlanta reactivity) influences. Traditional chamber experiments focus on the oxidation of one or two volatile organic compound (VOC) precursors, allowing the reactivity of the system to be dictated by those compounds. Surrogate ROG mixtures control the overall reactivity of the system, allowing for the incremental aerosol formation from an added VOC to be observed. The surrogate ROG mixtures were developed based on that used to determine maximum incremental reactivity (MIR) scales for O3 formation from VOC precursors in a Los Angeles smog environment. Environmental chamber experiments were designed to highlight the incremental aerosol formation in the simulated environment due to the addition of an added anthropogenic (aromatic) or biogenic (terpene) VOC. All experiments were conducted in the UC Riverside/CE-CERT dual 90m3 environmental chambers. It was found that the aerosol precursors behaved differently under the two altered reactivity conditions, with more incremental aerosol being formed in the anthropogenic ROG system than in the biogenic ROG system. Further, the biogenic reactivity condition inhibited the oxidation of added anthropogenic aerosol precursors, such as m-xylene. Data will be presented on aerosol properties (density, volatility, hygroscopicity) and bulk chemical composition in the gas and particle phases (from a SYFT Technologies selected ion flow tube mass spectrometer, SIFT-MS, and Aerodyne high resolution time of flight aerosol mass spectrometer, HR-ToF-AMS, respectively) comparing the two controlled reactivity systems and single precursor VOC/NOx studies. Incremental aerosol yield data at different controlled reactivities provide a novel and valuable insight in the attempt to extrapolate environmental chamber

  11. Formation of nitroaromatic compounds in advanced oxidation processes: Photolysis versus photocatalysis

    SciTech Connect

    Dzengel, J.; Theurich, J.; Bahnemann, D.W.

    1999-01-15

    There is a growing demand for efficient treatment of organic polluted wastewaters by advanced oxidation processes (AOPs). Besides optimization of the processes, the detailed understanding of degradation mechanisms and interactions of organic pollutants with inorganic substrates is important for technical applications of AOPs. Therefore, the aim of the present study was to investigate the influence of nitrate ions on the photooxidation of phenol for various AOPs at different pH values. Three different oxidation processes were compared in these studies: direct photolysis, TiO{sub 2}/UV, and H{sub 2}O{sub 2}/UV. Special emphasis has been laid on the analysis of byproducts especially on the formation of nitroaromatic compounds. The formation of intermediates as well as the depletion of phenol were monitored by HPLC technique. The total organic carbon content, TOC, was measured to monitor the mineralization. Highest degradation rates and lowest concentrations of intermediates were observed with TiO{sub 2}/UV being the AOP. Formation of highly toxic nitrophenols was only observed when homogeneous AOPs were employed. For the TiO{sub 2}/UV process no formation of Nitroaromatic byproducts occurred. At pH 5 formation of nitrophenols was observed employing direct photolysis in the presence of NO{sub 2}{sup {minus}}, while with H{sub 2}O{sub 2}/UV nitrophenols were detected only when the concentration of NO{sub 2}{sup {minus}} was higher than that of H{sub 2}O{sub 2}. At pH 11 no nitroaromatic intermediates were found for any AOPs compared in this study.

  12. Quaternary borocarbides: New class of intermetallic superconductors

    NASA Technical Reports Server (NTRS)

    Nagarajan, R.; Gupta, L. C.; Dhar, S. K.; Mazumdar, Chandan; Hossain, Zakir; Godart, C.; Levy-Clement, C.; Padalia, B. D.; Vijayaraghavan, R.

    1995-01-01

    Our recent discovery of superconductivity (SC) in the four-element multiphase Y-Ni-B-C system at an elevated temperature (TC approximately 12 K) has opened up great possibilities of identifying new superconducting materials and generating new physics. Superconductivity with Tc (greater than 20 K) higher than that known so far in bulk intermetallics has been observed in multiphase Y-Pd-B-C and Th-Pd-B-C systems and a family of single phase materials RENi2B2C (RE= Y, rare earth) have been found. Our investigations show YNi2B2C to be a strong coupling hard type-II SC. HC2(T) exhibits an unconventional temperature dependence. Specific heat and magnetization studies reveal coexistence of SC and magnetism in RNi2B2C (R = Ho, Er, Tm) with magnetic ordering temperatures (Tc approximately 8 K, 10.5 K, 11 K and Tm approximately 5 K, approximately 7K, approximately 4 K respectively) that are remarkably higher than those in known magnetic superconductors . Mu-SR studies suggest the possibility of Ni atoms carrying a moment in TmNi2B2C. Resistivity results suggests a double re-entrant transition (SC-normal-SC) in HoNi2B2C. RENi2B2C (RE = Ce, Nd, Gd) do not show SC down to 4.2 K. The Nd- and Gd-compounds order magnetically at approximately 4.5 K and approximately 19.5 K, respectively. Two SC transitions are observed in Y-Pd-B-C (Tc approximately 22 K, approximately 10 K) and in Th-Pd-B-C (Tc approximately 20 K, approximately 14 K) systems, which indicate that there are at least two structures which support SC in these borocarbides. In our multiphase ThNi2B2C we observe SC at approximately 6 K. No SC was seen in multiphase UNi2B2C, UPd2B2C, UOs2Ge2C and UPd5B3C(0.35) down to 4.2 K. Tc in YNi2B2C is depressed by substitutions (Gd, Th and U at Y-sites and Fe, Co at Ni-sites).

  13. Cloud processing of organic compounds: Secondary organic aerosol and nitrosamine formation

    NASA Astrophysics Data System (ADS)

    Hutchings, James W., III

    Cloud processing of atmospheric organic compounds has been investigated through field studies, laboratory experiments, and numerical modeling. Observational cloud chemistry studies were performed in northern Arizona and fog studies in central Pennsylvania. At both locations, the cloud and fogs showed low acidity due to neutralization by soil dust components (Arizona) and ammonia (Pennsylvania). The field observations showed substantial concentrations (20-5500 ng•L -1) of volatile organic compounds (VOC) in the cloud droplets. The potential generation of secondary organic aerosol mass through the processing of these anthropogenic VOCs was investigated through laboratory and modeling studies. Under simulated atmospheric conditions, in idealized solutions, benzene, toluene, ethylbenzene, and xylene (BTEX) degraded quickly in the aqueous phase with half lives of approximately three hours. The degradation process yielded less volatile products which would contribute to new aerosol mass upon cloud evaporation. However, when realistic cloud solutions containing natural organic matter were used in the experiments, the reaction kinetics decreased with increasing organic carbon content, resulting in half lives of approximately 7 hours. The secondary organic aerosol (SUA) mass formation potential of cloud processing of BTEX was evaluated. SOA mass formation by cloud processing of BTEX, while strongly dependent on the atmospheric conditions, could contribute up to 9% of the ambient atmospheric aerosol mass, although typically ˜1% appears realistic. Field observations also showed the occurrence of N-nitrosodimethylamine (NDMA), a potent carcinogen, in fogs and clouds (100-340 ng•L -1). Laboratory studies were conducted to investigate the formation of NDMA from nitrous acid and dimethylamine in the homogeneous aqueous phase within cloud droplets. While NDMA was produced in the cloud droplets, the low yields (<1%) observed could not explain observational concentrations

  14. Effect of ajoene, the major antiplatelet compound from garlic, on platelet thrombus formation.

    PubMed

    Apitz-Castro, R; Badimon, J J; Badimon, L

    1992-10-15

    Ajoene, (E,Z)-4,5,9-trithiadodeca-1,6,11-triene 9-oxide, is a potent antiplatelet compound isolated from alcoholic extracts of garlic (Allium sativum). Ajoene reversibly inhibits in vitro platelet aggregation as well as release reaction induced by all known agonists. We used a well characterized cylindrical perfusion chamber to study the effect of ajoene on platelet deposition onto physiological substrates such as pig aortic subendothelium and tunica media as a model of mildly and severely damaged vessel wall respectively. Experiments were performed under flow conditions of high and low shear rate that mimic laminar blood flow in small and medium size arteries (1690 sec-1 and 212 sec-1). Our results indicate that ajoene prevents thrombus formation both at low and high shear rate in citrated whole blood. The inhibitory effect of ajoene on platelet-thrombus formation seems to be dependent on its inhibition of fibrinogen binding, since significantly higher concentrations of ajoene are needed to affect von Willebrand factor binding to GPIIb/IIIa receptors. Further, ajoene does not impair Ristocetin-induced platelet agglutination, mediated by GPIb. Our results suggest that ajoene may be useful for the acute prevention of thrombus formation induced by vascular damage.

  15. SOA formation by biogenic and carbonyl compounds: data evaluation and application.

    PubMed

    Ervens, Barbara; Kreidenweis, Sonia M

    2007-06-01

    The organic fraction of atmospheric aerosols affects the physical and chemical properties of the particles and their role in the climate system. Current models greatly underpredict secondary organic aerosol (SOA) mass. Based on a compilation of literature studies that address SOA formation, we discuss different parameters that affect the SOA formation efficiency of biogenic compounds (alpha-pinene, isoprene) and aliphatic aldehydes (glyoxal, hexanal, octanal, hexadienal). Applying a simple model, we find that the estimated SOA mass after one week of aerosol processing under typical atmospheric conditions is increased by a few microg m(-3) (low NO(x) conditions). Acid-catalyzed reactions can create > 50% more SOA mass than processes under neutral conditions; however, other parameters such as the concentration ratio of organics/NO(x), relative humidity, and absorbing mass are more significant. The assumption of irreversible SOA formation not limited by equilibrium in the particle phase or by depletion of the precursor leads to unrealistically high SOA masses for some of the assumptions we made (surface vs volume controlled processes).

  16. Design of Bulk Metallic Glasses and Glass Matrix Composites Near Intermetallic Composition by the Principle of Competitive Growth

    NASA Astrophysics Data System (ADS)

    Ma, G. Z.; Chen, D.

    2016-11-01

    A Cu49Zr51 intermetallic is used as a base for synthesizing metallic glasses and composites with glass matrixes [(Cu49Zr51)100 - x Al x , where x = 0, 2, 4, 6, 8, 10 and 12 at.%]. The introduction of aluminum raises the microhardness and the ultimate compressive strength. In addition, the suppression of formation of crystalline phase upon the introduction of 8 at.% Al provides a glass-like structure in alloy (Cu49Zr51)92Al8. The formation of the glass-like structure is discussed within the concept of competitive nucleation of different intermetallics.

  17. Negative thermal expansion induced by intermetallic charge transfer

    PubMed Central

    Azuma, Masaki; Oka, Kengo; Nabetani, Koichiro

    2015-01-01

    Suppression of thermal expansion is of great importance for industry. Negative thermal expansion (NTE) materials which shrink on heating and expand on cooling are therefore attracting keen attention. Here we provide a brief overview of NTE induced by intermetallic charge transfer in A-site ordered double perovskites SaCu3Fe4O12 and LaCu3Fe4−xMnxO12, as well as in Bi or Ni substituted BiNiO3. The last compound shows a colossal dilatometric linear thermal expansion coefficient exceeding −70 × 10−6 K−1 near room temperature, in the temperature range which can be controlled by substitution. PMID:27877801

  18. High pressure Mössbauer studies of magnetic Np intermetallics

    NASA Astrophysics Data System (ADS)

    Moser, J.; Gal, J.; Potzel, W.; Wortmann, G.; Kalvius, G. M.; Dunlap, B. D.; Lam, D. J.; Spirlet, J. C.

    1980-10-01

    A high pressure (50 kbar) Mössbauer spectrometer for the 60 keV resonance in 237Np for temperatures between 1.4 and 100 K is described. It was used to study the magnetic properties of some neptunium intermetallics under pressure. For the cubic Laves phase compounds NpOs 2 and NpAl 2 a drastic decrease of the ordering temperature, the hyperfine field, and the isomer shift under increasing pressure was observed. It shows that their magnetic properties are primarily determined by the Np-Np separation which controls the width and hybridization of the 5f band. In contrast, an increase of ordering temperature coupled with a decrease of isomer shift with pressure was found in tetragonal NpCo 2Si 2, while the hyperfine field remains constant. This suggests that its magnetic properties must arise from different sources.

  19. Process for synthesizing compounds from elemental powders and product

    DOEpatents

    Rabin, Barry H.; Wright, Richard N.

    1993-01-01

    A process for synthesizing intermetallic compounds from elemental powders. The elemental powders are initially combined in a ratio which approximates the stoichiometric composition of the intermetallic compound. The mixed powders are then formed into a compact which is heat treated at a controlled rate of heating such that an exothermic reaction between the elements is initiated. The heat treatment may be performed under controlled conditions ranging from a vacuum (pressureless sintering) to compression (hot pressing) to produce a desired densification of the intermetallic compound. In a preferred form of the invention, elemental powders of Fe and Al are combined to form aluminide compounds of Fe.sub.3 Al and FeAl.

  20. [Effect of cyclic compounds on pigment formation in Aspergillus niger cultures].

    PubMed

    Malama, A A; Smirnova, L A

    1975-01-01

    The mycelial pigment os Asp. niger VP has been fractionated into four fractions ehose solubility is similar to melanin pigments obtained from other sources. The addition of pyrocatechol, L-aspartic, benzoic, kojic and salicylic acids to the liquid Capek medium stimulates the fungal growth but diminishes the yield of fractions of the melanin pigment from the mycelium. Cinnamic acid does not influence the growth but also decreases the yield of the pigment. DL-tyrosine stimulates the fungal growth and produces no influence on the total yield of fractions 2, 3 and 4 from the mycelial pigment. All the cyclic compounds enhance the pigmentation of the culture liquid and give rise to the formation of fractions 2 and 3 of the melanin pigment. This latter constitutes a substantial portion of the dry matter of the fungal cell. The pigment content in the mycelium is much higher than that in the culture liquid of the corresponding culture.

  1. Identification of volatile organic compounds in suburban Bangkok, Thailand and their potential for ozone formation

    NASA Astrophysics Data System (ADS)

    Suthawaree, Jeeranut; Tajima, Yosuke; Khunchornyakong, Alisa; Kato, Shungo; Sharp, Alice; Kajii, Yoshizumi

    2012-02-01

    Measurement of Volatile Organic Compound (VOC) was carried out in suburban Bangkok during July 2-8, 2008. Analysis was performed using GC-FID and GC-MS. High mixing ratios of VOCs detected during the morning and evening are most likely due to vehicular emissions. Averaged VOC mixing ratios revealed distinct difference between mixing ratios of weekdays and weekend, which the latter were found to be lower. The most abundance species were propane and toluene. Ratios of benzene over toluene suggested that additional toluene mixing ratios was owing to industrial emission, which was particularly larger during weekdays. Comparison between C2Cl4 and CH3Cl mixing ratios obtained for suburban Tokyo reveal a relatively lower influence of biomass burning than suburban Bangkok. Elucidating by Ozone Formation Potential, toluene was found to contribute the most to O3 production followed by ethylene, m-,p-xylene, and propylene.

  2. Formation, characterization and computational studies of mono- and dinuclear rhenium(I) chromone compounds

    NASA Astrophysics Data System (ADS)

    Ebinumoliseh, Ifeoma; Booysen, Irvin Noel; Akerman, Matthew Piers; Xulu, Bheki

    2016-11-01

    Herein, we report the formation and characterization of a novel dinuclear rhenium(I) compound, fac-(Re(CO)3Br)2(μ-chret) (1) [chret = N, N'-bis(2-amino-3-imino)methylenechromone-1,2-ethane] and a mononuclear metal complex, fac-[Re(CO)3(bzch)Br] (2) [bzch = 2-benzimidazole-4H-chromen-4-one]. The metal complexes were characterized by 1H NMR-, IR-, UV-Vis, melting point and conductivity measurements. The solid-state structures for 1 and 2 were confirmed via single crystal X-ray analysis. X-ray studies of 2 revealed the transformation of the chb diimine into the bzch chelator (in 2). The simulated IR spectra for the respective metal complexes provided insight in the interpretation of their corresponding experimental spectra.

  3. Induction of contact drematitis in guinea pigs by quaternary ammonium compounds: the mechanisms of antigen formation

    SciTech Connect

    Schallreuter, K.R.; Schulz, K.H.; Wood, J.M.

    1986-12-01

    Eight quaternary ammonium compounds were tested for their ability to induce contact dermatitis in guinea pigs by using a modified Freund's complete adjuvant test together with the guinea pig maximization test. Only two quaternary ammonium salts of eight tested could be designated as strong allergens. These two active substances were shown to be capable of stable association with membrane lipids in forming immunogenic complexes. This surface complexation phenomenon was confirmed by using a spin-labeled quaternary ammonium salt which competed for binding sites to the surface of epidermal cells in vivo. Electron spin resonance was used to demonstrate that stable ion-pairs are formed between binding sites and the two allergenic preservatives. Furthermore, information was obtained on the kinetics of immunogenic complex formation as well as on the position and orientation of the quaternary ammonium ion at the cell surface.

  4. Formation, occurrence and analysis of polychlorinated dibenzofurans, dioxins and related compounds.

    PubMed Central

    Buser, H R

    1985-01-01

    In several accidents (fires, explosions) involving electrical systems containing polychlorinated biphenyls (PCBs) or benzenes (PCBZs), the formation of polychlorinated tricyclic aromatic compounds such as polychlorinated dibenzofurans (PCDFs), dibenzo-p-dioxins (PCDDs) and biphenylenes (PCBPs) was observed. These findings were not surprising in light of our previous studies on the formation of PCDFs and PCDDs from the thermolysis (500-750 degrees C in presence of air) of PCBs or PCBZs. In these experiments we identified three main and a fourth minor reaction pathway leading to PCDFs from PCBs. The three main reactions involved the loss of ortho-Cl2, and the losses of ortho-HCl with and without a 2,3-chlorine shift. The fourth, minor reaction route found with some PCBs, involved the loss of ortho-H2. These reaction pathways were intramolecular cyclizations via oxidation to phenolic compounds. Thermolysis of commercial PCBs (Aroclor 1254 and 1260) yielded the same PCDF isomers as expected from the main PCB components via these four reaction pathways; the isomers formed included the toxic 2,3,7,8-substituted tetra-, penta- and hexa-CDFs. Thermolysis of PCBZs involved complex condensation reactions with multiple rearrangements leading to PCDFs as well as PCDDs. Again oxidation to phenolic products was involved but the reaction routes are not yet fully elucidated. The results of samples from transformer and capacitor accident sites showed very complex PCDF mixtures with 2,3,7,8-substituted isomers as main components and originating from the PCBs in the transformer liquid. The unusual presence of PCDDs in samples from the Binghamton accident originates from PCBZs present in transformer fluid of that specific installation, thus confirming our previous thermolysis findings.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:3928352

  5. Compound aircraft transport study: Wingtip-docking compared to formation flight

    NASA Astrophysics Data System (ADS)

    Magill, Samantha A.

    Compound Aircraft Transport (CAT) flight involves two or more aircraft using the resources of each other; a symbiotic relationship exists consisting of a host, the mothership aircraft and a parasite, the hitchhiker aircraft. Wingtip-docked flight is just as its name implies; the two aircraft are connected wingtip-to-wingtip. Formation flight describes multiple aircraft or flying objects that maintain a pattern or shape in the air. There are large aerodynamic advantages in CAT flight. The aforementioned wingtip-docked flight increases total span of the aircraft, system, and formation flight utilizes the upwash from the trailing wingtip vortex of the lead aircraft (mothership) to reduce the energy necessary to achieve and/or maintain a specific flight, goal for the hitchhiker and the system. The Stability Wind Tunnel (6 x 6 x 24 foot test section) at Virginia Tech, computational aerodynamic analysis with the vortex lattice method (VLM), and a desktop aircraft model were used to answer questions of the best location for a hitchhiker aircraft and analyze stability of the CAT system. Three CAT flight configurations were highlighted: wingtip-docked, close formation, and towed formation. The wingtip-docked configuration had a 20--40% performance benefit for the hitchhiker compared to solo flight. The close formation configuration had performance benefits for the hitchhiker approximately 10 times that of solo flight, and the towed formation was approximately 8 times better than solo flight. The VLM analysis completed and reenforced the experimental wind tunnel data. A modified VLM program (VLM CAT) incorporated multiple aircraft in various locations as well as additional calculations for induced drag. VLM CAT results clearly followed the trends seen in the wind tunnel data, but since VLM did not model the fuselage, has assumptions like a flat wake, and is an inviscid computation it did not predict the large benefits or excursions as seen in the wind tunnel data. Increases

  6. Electrocrystallization: A Synthetic Method for Intermetallic Phases with Polar Metal-Metal Bonding.

    PubMed

    Tambornino, Frank; Sappl, Jonathan; Pultar, Felix; Cong, Trung Minh; Hübner, Sabine; Giftthaler, Tobias; Hoch, Constantin

    2016-11-07

    Isothermal electrolysis is a convenient preparation technique for a large number of intermetallic phases. A solution of the salt of a less-noble metal is electrolyzed on a cathode consisting of a liquid metal or intermetallic system. This yields crystalline products at mild reaction conditions in a few hours. We show the aptness and the limitations of this approach. First, we give an introduction into the relevance of electrolytic synthesis for chemistry. Then we present materials and techniques our group has developed for electrocrystallization that are useful for electrochemical syntheses in general. Subsequently, we discuss different phase formation eventualities and propose basic rationalization concepts, illustrated with examples from our work. The scope of this report is to present electrocrystallization as a well-known yet underestimated synthetic process, especially in intermetallic chemistry. For this purpose we adduce literature examples (Li3Ga14, NaGa4, K8Ga8Sn38), technical advice, basic concepts, and new crystal structures only available by this method: Li3Ga13Sn and CsIn12. Electrocrystallization has recently proven especially helpful in our work concerning synthesis of intermetallic phases with polar metal-metal bonding, especially Hg-rich amalgams of less-noble metals. With the term "polar metal-metal bonding" we describe phases where the constituting elements have large electronegativity difference and yet show incomplete electron transfer from the less-noble to the nobler metal. This distinguishes polar intermetallic phases from classical Zintl phases where the electron transfer is virtually complete. Polar metallic phases can show "bad metal behavior" and interesting combinations of ionic and metallic properties. Amalgams of less-noble metals are preeminent representatives for this class of intermetallic phases as Hg is the only noble metal with endothermic electron affinity and thus a very low tendency toward anion formation. To illustrate both

  7. Apatite formation: why it may not work as planned, and how to conclusively identify apatite compounds.

    PubMed

    Drouet, Christophe

    2013-01-01

    Calcium phosphate apatites are inorganic compounds encountered in many different mineralized tissues. Bone mineral, for example, is constituted of nanocrystalline nonstoichiometric apatite, and the production of "analogs" through a variety of methods is frequently reported. In another context, the ability of solid surfaces to favor the nucleation and growth of "bone-like" apatite upon immersion in supersaturated fluids such as SFB is commonly used as one evaluation index of the "bioactivity" of such surfaces. Yet, the compounds or deposits obtained are not always thoroughly characterized, and their apatitic nature is sometimes not firmly assessed by appropriate physicochemical analyses. Of particular importance are the "actual" conditions in which the precipitation takes place. The precipitation of a white solid does not automatically indicate the formation of a "bone-like carbonate apatite layer" as is sometimes too hastily concluded: "all that glitters is not gold." The identification of an apatite phase should be carefully demonstrated by appropriate characterization, preferably using complementary techniques. This review considers the fundamentals of calcium phosphate apatite characterization discussing several techniques: electron microscopy/EDX, XRD, FTIR/Raman spectroscopies, chemical analyses, and solid state NMR. It also underlines frequent problems that should be kept in mind when making "bone-like apatites."

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

    PubMed

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

    2014-01-21

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

  9. Formation of flavor components by the reaction of amino acid and carbonyl compounds in mild conditions.

    PubMed

    Pripis-Nicolau, L; de Revel, G; Bertrand, A; Maujean, A

    2000-09-01

    This work describe products of reactions between four alpha-dicarbonyl compounds (diacetyl, pentan-2,3-dione, glyoxal, and methylglyoxal) or two alpha-hydroxy ketones, (acetoine and acetol) and amino acids present in wines. The results shows the formation of odorous products or strong-smelling additives resulting from the Maillard and Strecker reaction in a primarily aqueous medium, at low temperature and low pH ( approximately pH 3.5) of the wine. GC/FID, GC/FPD, GC/NPD and GC/MS techniques were used. The olfactive characteristics of the products are described. In the presence of sulfur amino acids and in particular cysteine, many products were formed with a heterocycle production such as pyrazines and methylpyrazines, methylthiazoles, acetylthiazoles, acetylthiazolines, acetylthiazolidines, trimethyloxazole, and dimethylethyloxazoles. These various compounds present odors of sulfur, cornlike, pungent, nut, popcorn, roasted hazelnut, toasted, roasted, and ripe fruits. The chemical conditions of the model reactions are specified. The influence of temperature and pH on the reactions in the presence of cysteine were also studied.

  10. Apatite Formation: Why It May Not Work as Planned, and How to Conclusively Identify Apatite Compounds

    PubMed Central

    2013-01-01

    Calcium phosphate apatites are inorganic compounds encountered in many different mineralized tissues. Bone mineral, for example, is constituted of nanocrystalline nonstoichiometric apatite, and the production of “analogs” through a variety of methods is frequently reported. In another context, the ability of solid surfaces to favor the nucleation and growth of “bone-like” apatite upon immersion in supersaturated fluids such as SFB is commonly used as one evaluation index of the “bioactivity” of such surfaces. Yet, the compounds or deposits obtained are not always thoroughly characterized, and their apatitic nature is sometimes not firmly assessed by appropriate physicochemical analyses. Of particular importance are the “actual” conditions in which the precipitation takes place. The precipitation of a white solid does not automatically indicate the formation of a “bone-like carbonate apatite layer” as is sometimes too hastily concluded: “all that glitters is not gold.” The identification of an apatite phase should be carefully demonstrated by appropriate characterization, preferably using complementary techniques. This review considers the fundamentals of calcium phosphate apatite characterization discussing several techniques: electron microscopy/EDX, XRD, FTIR/Raman spectroscopies, chemical analyses, and solid state NMR. It also underlines frequent problems that should be kept in mind when making “bone-like apatites.” PMID:23984373

  11. The Formation of Organic Compounds of Astrobiological Interest by the Irradiation Processing of Astrophysical Ices

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.

    2015-01-01

    Many environments in space contain very low temperature mixed molecular ices that are exposed to ionizing radiation in the form of cosmic rays and high-energy photons. While traditional chemistry would not be expected to occur at the temperatures typical of these ices (T < 50 K), ionizing radiation can break bonds in the original molecules in the ices to form highly reactive ions and radicals. These ions and radicals are subsequently free to react despite the low temperatures of the original ices. Laboratory experiments, many of them carried out at the Astrochemistry Laboratory at NASA-Ames, show that the irradiation of ices made of even simple molecules like H2O, CO, CO2, CH4, NH3, etc. can result in the robust formation of large numbers of far more complex organic compounds. Many of these new products are of direct interest to astrobiology. For example, the irradiation of mixed molecular ices has been shown to produce amino acids, amphiphiles, quinones, sugars, heterocyclic compounds, and nucleobases, all molecular building blocks used by terrestrial life. Insofar as the presence of these materials plays a role in the origin of life on planets, this has profound implications for the potential abundance of life in the universe since these experiments simulate universal conditions that are expected to be found wherever new stars and planets form.

  12. 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.

  13. Kinetics and mechanisms of formation of earthy and musty odor compounds: Chloroanisoles during water chlorination.

    PubMed

    Zhang, Kejia; Zhou, Xinyan; Zhang, Tuqiao; Mao, Minmin; Li, Lei; Liao, Wenchao

    2016-11-01

    Chloroanisoles are often reported as off-flavor compounds which produce an earthy and musty flavors and odors in drinking water. To improve understanding and ultimately minimize the formation of 2,4-dichloroanisole (2,4-DCA), 2,6-dichloroanisole (2,6-DCA) and 2,4,6-trichloroanisole (2,4,6-TCA), which have low odor threshold concentrations (OTC: 0.03-4 ng L(-1)), a kinetic database for the chlorination of anisole was established by kinetic measurements. The results showed that HOCl reacted with anisole in acidic solution, with the hydrogen ion as an important catalyst. Quantification of product distribution of the produced chloroanisoles demonstrated that a chlorine attack in the para-position was favored over the ortho-position. A kinetic model was formulated, which permitted investigation of the relative importance of the chlorine dose and other water quality parameters including the concentrations of anisole and several metal ions, as well as temperature, on the product distribution of chloroanisoles. In general, high chlorine doses led to low concentrations of intermediates. The presence of ions such as Fe(3+) and Al(3+) facilitated the formation of chloroanisoles, but Zn(2+) and Mn(2+) did not. The kinetic model can be applied to optimize water chlorination and minimize earthy and musty odors.

  14. Study of the formation mechanisms of some volatile compounds during the aging of sweet fortified wines.

    PubMed

    Cutzach, I; Chatonnet, P; Dubourdieu, D

    1999-07-01

    Sweet fortified wines, traditionally aged under strong oxidation conditions, have a characteristic aroma. An experimental laboratory study investigated the aging of red and white sweet fortified wines under various conditions. The formation of various molecules, previously identified as characteristic of the aroma of this type of wine, was monitored by analysis. The development of these compounds during accelerated aging was affected by oxidation and the color of the wine. Among the molecules studied, sotolon [3-hydroxy-4, 5-dimethyl-2(5H)-furanone] was one of the few molecules present in concentrations above the perception threshold, in both red and white wines. Buildup was strongly affected by the presence of oxygen in white wine subjected to accelerated aging. (Ethoxymethyl)furfural, formed from 5-(hydroxymethyl)furfural, and furfural, derived from sugars, are also involved in the aroma of sweet fortified white wines aged in oxygen-free conditions. The substances most characteristic of accelerated aging of sweet fortified red wines were 5-(hydroxymethyl)furfural, acetylformoin, and hydroxymaltol, the formation of which is affected by oxidation, and dihydromaltol, formed in the absence of oxidation.

  15. Role of Aerosol Liquid Water in Secondary Organic Aerosol Formation from Volatile Organic Compounds.

    PubMed

    Faust, Jennifer A; Wong, Jenny P S; Lee, Alex K Y; Abbatt, Jonathan P D

    2017-02-07

    A key mechanism for atmospheric secondary organic aerosol (SOA) formation occurs when oxidation products of volatile organic compounds condense onto pre-existing particles. Here, we examine effects of aerosol liquid water (ALW) on relative SOA yield and composition from α-pinene ozonolysis and the photooxidation of toluene and acetylene by OH. Reactions were conducted in a room-temperature flow tube under low-NOx conditions in the presence of equivalent loadings of deliquesced (∼20 μg m(-3) ALW) or effloresced (∼0.2 μg m(-3) ALW) ammonium sulfate seeds at exactly the same relative humidity (RH = 70%) and state of wall conditioning. We found 13% and 19% enhancements in relative SOA yield for the α-pinene and toluene systems, respectively, when seeds were deliquesced rather than effloresced. The relative yield doubled in the acetylene system, and this enhancement was partially reversible upon drying the prepared SOA, which reduced the yield by 40% within a time scale of seconds. We attribute the high relative yield of acetylene SOA on deliquesced seeds to aqueous partitioning and particle-phase reactions of the photooxidation product glyoxal. The observed range of relative yields for α-pinene, toluene, and acetylene SOA on deliquesced and effloresced seeds suggests that ALW plays a complicated, system-dependent role in SOA formation.

  16. [Chemical Loss of Volatile Organic Compounds and Its Impact on the Formation of Ozone in Shanghai].

    PubMed

    Wang, Hong-li

    2015-09-01

    The spatial characterization of ozone (O3) and its precursors was studied based on the field measurements in urban and rural areas of Shanghai during the summer of 2014. The chemical loss of volatile organic compounds (VOCs) was estimated by the parameterization method. The mixing ratio of VOCs was 20 x 10(-9) in urban area and 17 x 10(-9) in the west rural area during the measurements. The average values of the maximum incremental reactivity were comparable in urban and rural areas, namely 5. 0 mol.mol-1 (O3/VOCs). By contrast, the chemical loss of VOCs was 8. 3 x 10(-9) in west rural area, which was two times as that in urban area. The more chemical loss of VOCs was probably one of the important reasons leading to the higher O3 concentration in west rural area. The regional transport might be important reason of the variation of O3 in the eastern coastal rural area. The chemical loss of VOCs showed good agreement with the local formation of O3 in both urban and rural areas, suggesting a similar efficiency of O3 formation from the chemical loss of VOCs. Among the chemical loss, aromatics and alkenes are the dominant VOC species of the atmospheric chemistry which accounts for more than 90% . The diurnal profile of VOC chemical loss matched well with the production of O3 with one-hour postponement.

  17. Plasma spray forming metals, intermetallics, and composites

    NASA Astrophysics Data System (ADS)

    Sampath, Sanjay; Herman, Herbert

    1993-07-01

    Plasma spray processing is a droplet deposition method that combines the steps of melting, rapid solidification, and consolidation into a single step. The versatility of the technology enables the processing of freestanding bulk, near-net shapes of a wide range of alloys, intermetallics, ceramics, and composites, while still retaining the benefits of rapid solidification processing. In particular, it is possible to produce dense forms through vacuum plasma spraying.

  18. Compton Profile Study of Intermetallic Ti{sub 3}Al

    SciTech Connect

    Vyas, V.; Sharma, G.; Mishra, M. C.; Sharma, B. K.; Joshi, K. B.

    2011-10-20

    The Compton scattering measurement on intermetallic alloy Ti{sub 3}Al is reported in this work. The measurement is made using 59.54 keV gamma-rays from Am{sup 241} source. Theoretical calculation of Compton profile is also performed employing CRYSTAL code within the framework of density functional theory to compare with the measurement. The theoretical profile of the alloy is also synthesized following the superposition model taking the published Compton profiles of elemental solids from the APW method. The experimental study of charge transfer in the alloys has also been done by performing the experimental Compton profile measurements on Ti and Al following the superposition model and charge transfer from Al to Ti is clearly seen on the alloy formation.

  19. Kinetics and activation thermodynamics of methane monooxygenase compound Q formation and reaction with substrates.

    PubMed

    Brazeau, B J; Lipscomb, J D

    2000-11-07

    The transient kinetics of formation and decay of the reaction cycle intermediates of the Methylosinus trichosporium OB3b methane monooxygenase (MMO) catalytic cycle are studied as a function of temperature and substrate type and deuteration. Kinetic evidence is presented for the existence of three intermediates termed compounds O, P, and P forming after the addition of O(2) to diferrous MMO hydroxylase (H(r)) and before the formation of the reactive intermediate compound Q. The Arrhenius plots for these reactions are linear and independent of substrate concentration and type, showing that substrate does not participate directly in the oxygen activation phase of the catalytic cycle. Analysis of the transient kinetic data revealed only small changes relative to the weak optical spectrum of H(r) for any of these intermediates. In contrast, large changes in the 430 nm spectral region are associated with the formation of Q. The decay reaction of Q exhibits an apparent first-order concentration dependence for all substrates tested, and the observed rate constant depends on the substrate type. The kinetics of the decay reaction of Q yield a nonlinear Arrhenius plot when methane is the substrate, and the rates in both segments of the plot increase linearly with methane concentration. Together these observations suggest that at least two reactions with a methane concentration dependence, and perhaps two methane molecules, are involved in the decay process. When CD(4) is used as the substrate, a large isotope effect and a linear Arrhenius plot are observed. Analogous plots for all other MMO substrates tested (e.g., ethane) are linear, and no isotope effect for deuterated analogues is observed. This demonstrates that a step other than C-H bond breaking is rate limiting for alternative MMO substrates. A two step Q decay mechanism is proposed that provides an explanation for the lack of an isotope effect for alternative MMO substrates and the fact that rate of oxidation of

  20. A study on the formation of solid state nanoscale materials using polyhedral borane compounds

    NASA Astrophysics Data System (ADS)

    Romero, Jennifer V.

    The formation of boron containing materials using a variety of methods was explored. The pyrolysis of a metal boride precursor solution can be accomplished using a one-source method by combining TiCl4, B10H 14 and CH3CN in one reaction vessel and pyrolyzing it at temperatures above 900 °C. Amorphous dark blue colored films were obtained after the pyrolysis reactions. Well-defined spherical shaped grains or particles were observed by SEM. The amorphous films generated contained titanium, however, the determination of the boron content of the films was inconclusive. This one pot method making metal boride thin films has the advantage of being able to dictate the stoichiometry of the reactants. Another part of this work represents the first report of both the use of metal boride materials and the use of a titanium-based compound for the formation of nanotubes. This method provides a facile method for generating well-formed boron-containing carbon nanotubes in a "one-pot" process through an efficient aerosol process. The formation of metal boride corrosion resistant layers was also explored. It was shown that metallic substrates can be effectively boronized using paste mixtures containing boron carbide and borax. The formation of a Fe4B 2 iron boride phase was achieved, however, this iron boride phase does not give enough corrosion protection. The formation of a corrosion resistant metal boride coating with strong adhesion was accomplished by boronization of a thermal sprayed nickel layer on the surface of steel. Surfactants were explored as possible nanoreactors in which metal boride nanoparticles could be formed to use as nanotube growth catalyst via room temperature reaction. Different surfactants were used, but none of them successfully generated very well dispersed metal boride nanoparticles. Nanoparticles with varying shapes and sizes were generated which were highly amorphous. The carboxylic acid derivative of closo-C2B 10 cages was explored as a ligand in the

  1. Formation of Secondary Organic Aerosol from Non-traditional Intermediate Volatility Organic Compounds

    NASA Astrophysics Data System (ADS)

    Donahue, N. M.; Presto, A. A.; Robinson, A. L.; Kroll, J. H.; Worsnop, D. R.

    2009-04-01

    Secondary organic aerosol (SOA) formation from 'traditional' precursors such as monoterpenes and alkylbenzenes has received substantial attention for the past decade. These traditional sources have relatively high emissions into the atmosphere, but they are also relatively volatile. As a consequence, the oxidation products from those precursors must be more than one million times less volatile in order to form SOA. We have recently begun to investigate the role of 'nontraditional' SOA precursors with much lower volatility than the traditional precursors. These intermediate volatility organic compounds (IVOC) are typically co-emitted with traditional primary organic aerosol (POA) sources at elevated temperatures, including biomass burning and internal combustion processes. While their emissions are much lower than the traditional precursors, the volatility reduction required of the reaction products is much less drastic, making high-yield SOA formation much more likely. Here we describe the formation of SOA from two precursors in the CMU environmental chamber - heptadecane and pentacosane - under high- and low-NOx conditions. Analysis of the resulting SOA with a high-resolution aerosol mass spectrometer coupled to a thermodenuder allows us to asses the oxidation state and volatility distribution of the condensible products, revealing a high degree of oxidation under high-NOx conditions where most of the organics remain in the vapor phase for at least 2 generations of oxidation chemistry, but a lower (though progressive) degree of oxidation under other conditions. These results will be place in context using a two-dimensional volatility basis set that incorporates both the volatility distribution and oxidation state of complex organic mixtures.

  2. Modelling the contribution of biogenic volatile organic compounds to new particle formation in the Jülich plant atmosphere chamber

    NASA Astrophysics Data System (ADS)

    Roldin, P.; Liao, L.; Mogensen, D.; Dal Maso, M.; Rusanen, A.; Kerminen, V.-M.; Mentel, T. F.; Wildt, J.; Kleist, E.; Kiendler-Scharr, A.; Tillmann, R.; Ehn, M.; Kulmala, M.; Boy, M.

    2015-09-01

    We used the Aerosol Dynamics gas- and particle-phase chemistry model for laboratory CHAMber studies (ADCHAM) to simulate the contribution of BVOC plant emissions to the observed new particle formation during photooxidation experiments performed in the Jülich Plant-Atmosphere Chamber and to evaluate how well smog chamber experiments can mimic the atmospheric conditions during new particle formation events. ADCHAM couples the detailed gas-phase chemistry from Master Chemical Mechanism with a novel aerosol dynamics and particle phase chemistry module. Our model simulations reveal that the observed particle growth may have either been controlled by the formation rate of semi- and low-volatility organic compounds in the gas phase or by acid catalysed heterogeneous reactions between semi-volatility organic compounds in the particle surface layer (e.g. peroxyhemiacetal dimer formation). The contribution of extremely low-volatility organic gas-phase compounds to the particle formation and growth was suppressed because of their rapid and irreversible wall losses, which decreased their contribution to the nano-CN formation and growth compared to the atmospheric situation. The best agreement between the modelled and measured total particle number concentration (R2 > 0.95) was achieved if the nano-CN was formed by kinetic nucleation involving both sulphuric acid and organic compounds formed from OH oxidation of BVOCs.

  3. Theoretical studies on the heats of formation, densities, and detonation properties of substituted s-tetrazine compounds.

    PubMed

    Zhou, Yang; Long, XinPing; Shu, YuanJie

    2010-05-01

    Substituted s-tetrazine compounds were designed and investigated in order to find comprehensive relationships between the structures and performances of high-nitrogen energetic compounds. Density functional theory (DFT) was used to predict the optimized geometries, electronic structures, heats of formation and densities, and the detonation properties were evaluated by using the VLW equation of state (EOS). Calculation results show that there are good linear relationships between heats of formation, densities, detonation properties and the number of N atom in all designed high-nitrogen compounds. Furthermore, several designed high-nitrogen compounds show good detonation velocities and pressures compared with octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), making them potential candidates for high-energy-density materials (HEDM).

  4. Formation of nitrate and ammonium ions in titanium dioxide mediated photocatalytic degradation of organic compounds containing nitrogen atoms

    SciTech Connect

    Low, G.K.-C.; McEvoy, S.R.; Matthews, R.W. )

    1991-03-01

    The photocatalytic oxidation of a related series of primary, secondary, and tertiary amines and other nitrogen- and sulfur-containing organic compounds over a UV-illuminated film of TiO{sub 2} has been studied. The compounds were as follows: n-pentylamine, piperidine, pyridine, phenylalanine, desipramine, thioridazine, penicillamine, isosorbide dinitrate, 4-nitrocatechol, 2,4-dinitrophenol, cyclophosphamide, 5-fluorouracil, atrazine, ethylenediaminetetracetic acid, and tetrabutylammonium phosphate. Both ammonium and nitrate ions were formed. The relative concentration of the two ions depended on the nature of the nitrogen in a compound, but was also influenced by the illumination time and concentration of the solute. It was found that for n-pentylamine, piperidine and pyridine, the rate of formation of ammonium ions was n-pentylamine {much gt} pyridine > piperidine. The order of rates of nitrate formation was pyridine = piperidine {much gt} pentylamine. For n-pentylamine the rate of formation of ammonium ions was {approximately}100 times that of nitrate.

  5. Spectral and kinetic studies on the formation of eosinophil peroxidase compound I and its reaction with halides and thiocyanate.

    PubMed

    Furtmüller, P G; Burner, U; Regelsberger, G; Obinger, C

    2000-12-19

    Compound I of peroxidases takes part in both the peroxidation and the halogenation reaction. This study for the first time presents transient kinetic measurements of the formation of compound I of human eosinophil peroxidase (EPO) and its reaction with halides and thiocyanate, using the sequential-mixing stopped-flow technique. Addition of 1 equiv of hydrogen peroxide to native EPO leads to complete formation of compound I. At pH 7 and 15 degrees C, the apparent second-order rate constant is (4.3 +/- 0.4) x 10(7) M(-1) s(-1). The rate for compound I formation by hypochlorous acid is (5.6 +/- 0.7) x 10(7) M(-1) s(-1). EPO compound I is unstable and decays to a stable intermediate with a compound II-like spectrum. At pH 7, the two-electron reduction of compound I to the native enzyme by thiocyanate has a second-order rate constant of (1.0 +/- 0. 5) x 10(8) M(-1) s(-1). Iodide [(9.3 +/- 0.7) x 10(7) M(-1) s(-1)] is shown to be a better electron donor than bromide [(1.9 +/- 0.1) x 10(7) M(-1) s(-1)], whereas chloride oxidation by EPO compound I is extremely slow [(3.1 +/- 0.3) x 10(3) M(-1) s(-1)]. The pH dependence studies suggest that a protonated form of compound I is more competent in oxidizing the anions. The results are discussed in comparison with those of the homologous peroxidases myeloperoxidase and lactoperoxidase and with respect to the role of EPO in host defense and tissue injury.

  6. A kinetic model for the formation of hierarchical nanostructures during the evaporation of phase-forming compound solutions

    NASA Astrophysics Data System (ADS)

    Melikhov, I. V.; Alekseeva, O. V.; Rudin, V. N.; Kozlovskaya, E. D.; Noskov, A. V.

    2016-03-01

    A kinetic model for the precipitation of a dispersed compound from solutions is formulated, based on a description of the evolution in the function of its particle distribution according to its states during precipitation. A boundary problem about the precipitation of a compound during the evaporation of a solvent from a solution under conditions in which the rate of aggregate formation is high is considered. The solution to this boundary problem can be used to describe the formation of a film of polystyrene during the evaporation of its solution in toluene and o-xylene deposited onto a substrate.

  7. Plasma sprayed ceramic thermal barrier coating for NiAl-based intermetallic alloys

    NASA Technical Reports Server (NTRS)

    Miller, Robert A. (Inventor); Doychak, Joseph (Inventor)

    1994-01-01

    A thermal barrier coating system consists of two layers of a zirconia-yttria ceramic. The first layer is applied by low pressure plasma spraying. The second layer is applied by conventional atmospheric pressure plasma spraying. This facilitates the attachment of a durable thermally insulating ceramic coating directly to the surface of a highly oxidation resistant NiAl-based intermetallic alloy after the alloy has been preoxidized to promote the formation of a desirable Al2O3 scale.

  8. High-Performance Pd3Pb Intermetallic Catalyst for Electrochemical Oxygen Reduction.

    PubMed

    Cui, Zhiming; Chen, Hao; Zhao, Mengtian; DiSalvo, Francis J

    2016-04-13

    Extensive efforts to develop highly active and strongly durable electrocatalyst for oxygen reduction are motivated by a need for metal-air batteries and fuel cells. Here, we report a very promising catalyst prototype of structurally ordered Pd-based alloys, Pd3Pb intermetallic compound. Such structurally ordered Pd3Pb/C exhibits a significant increase in mass activity. More importantly, compared to the conventional Pt/C catalysts, ordered Pd3Pb/C is highly durable and exhibits a much longer cycle life and higher cell efficiency in Zn-air batteries. Interestingly, ordered Pd3Pb/C possesses very high methanol tolerance during electrochemical oxygen reduction, which make it an excellent methanol-tolerant cathode catalyst for alkaline polymer electrolyte membrane fuel cells. This study provides a promising route to optimize the synthesis of ordered Pd-based intermetallic catalysts for fuel cells and metal-air batteries.

  9. High Temperature Oxidation of Superalloys and Intermetallic Compounds

    DTIC Science & Technology

    2010-02-28

    material cost and density than austenitic and ferritic stainless steels [3,4]. They contain enough aluminum to form a thin film of aluminum oxide (in...1 t-\\ a) > —, :— sm . c) • / ""•••• Figure 8. Surface morphologies of...low material cost and density than austenitic and ferritic stainless steels [3,4]. They contain enough aluminum to form a thin film of aluminum oxide

  10. Addressing Machining Issues for the Intermetallic Compound 60-NITINOL

    NASA Technical Reports Server (NTRS)

    Stanford, Malcolm K.; Wozniak, Walter A.; McCue, Terry R.

    2012-01-01

    60-NITINOL (60 wt.% Ni - 40 wt.% Ti) is being studied as a material for advanced aerospace components. Frequent wire breakage during electrical-discharge machining of this material was investigated. The studied material was fabricated from hot isostatically pressed 60-NITINOL powder obtained through a commercial source. Bulk chemical analysis of the material showed that the composition was nominal but had relatively high levels of certain impurities, including Al and O. It was later determined that Al2O3 particles had contaminated the material during the hot isostatic pressing procedure and that these particles were the most likely cause of the wire breakage. The results of this investigation highlight the importance of material cleanliness to its further implementation.

  11. Photochemical formation of hydroxyl radical in red-soil-polluted seawater - effects of dissolved organic compounds

    NASA Astrophysics Data System (ADS)

    Uehara, M.; Arakaki, T.

    2006-12-01

    Development of pineapple farmlands and construction of recreational facilities caused runoff of red soil into the coastal ocean (locally termed as red soil pollution) in the north of Okinawa Island, Japan. Red soil is acidic and contains a few percent of iron oxide. We were interested in the formation of hydroxyl radical (·OH), the most potent oxidant in the environment, from the photo-Fenton reaction (reaction between Fe(II) and HOOH) in red-soil-polluted seawater. Various artificial seawater solutions were prepared by adding red soil, HOOH, and/or humic acid to clean seawater, and were used for photochemical experiments. Commercially available humic acid was used to represent natural organic compounds. All the solutions were filtered through 0.45 micron filter before conducting photochemical experiments. Comparisons among the solutions indicated that dissolved chemicals from the red-soil only slightly increased the OH radical photoformation. Photoformation rates of OH radicals of the HOOH + red soil solutions were similar to the calculated rates from direct photolysis of HOOH. Furthermore, addition of humic acid to the HOOH + red soil solutions did not significantly enhance the photo-Fenton reaction, suggesting that Fe(II), even if it had been formed, did not react with HOOH to form OH radicals at detectable level in seawater.

  12. Towards an understanding of the propensity for crystalline hydrate formation by molecular compounds

    PubMed Central

    Bajpai, Alankriti; Scott, Hayley S.; Pham, Tony; Chen, Kai-Jie; Space, Brian; Lusi, Matteo; Perry, Miranda L.; Zaworotko, Michael J.

    2016-01-01

    Hydrates are technologically important and ubiquitous yet they remain a poorly understood and understudied class of molecular crystals. In this work, we attempt to rationalize propensity towards hydrate formation through crystallization studies of molecules that lack strong hydrogen-bond donor groups. A Cambridge Structural Database (CSD) survey indicates that the statistical occurrence of hydrates in 124 molecules that contain five- and six-membered N-heterocyclic aromatic moieties is 18.5%. However, hydrate screening experiments on a library of 11 N-heterocyclic aromatic compounds with at least two acceptor moieties and no competing hydrogen-bond donors or acceptors reveals that over 70% of this group form hydrates, suggesting that extrapolation from CSD statistics might, at least in some cases, be deceiving. Slurrying in water and exposure to humidity were found to be the most effective discovery methods. Electrostatic potential maps and/or analysis of the crystal packing in anhydrate structures was used to rationalize why certain molecules did not readily form hydrates. PMID:27840682

  13. Towards an understanding of the propensity for crystalline hydrate formation by molecular compounds.

    PubMed

    Bajpai, Alankriti; Scott, Hayley S; Pham, Tony; Chen, Kai-Jie; Space, Brian; Lusi, Matteo; Perry, Miranda L; Zaworotko, Michael J

    2016-11-01

    Hydrates are technologically important and ubiquitous yet they remain a poorly understood and understudied class of molecular crystals. In this work, we attempt to rationalize propensity towards hydrate formation through crystallization studies of molecules that lack strong hydrogen-bond donor groups. A Cambridge Structural Database (CSD) survey indicates that the statistical occurrence of hydrates in 124 molecules that contain five- and six-membered N-heterocyclic aromatic moieties is 18.5%. However, hydrate screening experiments on a library of 11 N-heterocyclic aromatic compounds with at least two acceptor moieties and no competing hydrogen-bond donors or acceptors reveals that over 70% of this group form hydrates, suggesting that extrapolation from CSD statistics might, at least in some cases, be deceiving. Slurrying in water and exposure to humidity were found to be the most effective discovery methods. Electrostatic potential maps and/or analysis of the crystal packing in anhydrate structures was used to rationalize why certain molecules did not readily form hydrates.

  14. Characterization of Atmospheric Volatile Organic Compounds in the North Dakota Bakken Formation

    NASA Astrophysics Data System (ADS)

    Sive, B. C.; Zhou, Y.; Day, D.; Desyaterik, Y.; Evanoski-Cole, A. R.; Gebhart, K.; Hecobian, A.; Li, Y.; Malm, W. C.; Prenni, A. J.; Schichtel, B. A.; Schurman, M. I.; Sullivan, A.; Vimont, J.; Collett, J. L., Jr.

    2014-12-01

    A field campaign was conducted from 23 November 2013 through 28 March 2014 in the Bakken formation of North Dakota to investigate the impacts of rapidly increasing oil and gas production operations on air quality throughout the region. Whole air samples were collected at three different sites during the study period for volatile organic compound (VOC) measurements. The main sampling location was the north unit of Theodore Roosevelt National Park (THRO), where one daytime and one nighttime sample were collected each day throughout the campaign period. Daytime samples were also collected every second day at the Fort Union Trading Post National Historic Site (FOUS) and once a week at the Medicine Lake National Wildlife Refuge, MT. A signature of elevated nonmethane hydrocarbon (NMHC) mixing ratios was observed throughout the campaign at all three sites; THRO and FOUS had the highest levels as they are located in high well density areas. Moreover, the C2-C5 alkane mixing ratios were approximately an order of magnitude greater than regional background levels. Light alkane mixing ratios at THRO, the most impacted site, were similar to those at urban sites influenced by petrochemical industry emissions, with ethane and propane reaching maximums of 95 ppbv and 164 ppbv, respectively. The i-pentane to n-pentane ratio for all sites was ~0.75, clearly demonstrating the widespread impact from oil and gas production emissions throughout the region. Alkanes dominated the hydroxyl radical reactivity, and their overall influence on regional air quality will be explored.

  15. On the formation of metal cyanides and related compounds in the circumstellar envelope of IRC+10216

    NASA Astrophysics Data System (ADS)

    Petrie, Simon

    1996-10-01

    Various pathways to the metal cyanides Na(CN), Mg(CN) and Al(CN) - some of which have been detected in the circumstellar envelope IRC+10216 - are critically assessed. Calculations of rate coefficients for radiative association processes of the types M^++HCN, M^++HNC and M+CN, which are supported by ab initio calculations of the relevant bond strengths, molecular geometries and vibrational frequencies, allow us to conclude that none of these previously proposed pathways to M(CN) can account for the observed abundances of T-Na(CN), MgCN and MgNC within IRC+10216. We propose that the observed sodium and magnesium cyanides are best accounted for by a mechanism involving radiative association of Na^+ and Mg^+ with cyanopolyynes such as HC_5N and HC_7N, and discuss prospects for the formation of Al(CN) by an analogous mechanism. We also estimate the abundance ratios n(NaCN):n(T-Na(CN)) and n(AlCN):n(AlNC), assuming an ion/molecule source for these species and based on calculated themochemical and spectroscopic properties for these isomers; the results suggest that virtually all Na(CN) and Al(CN) should be in the form of T-Na(CN) and linear AlNC respectively, with poor prospects for the detection of the higher energy isomers NaCN and AlCN. Larger homologues of the metal cyanides, such as MNC_2n-1 (M=Na, Mg, Al; n=1,2,3,4...), may also arise in the dissociative recombination of MNC_2n+1H^+ ions. We assess the prospects for formation of the species MgC_2 and MgCCH, and propose also that the metal amides MNH_2 (M=Na, Mg, Al) constitute another class of compound whose formation in IRC+10216 via an ion/molecule mechanism, namely the reaction of M^+ with NH_3, appears highly likely.

  16. Study of the formation of carbonyl compounds in edible oils and fats by 1H-NMR and FTIR

    NASA Astrophysics Data System (ADS)

    Moya Moreno, M. C. M.; Mendoza Olivares, D.; Amézquita López, F. J.; Peris Martínez, V.; Bosch Reig, F.

    1999-05-01

    Oils and fats start decomposing from the moment they are isolated from their natural environment. Heating accelerates oxidative rancidity and frying at high temperatures produces thermal degradation with the formation of decomposition products, such as aldehydes, ketones, free acids and hydroxilic compounds that in high levels can be harmful to human health. The decomposition products formed up to 300°C were determined by means of 1H-NMR spectroscopy and an FTIR spectroscopic method was developed for the quantification of carbonyl compounds generated during heating. The results show that there is a formation of carbonyl compounds starting at 150°C and when the sample was heated at 300°C for 40 min, the following contents (expressed as butyraldehyde mass fraction) were found: olive oil 10.5%, sunflower oil 11.3%, corn oil 3.0%, seeds oil (sunflower, safflower and canola seed) 6.6% and lard 3.5%.

  17. Key volatile compounds in red koji-shochu, a Monascus-fermented product, and their formation steps during fermentation.

    PubMed

    Rahayu, Yen Yen Sally; Yoshizaki, Yumiko; Yamaguchi, Keiko; Okutsu, Kayu; Futagami, Taiki; Tamaki, Hisanori; Sameshima, Yoshihiro; Takamine, Kazunori

    2017-06-01

    Red koji, which refers the solid culture grown koji mold on the steamed rice, is one of the ingredients of Asian fermented foods including the Japanese spirit shochu. This study was aimed at elucidating the characteristic flavor and key volatile compounds of red koji-shochu as well as the mechanism of their formation. Sensory evaluation showed that red koji-shochu has the distinctive flavors cheese, sour, milky, and oily. Fifteen key volatile compounds of red koji-shochu were identified by gas chromatography-mass spectrometry and high-performance liquid chromatography, and by comparison between red koji-shochu and white koji-shochu, as another typical shochu. The mash analysis revealed that ketone compounds and short-chain acids derive from red koji. Furthermore, although other key compounds were produced by yeast, it is highly likely that their concentrations were affected directly or indirectly by the high activities of protease and lipase in red koji.

  18. Intermetallics Characterization of Lead-Free Solder Joints under Isothermal Aging

    NASA Astrophysics Data System (ADS)

    Choubey, Anupam; Yu, Hao; Osterman, Michael; Pecht, Michael; Yun, Fu; Yonghong, Li; Ming, Xu

    2008-08-01

    Solder interconnect reliability is influenced by environmentally imposed loads, solder material properties, and the intermetallics formed within the solder and the metal surfaces to which the solder is bonded. Several lead-free metallurgies are being used for component terminal plating, board pad plating, and solder materials. These metallurgies react together and form intermetallic compounds (IMCs) that affect the metallurgical bond strength and the reliability of solder joint connections. This study evaluates the composition and extent of intermetallic growth in solder joints of ball grid array components for several printed circuit board pad finishes and solder materials. Intermetallic growth during solid state aging at 100°C and 125°C up to 1000 h for two solder alloys, Sn-3.5Ag and Sn-3.0Ag-0.5Cu, was investigated. For Sn-3.5Ag solder, the electroless nickel immersion gold (ENIG) pad finish was found to result in the lowest IMC thickness compared to immersion tin (ImSn), immersion silver (ImAg), and organic solderability preservative (OSP). Due to the brittle nature of the IMC, a lower IMC thickness is generally preferred for optimal solder joint reliability. A lower IMC thickness may make ENIG a desirable finish for long-life applications. Activation energies of IMC growth in solid-state aging were found to be 0.54 ± 0.1 eV for ENIG, 0.91 ± 0.12 eV for ImSn, and 1.03 ± 0.1 eV for ImAg. Cu3Sn and Cu6Sn5 IMCs were found between the solder and the copper pad on boards with the ImSn and ImAg pad finishes. Ternary (Cu,Ni)6Sn5 intermetallics were found for the ENIG pad finish on the board side. On the component side, a ternary IMC layer composed of Ni-Cu-Sn was found. Along with intermetallics, microvoids were observed at the interface between the copper pad and solder, which presents some concern if devices are subject to shock and vibration loading.

  19. A Novel Low-Molecular-Weight Compound Enhances Ectopic Bone Formation and Fracture Repair

    PubMed Central

    Wong, Eugene; Sangadala, Sreedhara; Boden, Scott D.; Yoshioka, Katsuhito; Hutton, William C.; Oliver, Colleen; Titus, Louisa

    2013-01-01

    Background: Use of recombinant human bone morphogenetic protein-2 (rhBMP-2) is expensive and may cause local side effects. A small synthetic molecule, SVAK-12, has recently been shown in vitro to potentiate rhBMP-2-induced transdifferentiation of myoblasts into the osteoblastic phenotype. The aims of this study were to test the ability of SVAK-12 to enhance bone formation in a rodent ectopic model and to test whether a single percutaneous injection of SVAK-12 can accelerate callus formation in a rodent femoral fracture model. Methods: Collagen disks with rhBMP-2 alone or with rhBMP-2 and SVAK-12 were implanted in a standard athymic rat chest ectopic model, and radiographic analysis was performed at four weeks. In a second set of rats (Sprague-Dawley), SVAK-12 was percutaneously injected into the site of a closed femoral fracture. The fractures were analyzed radiographically and biomechanically (with torsional testing) five weeks after surgery. Results: In the ectopic model, there was dose-dependent enhancement of rhBMP-2 activity with use of SVAK-12 at doses of 100 to 500 μg. In the fracture model, the SVAK-12-treated group had significantly higher radiographic healing scores than the untreated group (p = 0.028). Biomechanical testing revealed that the fractured femora in the 200 to 250-μg SVAK-12 group were 43% stronger (p = 0.008) and 93% stiffer (p = 0.014) than those in the control group. In summary, at five weeks the femoral fracture group injected with SVAK-12 showed significantly improved radiographic and biomechanical evidence of healing compared with the controls. Conclusions: A single local dose of a low-molecular-weight compound, SVAK-12, enhanced bone-healing in the presence of low-dose exogenous rhBMP-2 (in the ectopic model) and endogenous rhBMPs (in the femoral fracture model). Clinical Relevance: This study demonstrates that rhBMP-2 responsiveness can be enhanced by a novel small molecule, SVAK-12. Local application of anabolic small molecules has

  20. Volatile organic compounds in pesticide formulations: Methods to estimate ozone formation potential

    NASA Astrophysics Data System (ADS)

    Zeinali, Mazyar; McConnell, Laura L.; Hapeman, Cathleen J.; Nguyen, Anh; Schmidt, Walter F.; Howard, Cody J.

    2011-05-01

    The environmental fate and toxicity of active ingredients in pesticide formulations has been investigated for many decades, but relatively little research has been conducted on the fate of pesticide co-formulants or inerts. Some co-formulants are volatile organic compounds (VOCs) and can contribute to ground-level ozone pollution. Effective product assessment methods are required to reduce emissions of the most reactive VOCs. Six emulsifiable concentrate pesticide products were characterized for percent VOC by thermogravimetric analysis (TGA) and gas chromatography-mass spectrometry (GC-MS). TGA estimates exceeded GC-MS by 10-50% in all but one product, indicating that for some products a fraction of active ingredient is released during TGA or that VOC contribution was underestimated by GC-MS. VOC profiles were examined using TGA-Fourier transform infrared (FTIR) evolved gas analysis and were compared to GC-MS results. The TGA-FTIR method worked best for products with the simplest and most volatile formulations, but could be developed into an effective product screening tool. An ozone formation potential ( OFP) for each product was calculated using the chemical composition from GC-MS and published maximum incremental reactivity ( MIR) values. OFP values ranged from 0.1 to 3.1 g ozone g -1 product. A 24-h VOC emission simulation was developed for each product assuming a constant emission rate calculated from an equation relating maximum flux rate to vapor pressure. Results indicate 100% VOC loss for some products within a few hours, while other products containing less volatile components will remain in the field for several days after application. An alternate method to calculate a product OFP was investigated utilizing the fraction of the total mass of each chemical emitted at the end of the 24-h simulation. The ideal assessment approach will include: 1) unambiguous chemical composition information; 2) flexible simulation models to estimate emissions under

  1. Compound-Specific Isotopic Analysis of Meteoritic Amino Acids as a Tool for Evaluating Potential Formation Pathways

    NASA Technical Reports Server (NTRS)

    Elsila, Jamie E.; Burton, Aaron S.; Callahan, Michael C.; Charnley, Steven B.; Glavin, Daniel P.; Dworkin, Jason P.

    2012-01-01

    Measurements of stable hydrogen, carbon, and nitrogen isotopic ratios (delta D, delta C-13, delta N-15) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may point towards the most likely of these proposed pathways. The technique of gas chromatography coupled with mass spectrometry and isotope ratio mass spectrometry provides compound-specific structural and isotopic information from a single splitless injection, enhancing the amount of information gained from small amounts of precious samples such as carbonaceous chondrites. We have applied this technique to measure the compound-specific C, N, and H isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites. We are using these measurements to evaluate predictions of expected isotopic enrichments from potential formation pathways and environments, leading to a better understanding of the origin of these compounds.

  2. Emission control of sodium compounds and their formation mechanisms during coal combustion

    SciTech Connect

    Tsuyoshi Takuwa; Ichiro Naruse

    2007-07-01

    In order to control emissions of sodium compounds during coal combustion, the sorbent injection technology is tested during coal combustion. Kaolin is selected as the sorbent to absorb vapors of sodium compounds evolved from the coals. In the combustion experiments, the kaolin is physically mixed with coal. Two types of coal, which have the similar coal properties, are burned. Combustion tests are conducted, using an electrically heated drop tube furnace, to study effect of kaolin addition on the capture characteristics of sodium compounds. In order to elucidate fundamentals on transformation behaviors of sodium compounds during hydrogen-air combustion, chemical kinetic simulation by elementary reactions relating to sodium compounds is also performed, varying the reaction atmosphere. As a result, the kaolin can effectively capture the vapor of sodium compounds even during coal combustion. The capture efficiency depends on the coal type. The sodium compounds for the coals, which produce many fine particles with size of less than 1 {mu}m, tend to be effectively captured by the kaolin. According to the kinetic simulation of sodium species, difference of the reaction atmosphere affects occurrence species of sodium vapor. In the combustion region, the sodium compounds become metallic sodium vapor in any reaction atmospheres due to occurrence of the reducing radical species. HCl gas rather than SO{sub 2} gas plays an important role to transform gaseous sodium compounds. 44 refs., 8 figs., 3 tabs.

  3. Inhibition of heterocyclic aromatic amine formation in fried ground beef patties by garlic and selected garlic-related sulfur compounds.

    PubMed

    Shin, Inn-Seung; Rodgers, W John; Gomaa, Enayat A; Strasburg, Gale M; Gray, J Ian

    2002-11-01

    The effects of garlic and selected organosulfur compounds (diallyl disulfide, dipropyl disulfide, diallyl sulfide, allyl methyl sulfide, allyl mercaptan, cysteine, and cystine) on the formation of heterocyclic aromatic amines (HAAs) in fried ground beef patties were evaluated. Minced garlic cloves (ca. 4.8 to 16.7%, wt/wt) or organosulfur compounds (0.67 mmol) were added directly to ground beef. Patties (100 g) were fried at 225 degrees C (surface temperature) for 10 min per side. Two patties were fried for each replication, and five replicates were analyzed for each treatment. For each replicate, four subsamples were analyzed (two unspiked subsamples for concentration and two spiked subsamples for the recovery of HAA standards). The volatile sulfur compounds significantly (P < 0.05) reduced concentrations of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine by reductions of 46 to 81%, while average reductions of 35, 22, and 71%, were achieved with cystine, cysteine, and whole garlic, respectively. The volatile sulfur compounds reduced concentrations of 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline by 34 to 67%, while reductions of 25, 19, and 63% (P < 0.05) were achieved with cystine, cysteine, and whole garlic, respectively. These studies confirm that garlic and some organosulfur compounds have the potential to reduce HAA formation incooked beef patties.

  4. Strong, ductile, and thermally stable Cu-based metal-intermetallic nanostructured composites

    NASA Astrophysics Data System (ADS)

    Dusoe, Keith J.; Vijayan, Sriram; Bissell, Thomas R.; Chen, Jie; Morley, Jack E.; Valencia, Leopolodo; Dongare, Avinash M.; Aindow, Mark; Lee, Seok-Woo

    2017-01-01

    Bulk metallic glasses (BMGs) and nanocrystalline metals (NMs) have been extensively investigated due to their superior strengths and elastic limits. Despite these excellent mechanical properties, low ductility at room temperature and poor microstructural stability at elevated temperatures often limit their practical applications. Thus, there is a need for a metallic material system that can overcome these performance limits of BMGs and NMs. Here, we present novel Cu-based metal-intermetallic nanostructured composites (MINCs), which exhibit high ultimate compressive strengths (over 2 GPa), high compressive failure strain (over 20%), and superior microstructural stability even at temperatures above the glass transition temperature of Cu-based BMGs. Rapid solidification produces a unique ultra-fine microstructure that contains a large volume fraction of Cu5Zr superlattice intermetallic compound; this contributes to the high strength and superior thermal stability. Mechanical and microstructural characterizations reveal that substantial accumulation of phase boundary sliding at metal/intermetallic interfaces accounts for the extensive ductility observed.

  5. Strong, ductile, and thermally stable Cu-based metal-intermetallic nanostructured composites

    PubMed Central

    Dusoe, Keith J.; Vijayan, Sriram; Bissell, Thomas R.; Chen, Jie; Morley, Jack E.; Valencia, Leopolodo; Dongare, Avinash M.; Aindow, Mark; Lee, Seok-Woo

    2017-01-01

    Bulk metallic glasses (BMGs) and nanocrystalline metals (NMs) have been extensively investigated due to their superior strengths and elastic limits. Despite these excellent mechanical properties, low ductility at room temperature and poor microstructural stability at elevated temperatures often limit their practical applications. Thus, there is a need for a metallic material system that can overcome these performance limits of BMGs and NMs. Here, we present novel Cu-based metal-intermetallic nanostructured composites (MINCs), which exhibit high ultimate compressive strengths (over 2 GPa), high compressive failure strain (over 20%), and superior microstructural stability even at temperatures above the glass transition temperature of Cu-based BMGs. Rapid solidification produces a unique ultra-fine microstructure that contains a large volume fraction of Cu5Zr superlattice intermetallic compound; this contributes to the high strength and superior thermal stability. Mechanical and microstructural characterizations reveal that substantial accumulation of phase boundary sliding at metal/intermetallic interfaces accounts for the extensive ductility observed. PMID:28067334

  6. Effect of Different Flours on the Formation of Hydroxymethylfurfural, Furfural, and Dicarbonyl Compounds in Heated Glucose/Flour Systems

    PubMed Central

    Mesías, Marta; Morales, Francisco J.

    2017-01-01

    Traditional cereal-based foods usually include wheat flour in their formulations; however, the search for new products with new ingredients providing different properties to foods is widely pursued by food companies. Replacement of wheat by other flours can modify both nutritional properties and organoleptic characteristics of the final baked food, but can also impact the formation of potentially harmful compounds. The effect of the type of flour on the formation of furfurals and dicarbonyl compounds was studied in a dough model system during baking that contains water or glucose in order to promote the Maillard reaction and caramelization. The formation of methylglyoxal and glyoxal was significantly reduced in spelt and teff formulations compared to wheat flour formulations, respectively. In contrast, samples formulated with oat, teff, and rye showed a significant increase in the levels of 3-deoxyglucosone. Similarly, spelt and teff formulations presented significantly higher concentrations of hydroxymethylfurfural, and spelt, teff, and rye presented higher concentrations of furfural. Therefore, the formation of process contaminants and undesirable compounds in new food products formulated with different flours replacing the traditional wheat flour should be considered carefully in terms of food safety. PMID:28231092

  7. The vinyl-sulfonium bond in human myeloperoxidase: Impact on compound I formation and reduction by halides and thiocyanate

    SciTech Connect

    Zederbauer, Martina; Furtmueller, Paul Georg; Ganster, Bernadette; Moguilevsky, Nicole; Obinger, Christian . E-mail: christian.obinger@boku.ac.at

    2007-05-04

    In human myeloperoxidase (MPO) the heme is covalently attached to the protein via two ester linkages and a unique sulfonium ion linkage between the sulfur atom of Met243 and the {beta}-carbon of the vinyl ring on pyrrole ring A. Here, we have investigated the variant Met243Val produced in Chinese hamster ovary cells in order to elucidate the role of the electron withdrawing sulfonium bond in compound I formation and reduction. Disruption of this MPO-typical bond causes a blue-shifted UV-vis spectrum and an increase in the heme flexibility. This had no impact on compound I formation mediated by hydrogen peroxide (2.2 x 10{sup 7} M{sup -1} s{sup -1} at pH 7.0 and 25 {sup o}C). Compared with wild-type recombinant MPO the cyanide association rate with ferric Met243Val was significantly enhanced as were also the calculated apparent bimolecular compound I reduction rates by iodide (>10{sup 8} M{sup -1} s{sup -1}) and thiocyanate (>10{sup 8} M{sup -1} s{sup -1}). By contrast, the overall chlorination and bromination activities were decreased by 98.1% and 87.4%, respectively, compared with the wild-type protein. Compound I reduction by chloride was slower than compound I decay to a compound II-like species (0.4 s{sup -1}), whereas compound I reduction by bromide was about 10-times slower (1.3 x 10{sup 4} M{sup -1} s{sup -1}) than the wild-type rate. These findings are discussed with respect to the known crystal structure of MPO and its bromide complex as well as the known redox chemistry of its intermediates and substrates.

  8. Formation of a compound flux rope by the merging of two filament channels, the associated dynamics, and its stability

    SciTech Connect

    Joshi, Navin Chandra; Inoue, Satoshi; Magara, Tetsuya E-mail: njoshi98@gmail.com

    2014-11-01

    We present observations of compound flux rope formation, which occurred on 2014 January 1, via merging of two nearby filament channels, the associated dynamics, and its stability using multiwavelength data. We also discuss the dynamics of cool and hot plasma moving along the newly formed compound flux rope. The merging started after the interaction between the southern leg of the northward filament and the northern leg of the southward filament at ≈01:21 UT and continued until a compound flux rope formed at ≈01:33 UT. During the merging, the cool filament plasma heated up and started to move along both sides of the compound flux rope, i.e., toward the north (≈265 km s{sup –1}) and south (≈118 km s{sup –1}) from the point of merging. After traveling a distance of ≈150 Mm toward the north, the plasma cooled down and started to return back to the south (≈14 km s{sup –1}) after ≈02:00 UT. The observations provide a clear example of compound flux rope formation via merging of two different flux ropes and the occurrence of a flare through tether cutting reconnection. However, the compound flux rope remained stable in the corona and had a confined eruption. The coronal magnetic field decay index measurements revealed that both the filaments and the compound flux rope axis lie within the stability domain (decay index <1.5), which may be the possible cause for their stability. The present study also deals with the relationship between the filament's chirality (sinistral) and the helicity (positive) of the surrounding flux rope.

  9. Oligonuclear molecular models of intermetallic phases: a case study on [Pd2Zn6Ga2(Cp*)5(CH3)3].

    PubMed

    Bollermann, Timo; Molon, Mariusz; Gemel, Christian; Freitag, Kerstin; Seidel, Rüdiger W; von Hopffgarten, Moritz; Jerabek, Paul; Frenking, Gernot; Fischer, Roland A

    2012-04-16

    The synthesis, characterization, and theoretical investigation by means of quantum-chemical calculations of an oligonuclear metal-rich compound are presented. The reaction of homoleptic dinuclear palladium compound [Pd(2)(μ-GaCp*)(3)(GaCp*)(2)] with ZnMe(2) resulted in the formation of unprecedented ternary Pd/Ga/Zn compound [Pd(2)Zn(6)Ga(2)(Cp*)(5)(CH(3))(3)] (1), which was analyzed by (1)H and (13)C NMR spectroscopy, MS, elemental analysis, and single-crystal X-ray diffraction. Compound 1 consisted of two C(s)-symmetric molecular isomers, as revealed by NMR spectroscopy, at which distinct site-preferences related to the Ga and Zn positions were observed by quantum-chemical calculations. Structural characterization of compound 1 showed significantly different coordination environments for both palladium centers. Whilst one Pd atom sat in the central of a bi-capped trigonal prism, thereby resulting in a formal 18-valence electron fragment, {Pd(ZnMe)(2)(ZnCp*)(4)(GaMe)}, the other Pd atom occupied one capping unit, thereby resulting in a highly unsaturated 12-valence electron fragment, {Pd(GaCp*)}. The bonding situation, as determined by atoms-in-molecules analysis (AIM), NBO partial charges, and molecular orbital (MO) analysis, pointed out that significant Pd-Pd interactions had a large stake in the stabilization of this unusual molecule. The characterization and quantum-chemical calculations of compound 1 revealed distinct similarities to related M/Zn/Ga Hume-Rothery intermetallic solid-state compounds, such as Ga/Zn-exchange reactions, the site-preferences of the Zn/Ga positions, and direct M-M bonding, which contributes to the overall stability of the metal-rich compound.

  10. Formation and decay of the compound nucleus *220Th within the dynamical cluster-decay model

    NASA Astrophysics Data System (ADS)

    Hemdeep, Chopra, Sahila; Kaur, Arshdeep; Gupta, Raj K.

    2017-01-01

    Background: The radioactive *220Th compound nucleus (CN) is of interest since the evaporation residue (ER) cross sections are available for various entrance channels 16O+204Pb , 40Ar+180Hf , 48Ca+172Yb , and 82Se+138Ba at near barrier energies. Within the dynamical cluster-decay model (DCM), the radioactive CNs *215Fr, *242Pu, *246Bk, and *254Fm are studied where the main decay mode is fission, with very small predicted ER cross section. *220Th provides a first case with experimentally observed ER cross section instead of fission. Purpose: To look for the optimum "hot-compact" target-projectile (t-p) combinations for the synthesis of "cold"*. For best fitting of the measured ER cross sections, with quasifission (qf) content, if any, the fusion-fission (ff) component is predicted. The magic-shell structure and entrance channel mass-asymmetry effects are analyzed, and the behavior of CN formation and survival probabilities PCN and Psurv is studied. Methods: The quantum-mechanical fragmentation theory (QMFT) is used to predict the possible cold t-p combinations for synthesizing *220Th, and the QMFT-based DCM is used to analyze its decay channels for the experimentally studied entrance channels. The only parameter of the model, the neck length Δ R , varies smoothly with the excitation energy E* of CN and is used to best fit the ER data and predict qf and ff cross sections. Results: The hot-compact and "cold-elongated" fragmentation paths show dissimilar results, whose comparisons with measured fission yields result in t-p combinations, the cold reaction valleys. For the decay process, the fixed Δ R fit the measured ER cross section nicely, but not the individual decay-channel cross sections, which require the presence of qf effects, less so for asymmetric t-p combinations, and large (predicted) ff cross section. Conclusions: The calculated yields for hot-compact fragmentation path compared favorably with the observed asymmetric fission-mass distribution, resulting in

  11. Carbon-containing compounds on fusion-related surfaces: Thermal and ion-induced formation and erosion

    NASA Astrophysics Data System (ADS)

    Linsmeier, Christian

    2004-12-01

    The deposition of carbon on metals is the unavoidable consequence of the application of different wall materials in present and future fusion experiments like ITER. Presently used and prospected materials besides carbon (CFC materials in high heat load areas) are tungsten and beryllium. The simultaneous application of different materials leads to the formation of surface compounds due to the erosion, transport and re-deposition of material during plasma operations. The formation and erosion processes are governed by widely varying surface temperatures and kinetic energies as well as the spectrum of impinging particles from the plasma. The knowledge of the dependence on these parameters is crucial for the understanding and prediction of the compound formation on wall materials. The formation of surface layers is of great importance, since they not only determine erosion rates, but also influence the ability of the first wall for hydrogen isotope inventory accumulation and release. Surface compound formation, diffusion and erosion phenomena are studied under well-controlled ultra-high vacuum conditions using in-situ X-ray photoelectron spectroscopy (XPS) and ion beam analysis techniques available at a 3 MV tandem accelerator. XPS provides chemical information and allows distinguishing elemental and carbidic phases with high surface sensitivity. Accelerator-based spectroscopies provide quantitative compositional analysis and sensitivity for deuterium in the surface layers. Using these techniques, the formation of carbidic layers on metals is studied from room temperature up to 1700 K. The formation of an interfacial carbide of several monolayers thickness is not only observed for metals with exothermic carbide formation enthalpies, but also in the cases of Ni and Fe which form endothermic carbides. Additional carbon deposited at 300 K remains elemental. Depending on the substrate, carbon diffusion into the bulk starts at elevated temperatures together with additional

  12. Antimicrobial activity, synergism and inhibition of germ tube formation by Crocus sativus-derived compounds against Candida spp.

    PubMed

    Carradori, Simone; Chimenti, Paola; Fazzari, Marina; Granese, Arianna; Angiolella, Letizia

    2016-01-01

    The limited arsenal of synthetic antifungal agents and the emergence of resistant Candida strains have prompted the researchers towards the investigation of naturally occurring compounds or their semisynthetic derivatives in order to propose new innovative hit compounds or new antifungal combinations endowed with reduced toxicity. We explored the anti-Candida effects, for the first time, of two bioactive compounds from Crocus sativus stigmas, namely crocin 1 and safranal, and some semisynthetic derivatives of safranal obtaining promising biological results in terms of minimum inhibitory concentration/minimum fungicidal concentration (MIC/MFC) values, synergism and reduction in the germ tube formation. Safranal and its thiosemicarbazone derivative 5 were shown to display good activity against Candida spp.

  13. Titanium aluminide intermetallic alloys with improved wear resistance

    DOEpatents

    Qu, Jun; Lin, Hua-Tay; Blau, Peter J.; Sikka, Vinod K.

    2014-07-08

    The invention is directed to a method for producing a titanium aluminide intermetallic alloy composition having an improved wear resistance, the method comprising heating a titanium aluminide intermetallic alloy material in an oxygen-containing environment at a temperature and for a time sufficient to produce a top oxide layer and underlying oxygen-diffused layer, followed by removal of the top oxide layer such that the oxygen-diffused layer is exposed. The invention is also directed to the resulting oxygen-diffused titanium aluminide intermetallic alloy, as well as mechanical components or devices containing the improved alloy composition.

  14. Conserved valproic-acid-induced lipid droplet formation in Dictyostelium and human hepatocytes identifies structurally active compounds.

    PubMed

    Elphick, Lucy M; Pawolleck, Nadine; Guschina, Irina A; Chaieb, Leila; Eikel, Daniel; Nau, Heinz; Harwood, John L; Plant, Nick J; Williams, Robin S B

    2012-03-01

    Lipid droplet formation and subsequent steatosis (the abnormal retention of lipids within a cell) has been reported to contribute to hepatotoxicity and is an adverse effect of many pharmacological agents including the antiepileptic drug valproic acid (VPA). In this study, we have developed a simple model system (Dictyostelium discoideum) to investigate the effects of VPA and related compounds in lipid droplet formation. In mammalian hepatocytes, VPA increases lipid droplet accumulation over a 24-hour period, giving rise to liver cell damage, and we show a similar effect in Dictyostelium following 30 minutes of VPA treatment. Using (3)H-labelled polyunsaturated (arachidonic) or saturated (palmitic) fatty acids, we shown that VPA treatment of Dictyostelium gives rise to an increased accumulation of both types of fatty acids in phosphatidylcholine, phosphatidylethanolamine and non-polar lipids in this time period, with a similar trend observed in human hepatocytes (Huh7 cells) labelled with [(3)H]arachidonic acid. In addition, pharmacological inhibition of β-oxidation in Dictyostelium phenocopies fatty acid accumulation, in agreement with data reported in mammalian systems. Using Dictyostelium, we then screened a range of VPA-related compounds to identify those with high and low lipid-accumulation potential, and validated these activities for effects on lipid droplet formation by using human hepatocytes. Structure-activity relationships for these VPA-related compounds suggest that lipid accumulation is independent of VPA-catalysed teratogenicity and inositol depletion. These results suggest that Dictyostelium could provide both a novel model system for the analysis of lipid droplet formation in human hepatocytes and a rapid method for identifying VPA-related compounds that show liver toxicology.

  15. Inhibition of Biofilm Formation, Quorum Sensing and Infection in Pseudomonas aeruginosa by Natural Products-Inspired Organosulfur Compounds

    PubMed Central

    Cady, Nathaniel C.; McKean, Kurt A.; Behnke, Jason; Kubec, Roman; Mosier, Aaron P.; Kasper, Stephen H.; Burz, David S.; Musah, Rabi A.

    2012-01-01

    Using a microplate-based screening assay, the effects on Pseudomonas aeruginosa PAO1 biofilm formation of several S-substituted cysteine sulfoxides and their corresponding disulfide derivatives were evaluated. From our library of compounds, S-phenyl-L-cysteine sulfoxide and its breakdown product, diphenyl disulfide, significantly reduced the amount of biofilm formation by P. aeruginosa at levels equivalent to the active concentration of 4-nitropyridine-N-oxide (NPO) (1 mM). Unlike NPO, which is an established inhibitor of bacterial biofilms, our active compounds did not reduce planktonic cell growth and only affected biofilm formation. When used in a Drosophila-based infection model, both S-phenyl-L-cysteine sulfoxide and diphenyl disulfide significantly reduced the P. aeruginosa recovered 18 h post infection (relative to the control), and were non-lethal to the fly hosts. The possibility that the observed biofilm inhibitory effects were related to quorum sensing inhibition (QSI) was investigated using Escherichia coli-based reporters expressing P. aeruginosa lasR or rhIR response proteins, as well as an endogenous P. aeruginosa reporter from the lasI/lasR QS system. Inhibition of quorum sensing by S-phenyl-L-cysteine sulfoxide was observed in all of the reporter systems tested, whereas diphenyl disulfide did not exhibit QSI in either of the E. coli reporters, and showed very limited inhibition in the P. aeruginosa reporter. Since both compounds inhibit biofilm formation but do not show similar QSI activity, it is concluded that they may be functioning by different pathways. The hypothesis that biofilm inhibition by the two active compounds discovered in this work occurs through QSI is discussed. PMID:22715388

  16. A ship-in-a-bottle strategy to synthesize encapsulated intermetallic nanoparticle catalysts: Exemplified for furfural hydrogenation

    SciTech Connect

    Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; Goh, Tian Wei; Wang, Lin -Lin; Gustafson, Jeffrey; Pei, Yuchen; Qi, Zhiyuan; Johnson, Duane D.; Zhang, Shiran; Tao, Franklin; Huang, Wenyu

    2016-01-28

    In this paper, intermetallic compounds are garnering increasing attention as efficient catalysts for improved selectivity in chemical processes. Here, using a ship-in-a-bottle strategy, we synthesize single-phase platinum-based intermetallic nanoparticles (NPs) protected by a mesoporous silica (mSiO2) shell by heterogeneous reduction and nucleation of Sn, Pb, or Zn in mSiO2-encapsulated Pt NPs. For selective hydrogenation of furfural to furfuryl alcohol, a dramatic increase in activity and selectivity is observed when intermetallic NPs catalysts are used in comparison to Pt@mSiO2. Among the intermetallic NPs, PtSn@mSiO2 exhibits the best performance, requiring only one-tenth of the quantity of Pt used in Pt@mSiO2 for similar activity and near 100% selectivity to furfuryl alcohol. A high-temperature oxidation–reduction treatment easily reverses any carbon deposition-induced catalyst deactivation. X-ray photoelectron spectroscopy shows the importance of surface composition to the activity, whereas density functional theory calculations reveal that the enhanced selectivity on PtSn compared to Pt is due to the different furfural adsorption configurations on the two surfaces.

  17. A ship-in-a-bottle strategy to synthesize encapsulated intermetallic nanoparticle catalysts: Exemplified for furfural hydrogenation

    DOE PAGES

    Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; Goh, Tian Wei; ...

    2016-01-28

    In this paper, intermetallic compounds are garnering increasing attention as efficient catalysts for improved selectivity in chemical processes. Here, using a ship-in-a-bottle strategy, we synthesize single-phase platinum-based intermetallic nanoparticles (NPs) protected by a mesoporous silica (mSiO2) shell by heterogeneous reduction and nucleation of Sn, Pb, or Zn in mSiO2-encapsulated Pt NPs. For selective hydrogenation of furfural to furfuryl alcohol, a dramatic increase in activity and selectivity is observed when intermetallic NPs catalysts are used in comparison to Pt@mSiO2. Among the intermetallic NPs, PtSn@mSiO2 exhibits the best performance, requiring only one-tenth of the quantity of Pt used in Pt@mSiO2 for similarmore » activity and near 100% selectivity to furfuryl alcohol. A high-temperature oxidation–reduction treatment easily reverses any carbon deposition-induced catalyst deactivation. X-ray photoelectron spectroscopy shows the importance of surface composition to the activity, whereas density functional theory calculations reveal that the enhanced selectivity on PtSn compared to Pt is due to the different furfural adsorption configurations on the two surfaces.« less

  18. Hot isostatic pressing of intermetallic powders

    NASA Astrophysics Data System (ADS)

    Schaefer, R. J.; Kushner, B. G.

    The application of the intelligent processing of materials (IPM) approach to powder densification by hot isostatic pressing (HIP) is made possible by the development of in situ sensors, process models and adaptive control strategies. The challenge is to optimize the process schedule for new materials to achieve densification, shape and microstructural goals. The development of an IPM system for HIP of intermetallic powders is described. The primary sensor used in this system employs eddy currents to measure changes of sample dimensions, while the process model is that of Ashby et al., reformulated to more closely describe real materials in real HIP process cycles. Process cycles are developed by combining a knowledge base derived from experts with the process model refined by sensor measurements.

  19. Haloacetic acid and trihalomethane formation from the chlorination and bromination of aliphatic beta-dicarbonyl acid model compounds.

    PubMed

    Dickenson, Eric R V; Summers, R Scott; Croué, Jean-Philippe; Gallard, Hervé

    2008-05-01

    While it is known that resorcinol- and phenol-type aromatic structures within natural organic matter (NOM) react during drinking water chlorination to form trihalomethanes (THMs), limited studies have examined aliphatic-type structures as THM and haloacetic acid (HAA) precursors. A suite of aliphatic acid model compounds were chlorinated and brominated separately in controlled laboratory-scale batch experiments. Four and two beta-dicarbonyl acid compounds were found to be important precursors for the formation of THMs (chloroform and bromoform (71-91% mol/mol)), and dihaloacetic acids (DXAAs) (dichloroacetic acid and dibromoacetic acid (5-68% mol/mol)), respectively, after 24 h at pH 8. Based upon adsorbable organic halide formation, THMs and DXAAs, and to a lesser extent mono and trihaloacetic acids, were the majority (> 80%) of the byproducts produced for most of the aliphatic beta-dicarbonyl acid compounds. Aliphatic beta-diketone-acid-type and beta-keto-acid-type structures could be possible fast- and slow-reacting THM precursors, respectively, and aliphatic beta-keto-acid-type structures are possible slow-reacting DXAA precursors. Aliphatic beta-dicarbonyl acid moieties in natural organic matter, particularly in the hydrophilic fraction, could contribute to the significant formation of THMs and DXAAs observed after chlorination of natural waters.

  20. Compound selection for development - is salt formation the ultimate answer? Experiences with an extended concept of the "100mg approach".

    PubMed

    Korn, Christian; Balbach, Stefan

    2014-06-16

    In order to select the best candidates for development, physicochemical criteria such as solubility, chemical and physical stability, hygroscopicity, and thermal characteristics need to be evaluated as early as possible and balanced against other important criteria such as pharmacology or pharmacokinetics. It could be shown, that our miniaturized pharmaceutical profiling concept ("100mg approach"), is capable to reliably identify potential development issues of drug candidates, which, therefore, can be approached early on. Salt formation is a well established strategy to improve unfavorable properties, in particular poor solubility. This article describes our stepwise approach on salt screening, including selection criteria, and summarizes the observations we had during compound investigation. Considering a data base of 337 compounds (salts and uncharged substances), experiences with various counterions evaluated over the last 10years are discussed. We realized that salt formation usually improves poor solubility of a given candidate, but this is often at the cost of other attributes being relevant for pharmaceutical development. Surprisingly, in more than 50% of all cases the "free form" was finally selected after carefully weighing all compound characteristics. Therefore, we conclude that an early salt selection strategy is of utmost importance to predict potential development issues and to enable the provision of alternative physical forms. However, salt formation itself is not necessarily the best solution to meet all development requirements. The selection of a free form (acid or base) in combination with advanced formulation strategies should always be considered, sometimes as best compromise.

  1. Organic matrix effects on the formation of light-absorbing compounds from α-dicarbonyls in aqueous salt solution.

    PubMed

    Drozd, Greg T; McNeill, V Faye

    2014-04-01

    Aqueous-phase reactions of organic compounds are of general importance in environmental systems. Reactions of α-dicarbonyl compounds in the aqueous phase of atmospheric aerosols can impact their climate-relevant physical properties including hygroscopicity and absorption of light. Less-reactive water-soluble organic compounds may contribute an organic matrix component to the aqueous environment, potentially impacting the reaction kinetics. In this work we demonstrate the effects of organic matrices on the self-reactions of glyoxal (Gly) and methylglyoxal (mGly) in aqueous solutions containing ammonium sulfate. At an organic-to-sulfate mass ratio of 2 : 1, carbohydrate-like matrices resembling oxidized organic aerosol material reduce the rate of formation of light-absorbing products by up to an order of magnitude. The greatest decreases in the reaction rates were observed for organic matrices with smaller, more linear molecular structures. Initial UV-Vis spectra, product studies, relative rate data, acidity changes, and viscosity measurements suggest that shifts in carbonyl equilibria, due in part to (hemi)acetal formation with the matrix, reduce the rate of formation of light-absorbing imidazole and oligomer species.

  2. Thermomechanical processing of plasma sprayed intermetallic sheets

    DOEpatents

    Hajaligol, Mohammad R.; Scorey, Clive; Sikka, Vinod K.; Deevi, Seetharama C.; Fleischhauer, Grier; Lilly, Jr., A. Clifton; German, Randall M.

    2001-01-01

    A powder metallurgical process of preparing a sheet from a powder having an intermetallic alloy composition such as an iron, nickel or titanium aluminide. The sheet can be manufactured into electrical resistance heating elements having improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The iron aluminide has an entirely ferritic microstructure which is free of austenite and can include, in weight %, 4 to 32% Al, and optional additions such as .ltoreq.1% Cr, .gtoreq.0.05% Zr .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Ni, .ltoreq.0.75% C, .ltoreq.0.1% B, .ltoreq.1% submicron oxide particles and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, and/or .ltoreq.3% Cu. The process includes forming a non-densified metal sheet by consolidating a powder having an intermetallic alloy composition such as by roll compaction, tape casting or plasma spraying, forming a cold rolled sheet by cold rolling the non-densified metal sheet so as to increase the density and reduce the thickness thereof and annealing the cold rolled sheet. The powder can be a water, polymer or gas atomized powder which is subjecting to sieving and/or blending with a binder prior to the consolidation step. After the consolidation step, the sheet can be partially sintered. The cold rolling and/or annealing steps can be repeated to achieve the desired sheet thickness and properties. The annealing can be carried out in a vacuum furnace with a vacuum or inert atmosphere. During final annealing, the cold rolled sheet recrystallizes to an average grain size of about 10 to 30 .mu.m. Final stress relief annealing can be carried out in the B2 phase temperature range.

  3. A Density Functional Investigation of the Structural, Elastic and Thermodynamic Properties of the Au-Sn Intermetallics

    NASA Astrophysics Data System (ADS)

    Tian, Yali; Zhou, Wei; Wu, Ping

    2016-01-01

    The structural, elastic and thermodynamic properties of AuSn, AuSn2, AuSn4 and Au5Sn are investigated by first-principles calculations. Through calculation, the four intermetallic compounds are all thermodynamically stable and AuSn has the largest negative formation energy. They are all ductile, anisotropic and have low stiffness. In addition, Au5Sn is different from the others, since it is elastically unstable and possesses the highest anisotropy and hardness, mainly due to the strong Au-Au covalent bonds. Based on the quasi-harmonic Debye model, the thermodynamic properties of AuSn, such as the volume, thermal expansion coefficient, bulk modulus, Debye temperature and heat capacity with temperature variation in the range of 0-20 GPa, are obtained. The results indicate the increments of both the volume and thermal expansion coefficient with temperature become slow when the pressure is more than 10 GPa, and the bulk modulus and Debye temperature are almost constant below 100 K and then become linear decreasing as temperature increases. It is found that the influence of temperature on heat capacity is much more obvious than that of pressure.

  4. Ozone formation potentials of organic compounds from different emission sources in the South Coast Air Basin of California

    NASA Astrophysics Data System (ADS)

    Chen, Jianjun; Luo, Dongmin

    2012-08-01

    Different organic compounds exhibit different propensities for ozone formation. Two approaches were used to study the ozone formation potentials or source reactivities of different anthropogenic organic compounds emission categories in California's South Coast Air Basin (SoCAB). The first approach was based on the combination of total organic gases (TOG) emission speciation profiles and the maximum incremental reactivity (MIR) scale of organic species. The second approach quantified ozone impacts from different emission sources by performing 3-dimensional air quality model sensitivity analysis involving increased TOG emissions from particular sources. The source reactivities derived from these two approaches agree reasonably well for 58 anthropogenic organic compounds emission categories in the SoCAB. Both approaches identify TOG emissions from mobile sources as having the highest reactivity. Source reactivities from both approaches were also combined with TOG emissions from each source category to produce a 2005 reactivity-based anthropogenic TOG emission inventory for the SoCAB. The top five reactivity-based anthropogenic TOG emission sources in the SoCAB during 2005 were: light-duty passenger cars, off-road equipment, consumer products, light-duty trucks category 2 (i.e., 3751-5750 lb), and recreational boats. This is in contrast to the mass-based TOG emission inventory, which indicates that livestock waste and composting emission categories were two of the five largest mass-based anthropogenic TOG emission sources. The reactivity-based TOG emission inventory is an important addition to the mass-based TOG emission inventory because it represents the ozone formation potentials from emission sources and can be used to assist in determining targeted sources for developing organic compounds reduction policies.

  5. Local Strain Development and Property Variability in B2 Intermetallics

    DTIC Science & Technology

    2005-09-19

    COVERED (From - To) 19092005 Final Report 15 Jan 2001 - 30 Apr 2005 4 . TITLE AND SUBTITLE 5a. CONTRACT NUMBER Local Strain Development and Property...Variability in B2 Intermetallics 5b. GRANT NUMBER F49620-01-1-0159 5c. PROGRAM ELEMENT NUMBER 6 . AUTHOR(S) 5d. PROJECT NUMBER Professor Tresa M. Pollock 5e... 4 3.0 The Strain Mapping Technique .............................................. 4 4.0 Intermetallic

  6. Regulation of formation of volatile compounds of tea (Camellia sinensis) leaves by single light wavelength.

    PubMed

    Fu, Xiumin; Chen, Yiyong; Mei, Xin; Katsuno, Tsuyoshi; Kobayashi, Eiji; Dong, Fang; Watanabe, Naoharu; Yang, Ziyin

    2015-11-16

    Regulation of plant growth and development by light wavelength has been extensively studied. Less attention has been paid to effect of light wavelength on formation of plant metabolites. The objective of this study was to investigate whether formation of volatiles in preharvest and postharvest tea (Camellia sinensis) leaves can be regulated by light wavelength. In the present study, in contrast to the natural light or dark treatment, blue light (470 nm) and red light (660 nm) significantly increased most endogenous volatiles including volatile fatty acid derivatives (VFADs), volatile phenylpropanoids/benzenoids (VPBs), and volatile terpenes (VTs) in the preharvest tea leaves. Furthermore, blue and red lights significantly up-regulated the expression levels of 9/13-lipoxygenases involved in VFADs formation, phenylalanine ammonialyase involved in VPBs formation, and terpene synthases involved in VTs formation. Single light wavelength had less remarkable influences on formation of volatiles in the postharvest leaves compared with the preharvest leaves. These results suggest that blue and red lights can be promising technology for remodeling the aroma of preharvest tea leaves. Furthermore, our study provided evidence that light wavelength can activate the expression of key genes involved in formation of plant volatiles for the first time.

  7. Regulation of formation of volatile compounds of tea (Camellia sinensis) leaves by single light wavelength

    PubMed Central

    Fu, Xiumin; Chen, Yiyong; Mei, Xin; Katsuno, Tsuyoshi; Kobayashi, Eiji; Dong, Fang; Watanabe, Naoharu; Yang, Ziyin

    2015-01-01

    Regulation of plant growth and development by light wavelength has been extensively studied. Less attention has been paid to effect of light wavelength on formation of plant metabolites. The objective of this study was to investigate whether formation of volatiles in preharvest and postharvest tea (Camellia sinensis) leaves can be regulated by light wavelength. In the present study, in contrast to the natural light or dark treatment, blue light (470 nm) and red light (660 nm) significantly increased most endogenous volatiles including volatile fatty acid derivatives (VFADs), volatile phenylpropanoids/benzenoids (VPBs), and volatile terpenes (VTs) in the preharvest tea leaves. Furthermore, blue and red lights significantly up-regulated the expression levels of 9/13-lipoxygenases involved in VFADs formation, phenylalanine ammonialyase involved in VPBs formation, and terpene synthases involved in VTs formation. Single light wavelength had less remarkable influences on formation of volatiles in the postharvest leaves compared with the preharvest leaves. These results suggest that blue and red lights can be promising technology for remodeling the aroma of preharvest tea leaves. Furthermore, our study provided evidence that light wavelength can activate the expression of key genes involved in formation of plant volatiles for the first time. PMID:26567525

  8. Multiscale modeling of the influence of Fe content in a Al-Si-Cu alloy on the size distribution of intermetallic phases and micropores

    NASA Astrophysics Data System (ADS)

    Wang, Junsheng; Li, Mei; Allison, John; Lee, Peter D.

    2010-03-01

    A multiscale model was developed to simulate the formation of Fe-rich intermetallics and pores in quaternary Al-Si-Cu-Fe alloys. At the microscale, the multicomponent diffusion equations were solved for multiphase (liquid-solid-gas) materials via a finite difference framework to predict microstructure formation. A fast and robust decentered plate algorithm was developed to simulate the strong anisotropy of the solid/liquid interfacial energy for the Fe-rich intermetallic phase. The growth of porosity was controlled by local pressure drop due to solidification and interactions with surrounding solid phases, in addition to hydrogen diffusion. The microscale model was implemented as a subroutine in a commercial finite element package, producing a coupled multiscale model. This allows the influence of varying casting conditions on the Fe-rich intermetallics, the pores, and their interactions to be predicted. Synchrotron x-ray tomography experiments were performed to validate the model by comparing the three-dimensional morphology and size distribution of Fe-rich intermetallics as a function of Fe content. Large platelike Fe-rich β intermetallics were successfully simulated by the multiscale model and their influence on pore size distribution in shape castings was predicted as a function of casting conditions.

  9. A Nanocrystalline Ni2(Cr,Mo) Intermetallic with Potentially Useful Combination of Properties for Gas Turbine Seal Ring Applications

    NASA Astrophysics Data System (ADS)

    Tawancy, H. M.; Al-Hadhrami, Luai M.

    2012-07-01

    Seal rings are installed for each turbine stage in gas turbine engines to minimize the loss in gas pressure and maintain engine efficiency. During service, seal rings become susceptible to failure by thermal fatigue as demonstrated by a case study. Therefore, a lower coefficient of thermal expansion is among the most important requirements for these applications. We show that long-range ordering in a Ni-Cr-Mo alloy can be used to synthesize a nanocrystalline intermetallic compound combining high strength, high ductility, low coefficient of thermal expansion, and an adequate oxidation resistance up to at least 700 °C. Twinning rather than slip is found to be the predominant deformation mechanism of the intermetallic compound, which is correlated with the crystallography of the disorder-to-order transformation and microstructure evolution. This could explain the enhanced plasticity of the intermetallic compound. The combination of enhanced plasticity, low-thermal expansion, and nano-sized crystals is expected to improve the resistance to thermal fatigue failure.

  10. Modeling of Substitutional Site Preference in Ordered Intermetallic Alloys

    NASA Technical Reports Server (NTRS)

    Bozzolo, Guillermo; Noebe, Ronald D.; Honecy, Frank

    1998-01-01

    We investigate the site substitution scheme of specific alloying elements in ordered compounds and the dependence of site occupancy on compound stoichiometry, alloy concentration. This basic knowledge, and the interactions with other alloying additions are necessary in order to predict and understand the effect of various alloying schemes on the physical properties of a material, its response to various temperature treatments, and the resulting mechanical properties. Many theoretical methods can provide useful but limited insight in this area, since most techniques suffer from constraints in the type of elements and the crystallographic structures that can be modeled. With this in mind, the Bozzolo-Ferrante-Smith (BFS) method for alloys was designed to overcome these limitations, with the intent of providing an useful tool for the theoretical prediction of fundamental properties and structure of complex systems. After a brief description of the BFS method, its use for the determination of site substitution schemes for individual as well as collective alloying additions to intermetallic systems is described, including results for the concentration dependence of the lattice parameter. Focusing on B2 NiAl, FeAl and CoAl alloys, the energetics of Si, Ti, V, Cr, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Hf, Ta and W alloying additions are surveyed. The effect of single additions as well as the result of two simultaneous additions, discussing the interaction between additions and their influence on site preference schemes is considered. Finally, the BFS analysis is extended to ternary L1(sub 2) (Heusler phase) alloys. A comparison between experimental and theoretical results for the limited number of cases for which experimental data is available is also included.

  11. Effects of molecular weight of PVA on formation, stability and deformation of compound droplets for ICF polymer shells

    NASA Astrophysics Data System (ADS)

    Liu, Meifang; Zheng, Yueqing; Li, Jie; Chen, Sufen; Liu, Yiyang; Li, Jing; Li, Bo; Zhang, Zhanwen

    2017-01-01

    Sphericity and wall thickness uniformity are some of the hardest specifications to fulfill, as required by inertial confined fusion (ICF) research for polymer shells prepared by the microencapsulation technique. Driven by the need to control the deformation of compound droplets, the effects of the molecular weight of poly(vinyl alcohol) (PVA) on the formation and stability of the droplets, as well as the sphericity and wall thickness uniformity of the resulting shells, were investigated. On increasing the molecular weight of the PVA, the densities of the external water phases (W2) are almost the same, but the viscosity of the W2 phase increases more quickly than the interfacial tension. This makes the detaching force increase more quickly than the upward one, causing the formation of compound droplets and detachment from the oil tube. On the other hand, the increase in interfacial tension makes the maximum pressures ( P max) in the O phase (O) of the compound droplets increase, causing them to rupture easily and decreasing their stability. However, for PVA with the same molecular weight, the viscous shear force in the flowing field reduces the role of gravity and makes the inner water droplet move towards the center of the compound droplet, decreasing its P max in the flowing field and improving its stability. Moreover, during the solidifying process, the viscous shear force increases more quickly than the interfacial tension force due to the quicker increase in viscosity with an increase in the molecular weight of the PVA. The increase in the viscous shear force can make the droplets deform, resulting in a decrease in their sphericity. However, the appropriate viscous shear force can also center the compound droplet—although they become decentered when the viscous shear force is too large, leading to the wall thickness uniformity increasing at first before decreasing quickly. The results presented in this work provide a more in-depth understanding of the

  12. HIGHLY SENSITIVE ASSAY FOR ANTICHOLINESTERASE COMPOUNDS USING 96 WELL PLATE FORMAT

    EPA Science Inventory

    One of the approaches for reducing uncertainties in the assessment of human exposure is to better characterize concentrations of hazardous compounds that may be present in our immediate environment. A significant limitation to this approach, however, is that sampling and labora...

  13. Direct C-H alkylation and indole formation of anilines with diazo compounds under rhodium catalysis.

    PubMed

    Mishra, Neeraj Kumar; Choi, Miji; Jo, Hyeim; Oh, Yongguk; Sharma, Satyasheel; Han, Sang Hoon; Jeong, Taejoo; Han, Sangil; Lee, Seok-Yong; Kim, In Su

    2015-12-18

    The rhodium(III)-catalyzed direct functionalization of aniline C-H bonds with α-diazo compounds is described. These transformations provide a facile construction of ortho-alkylated anilines with diazo malonates or highly substituted indoles with diazo acetoacetates.

  14. Formation and Ecotoxicity of N-Heterocyclic Compounds on Ammoxidation of Mono- and Polysaccharides

    PubMed Central

    2013-01-01

    Ammoxidation of technical lignins under mild conditions is a suitable approach to artificial humic substances. However, carbohydrates as common minor constituents of technical lignins have been demonstrated to be a potential source of N-heterocyclic ecotoxic compounds. Ethyl acetate extracts of ammoxidation mixtures of the monosaccharides glucose and xylose exhibited considerable growth inhibiting activity in the OECD 201 test, with 4-methyl-1H-imidazole, 4-(hydroxymethyl)-1H-imidazole, and 3-hydroxypyridine being the most active compounds. The amount of N-heterocyclic compounds formed at moderate ammoxidation conditions (70 °C, 0.2 MPa O2, 3 h) was significantly lower for the polysaccharides cellulose and xylan (16–30 μg/g of educt) compared to glucose (15.4 mg). Ammoxidation at higher temperature is not recommendable for carbohydrate-rich materials as much higher amounts of N-heterocyclic compounds were formed from both monosaccharides (100 °C: 122.4–160.5 mg/g of educt) and polysaccharides (140 °C: 5.52–16.03 mg/g of educt). PMID:23967874

  15. Ionic Strength-Induced Formation of Smectite Quasicrystals Enhances Nitroaromatic Compound Sorption

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The influence of ionic strength on nitroaromatic compound sorption from water by K+- and Ca2+-saturated smectite (SWy-2) was examined. The results indicated that sorption of 1,3-dinitrobenzene by K-SWy-2 increased up to 2.2 times as KCl ionic strength increased from 0.01 to 0.30 M. In contrast, sorp...

  16. ISOTOPIC (14C) AND CHEMICAL COMPOSITION OF ATMOSPHERIC VOLATILE ORGANIC COMPOUND FRACTIONS - PRECURSORS TO OZONE FORMATION

    EPA Science Inventory

    Atmospheric volatile organic compounds (VOCs) are an important factor in the production of ozone near ground level [3]. Many hydrocarbons originate from auto exhaust. However, a number of VOCs, e.g., isoprene, are known to be natural in origin. To develop reliable models for un...

  17. Peculiarities in the formation of complex organic compounds in a nitrogen-methane atmosphere during hypervelocity impacts

    NASA Astrophysics Data System (ADS)

    Zaitsev, M. A.; Gerasimov, M. V.; Safonova, E. N.; Vasiljeva, A. S.

    2016-03-01

    Results of the experiments on model impact vaporization of peridotite, a mineral analogue of stony asteroids, in a nitrogen-methane atmosphere are presented. Nd-glass laser (γ = 1.06 µm) was used for simulation. Pulse energy was ~600-700 J, pulse duration ~10-3 s, vaporization tempereature ~4000-5000 K. The gaseous medium (96% vol. of N2 and 4% vol. of CH4, P = 1 atm) was a possible analogue of early atmospheres of terrestrial planets and corresponded to the present-day atmosphere composition of Titan, a satellite of Saturn. By means of pyrolytic gas chromatography/mass spectrometry, it is shown that solid condensates obtained in laser experiments contain relatively complex lowand high-molecular weight (kerogen-like) organic compounds. The main products of condensate pyrolysis were benzene and alkyl benzenes (including long-chain ones), unbranched aliphatic hydrocarbons, and various nitrogen-containing compounds (aliphatic and aromatic nitriles and pyrrol). It is shown that the nitrogen-methane atmosphere favors the formation of complex organic compounds upon hypervelocity impacts with the participation of stony bodies even with a small methane content in it. In this process, falling bodies may not contain carbon, hydrogen, and other chemical elements necessary for the formation of the organic matter. In such conditions, a noticeable contribution to the impact-induced synthesis of complex organic substances is probably made by heterogeneous catalytic reactions, in particular, Fischer-Tropsch type reactions.

  18. Heterologous production of methionine-gamma-lyase from Brevibacterium linens in Lactococcus lactis and formation of volatile sulfur compounds.

    PubMed

    Hanniffy, Sean B; Philo, Mark; Peláez, Carmen; Gasson, Michael J; Requena, Teresa; Martínez-Cuesta, M C

    2009-04-01

    The conversion of methionine to volatile sulfur compounds (VSCs) is of great importance in flavor formation during cheese ripening and is the focus of biotechnological approaches toward flavor improvement. A synthetic mgl gene encoding methionine-gamma-lyase (MGL) from Brevibacterium linens BL2 was cloned into a Lactococcus lactis expression plasmid under the control of the nisin-inducible promoter PnisA. When expressed in L. lactis and purified as a recombinant protein, MGL was shown to degrade L-methionine as well as other sulfur-containing compounds such as L-cysteine, L-cystathionine, and L-cystine. Overproduction of MGL in recombinant L. lactis also resulted in an increase in the degradation of these compounds compared to the wild-type strain. Importantly, gas chromatography-mass spectrometry analysis identified considerably higher formation of methanethiol (and its oxidized derivatives dimethyl disulfide and dimethyl trisulfide) in reactions containing either purified protein, whole cells, or cell extracts from the heterologous L. lactis strain. This is the first report of production of MGL from B. linens in L. lactis. Given their significance in cheese flavor development, the use of lactic acid bacteria with enhanced VSC-producing abilities could be an efficient way to enhance cheese flavor development.

  19. Electronic and optical properties of RESn3 (RE=Pr & Nd) intermetallics: A first principles study

    NASA Astrophysics Data System (ADS)

    Pagare, G.; Abraham, Jisha A.; Sanyal, S. P.

    2015-06-01

    A theoretical study of structural, electronic and optical properties of RESn3 (RE = Pr & Nd) intermetallics have been investigated systematically using first principles density functional theory. The calculations are carried out within the PBE-GGA and LSDA for the exchange correlation potential. The ground state properties such as lattice parameter (a0), bulk modulus (B) and its pressure derivative (B') are calculated and the calculated lattice parameters show well agreement with the experimental results. We first time predict elastic constants for these compounds. From energy dispersion curves, it is found that these compounds are metallic in nature. The linear optical response of these compounds are also studied and the higher value of static dielectric constant shows the possibility to use them as good dielectric materials.

  20. UV-based advanced oxidation processes for the treatment of odour compounds: efficiency and by-product formation.

    PubMed

    Zoschke, Kristin; Dietrich, Norman; Börnick, Hilmar; Worch, Eckhard

    2012-10-15

    The occurrence of the taste and odour compounds geosmin and 2-methyl isoborneol (2-MIB) affects the organoleptic quality of raw waters from drinking water reservoirs worldwide. UV-based oxidation processes for the removal of these substances are an alternative to adsorption and biological processes, since they additionally provide disinfection of the raw water. We could show that the concentration of geosmin and 2-MIB could be reduced by VUV irradiation and the combination of UV irradiation with ozone and hydrogen peroxide in pure water and water from a drinking water reservoir. The figure of merit EE/O is an appropriate tool to compare the AOPs and showed that VUV and UV/O(3) yielded the lowest treatment costs for the odour compounds in pure and raw water, respectively. Additionally, VUV irradiation with addition of ozone, generated by the VUV lamp, was evaluated. The generation of ozone and the irradiation were performed in a single reactor system using the same low-pressure mercury lamp, thereby reducing the energy consumption of the treatment process. The formation of the undesired by-products nitrite and bromate was investigated. The combination of VUV irradiation with ozone produced by a VUV lamp avoided the formation of relevant concentrations of the by-products. The internal generation of ozone is capable to produce ozone concentrations sufficient to reduce EE/O below 1 kWh m(-3) and without the risk of the formation of nitrite or bromate above the maximum contaminant level.

  1. Formation of volatile compounds during heating of spice paprika (Capsicum annuum) powder.

    PubMed

    Cremer, D R; Eichner, K

    2000-06-01

    Spice paprika (red pepper; Capsicum annuum) is the most cultivated spice worldwide and is used mainly for its color and pungency. However, current research is also focusing on the flavor as an important parameter. This paper deals with the kinetics of the formation of those volatiles that indicate a decrease in spice paprika quality due to Maillard reaction, hydrolytic reactions, and oxidative degradation reactions of lipids such as fatty acids and carotenoids. Spice paprika volatiles were quantitatively analyzed by means of headspace gas chromatography (HS-GC) and solid-phase microextraction (SPME) followed by gas chromatography-mass spectrometry (GC-MS). The kinetics of their formation were investigated, and the respective activation energies determined. Strecker aldehyde, acetone, and methanol formation followed a pseudo-zero-order reaction kinetic, and formation of dimethyl sulfide (DMS) was characterized by a first-order kinetic. The activation energies determined were between 86.3 and 101.8 for the Strecker aldehydes acetaldehyde (AA), 2-methylpropanal (2-MP), 3-methylbutanal (3-MB), and 2-methylbutanal (2-MB), 130.7 for acetone, 114.2 for methanol, and 109.7 kJ/mol for DMS. The amounts of Strecker aldehydes formed were correlated to the concentrations of the corresponding free amino acids present in the samples. The formation of hexanal and 6-methyl-5-hepten-2-one in Capsicum annuum during processing was confirmed, and the formation of beta-ionone was probably described for the first time. During heating, the concentration of hexanal increased rapidly. The formation of 6-methyl-5-hepten-2-one confirms that Capsicum annuum fruits contain lycopene.

  2. Change in haloacetic acid formation potential during UV and UV/H2O2 treatment of model organic compounds.

    PubMed

    Sakai, Hiroshi; Autin, Olivier; Parsons, Simon

    2013-07-01

    Haloacetic acids (HAAs) are disinfection by-products produced by the chlorination of organic matter, including amino acids. Advanced oxidation processes are expected to be effective for the destruction of HAA precursors; however, recent studies have reported the possible failure of these processes to reduce HAA formation potential. This study examined HAA formation potential during the course of UV or UV/H2O2 treatment of three organic compounds: leucine, serine, and resorcinol. HAA formation potential decreased in the treatment of resorcinol, while the potential increased slightly in the treatment of serine and greatly increased for leucine. The chemical structure required for HAA formation was assumed to be produced during the course of UV/H2O2 treatment of leucine and serine. Also, H abstraction from the δ carbon was assumed to result from the initial degradation of leucine by the hydroxyl radical during the UV/H2O2 treatment. The hydroxyl radical may have further reacted with leucine moiety to shorten its carbon chain. This would have produced a chemical structure capable of forming HAA, thus increasing HAA formation potential.

  3. The Formation of Complex Organic Compounds in Astrophysical Ices and their Implications for Astrobiology

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.

    2015-01-01

    Ices in astrophysical environments are generally dominated by very simple molecules like H2O, CH3OH, CH4, NH3, CO, CO2, etc, although they likely contain PAHs as well. These molecules, particularly H2O, are of direct interest to astrobiology in-and-of themselves since they represent some of the main carriers of the biogenic elements C, H, O, and N. In addition, these compounds are present in the dense interstellar clouds in which new stars and planetary systems are formed and may play a large role in the delivery of volatiles and organics to the surfaces of new planets. However, these molecules are all far simpler than the more complex organic compounds found in living systems.

  4. Formation of beta-fructosyl compounds of pyridoxine in growing culture of Aspergillus niger.

    PubMed

    Suzuki, Y; Uchida, K

    1993-06-01

    Two pyridoxine compounds were found to be formed in a culture filtrate of Aspergillus niger and A. sydowi, when grown in a medium containing sucrose and pyridoxine. Each of the two compounds I and II was obtained as a white powdered preparation by preparative paper chromatography, gel filtration on Toyopearl HW-40S and Sephadex G-10 columns, DEAE-cellulose column chromatography, and lyophilization. Compounds I and II were identified as 5'-O-(beta-D-fructofuranosyl)-pyridoxine and 5'-O-[beta-D-fructofuranosyl-(2-->1)-beta-D-fructofuranosyl]-pyridoxine, on the basis of the various experimental results, viz., elementary analyses, UV, 1H-, and 13C-NMR spectra, products by hydrolysis with acid and yeast beta-D-fructofuranosidase, migration on paper electrophoresis, and Gibbs reaction in the presence and absence of boric acid. Levansucrase from Microbacterium laevaniformans and yeast beta-D-fructofuranosidase did not catalyze the beta-D-fructofuranosyl transfer from sucrose to pyridoxine to give rise to beta-D-fructofuranosyl-pyridoxine.

  5. Elucidating the formation pathway of the off-flavor compound 6-propylbenzofuran-7-ol.

    PubMed

    Sakamaki, Kensuke; Ishizaki, Susumu; Ohkubo, Yasutaka; Tateno, Yoshiyuki; Nakanishi, Akira; Fujita, Akira

    2012-10-10

    In a previous work, we identified 6-propylbenzofuran-7-ol as an off-flavor compound formed from ascorbic acid and (E)-hex-2-enal in a test apple beverage. In this study, we elucidate the pathway by which 6-propylbenzofuran-7-ol formed. Isotope labeling studies revealed that the propyl group of 6-propylbenzofuran-7-ol derives from (E)-hex-2-enal and that 6-propylbenzofuran-7-ol contains carbons 2-6 of ascorbic acid. Two compounds, namely, 2,3-dihydro-6-propylbenzofuran-3,7-diol and 3-(2-furoyl)hexanal, were identified as byproducts of a model reaction of ascorbic acid and (E)-hex-2-enal. Each of these compounds was dissolved in an aqueous solution of citric acid and stored at 60 °C for 1 week. After storage, 6-propylbenzofuran-7-ol was detected from a solution of 2,3-dihydro-6-propylbenzofuran-3,7-diol, but not from 3-(2-furoyl)hexanal. 6-Propylbenzofuran-7-ol was formed by isolating tricyclic hemiacetal lactone derived from the Michael addition of ascorbic acid to (E)-hex-2-enal, mixing the tricyclic hemiacetal lactone with the aqueous solution of citric acid, and applying heat. This confirmed that 6-propylbenzofuran-7-ol was formed via the Michael adduct.

  6. Secondary brown carbon - Formation of light-absorbing compounds in atmospheric particulates from selected dicarbonyls and amines

    NASA Astrophysics Data System (ADS)

    Kampf, Christopher; Filippi, Alexander; Hoffmann, Thorsten

    2015-04-01

    One of the main open questions regarding organic compounds in atmospheric chemistry today is related to the formation of optically-active compounds and the occurrence of so called brown carbon (Andreae and Gelencsér, 2006). While organic compounds in ambient fine particles for decades have been assumed to not absorb solar radiation, thus resulting in a net cooling effect on climate (IPCC, 2007), it is now generally accepted that a continuum of light-absorbing carbonaceous species is present in fine aerosols (Pöschl, 2003). In this study, light-absorbing compounds from reactions between dicarbonyl compounds, i.e., glyoxal, methylglyoxal, acetylacetone, 2,3-butanedione, 2,5-hexanedione, and glutaraldehyde, and amine species, i.e., ammonia and glycine, were investigated at atmospherically relevant concentrations in bulk solution experiments mimicking atmospheric particulates. Product analyses were performed using UV/Vis spectrophotometry and (ultra) high performance liquid chromatography coupled to diode array detection and ion trap mass spectrometry (HPLC-DAD-ESI-MS/MS), as well as ultra-high resolution (Orbitrap) mass spectrometry (UHPLC-ESI-HRMS/MS). We demonstrate that light-absorbing compounds are formed from a variety of atmospherically relevant dicarbonyls via particle phase reactions with amine nucleophiles. Single dicarbonyl and mixed dicarbonyl experiments were performed and products were analyzed. The reaction products are suggested to be cyclic nitrogen containing compounds such as imidazoles or dihydropyridines as well as open chain compounds resulting from aldol condensation reactions. Further, the reactive turnover was found to be higher at increasing pH values. The aforementioned processes may be of higher relevance in regions with high aerosol pH, e.g., resulting from high ammonia emissions as for example in northern India (Clarisse et al., 2009). References Andreae, M.O., and Gelencsér, A. (2006): Black carbon or brown carbon? The nature of light

  7. Use of HμREL Human Coculture System for Prediction of Intrinsic Clearance and Metabolite Formation for Slowly Metabolized Compounds.

    PubMed

    Hultman, Ia; Vedin, Charlotta; Abrahamsson, Anna; Winiwarter, Susanne; Darnell, Malin

    2016-08-01

    Design of slowly metabolized compounds is an important goal in many drug discovery projects. Standard hepatocyte suspension intrinsic clearance (CLint) methods can only provide reliable CLint values above 2.5 μL/min/million cells. A method that permits extended incubation time with maintained performance and metabolic activity of the in vitro system is warranted to allow in vivo clearance predictions and metabolite identification of slowly metabolized drugs. The aim of this study was to evaluate the static HμREL coculture of human hepatocytes with stromal cells to be set up in-house as a standard method for in vivo clearance prediction and metabolite identification of slowly metabolized drugs. Fourteen low CLint compounds were incubated for 3 days, and seven intermediate to high CLint compounds and a cocktail of cytochrome P450 (P450) marker substrates were incubated for 3 h. In vivo clearance was predicted for 20 compounds applying the regression line approach, and HμREL coculture predicted the human intrinsic clearance for 45% of the drugs within 2-fold and 70% of the drugs within 3-fold of the clinical values. CLint values as low as 0.3 μL/min/million hepatocytes were robustly produced, giving 8-fold improved sensitivity of robust low CLint determination, over the cutoff in hepatocyte suspension CLint methods. The CLint values of intermediate to high CLint compounds were at similar levels both in HμREL coculture and in freshly thawed hepatocytes. In the HμREL coculture formation rates for five P450-isoform marker reactions, paracetamol (CYP1A2), 1-OH-bupropion (CYP2B6), 4-OH-diclofenac (CYP2C9), and 1-OH-midazolam (3A4) were within the range of literature values for freshly thawed hepatocytes, whereas 1-OH-bufuralol (CYP2D6) formation rate was lower. Further, both phase I and phase II metabolites were detected and an increased number of metabolites were observed in the HμREL coculture compared to hepatocyte suspension. In conclusion, HμREL coculture can

  8. High temperature intermetallic binders for HVOF carbides

    SciTech Connect

    Shaw, K.G.; Gruninger, M.F.; Jarosinski, W.J.

    1994-12-31

    Gas turbines technology has a long history of employing the desirable high temperature physical attributes of ceramic-metallic (cermet) materials. The most commonly used coatings incorporate combinations of WC-Co and Cr{sub 3}C{sub 2}-NiCr, which have also been successfully utilized in other non-turbine coating applications. Increased turbine operating temperatures and other high temperature service conditions have made apparent the attractive notion of increasing the temperature capability and corrosion resistance of these coatings. In this study the intermetallic binder NiAl has been used to replace the cobalt and NiCr constituents of conventional WC and Cr{sub 3}C{sub 2} cermet powders. The composite carbide thermal spray powders were fabricated for use in the HVOF coating process. The structure of HVOF deposited NiAl-carbide coatings are compared directly to the more familiar WC-Co and Cr{sub 3}C{sub 2}-NiCr coatings using X-ray diffraction, back-scattered electron imaging (BEI) and electron dispersive spectroscopy (EDS). Hardness variations with temperature are reported and compared between the NiAl and Co/NiCr binders.

  9. Thermal stress effects in intermetallic matrix composites

    NASA Technical Reports Server (NTRS)

    Wright, P. K.; Sensmeier, M. D.; Kupperman, D. S.; Wadley, H. N. G.

    1993-01-01

    Intermetallic matrix composites develop residual stresses from the large thermal expansion mismatch (delta-alpha) between the fibers and matrix. This work was undertaken to: establish improved techniques to measure these thermal stresses in IMC's; determine residual stresses in a variety of IMC systems by experiments and modeling; and, determine the effect of residual stresses on selected mechanical properties of an IMC. X ray diffraction (XRD), neutron diffraction (ND), synchrotron XRD (SXRD), and ultrasonics (US) techniques for measuring thermal stresses in IMC were examined and ND was selected as the most promising technique. ND was demonstrated on a variety of IMC systems encompassing Ti- and Ni-base matrices, SiC, W, and Al2O3 fibers, and different fiber fractions (Vf). Experimental results on these systems agreed with predictions of a concentric cylinder model. In SiC/Ti-base systems, little yielding was found and stresses were controlled primarily by delta-alpha and Vf. In Ni-base matrix systems, yield strength of the matrix and Vf controlled stress levels. The longitudinal residual stresses in SCS-6/Ti-24Al-llNb composite were modified by thermomechanical processing. Increasing residual stress decreased ultimate tensile strength in agreement with model predictions. Fiber pushout strength showed an unexpected inverse correlation with residual stress. In-plane shear yield strength showed no dependence on residual stress. Higher levels of residual tension led to higher fatigue crack growth rates, as suggested by matrix mean stress effects.

  10. Ground state searches in fcc intermetallics

    SciTech Connect

    Wolverton, C.; de Fontaine, D. ); Ceder, G. ); Dreysse, H. . Lab. de Physique du Solide)

    1991-12-01

    A cluster expansion is used to predict the fcc ground states, i.e., the stable phases at zero Kelvin as a function of composition, for alloy systems. The intermetallic structures are not assumed, but derived regorously by minimizing the configurational energy subject to linear constraints. This ground state search includes pair and multiplet interactions which spatially extend to fourth nearest neighbor. A large number of these concentration-independent interactions are computed by the method of direct configurational averaging using a linearized-muffin-tin orbital Hamiltonian cast into tight binding form (TB-LMTO). The interactions, derived without the use of any adjustable or experimentally obtained parameters, are compared to those calculated via the generalized perturbation method extention of the coherent potential approximation within the context of a KKR Hamiltonian (KKR-CPA-GPM). Agreement with the KKR-CPA-GPM results is quite excellent, as is the comparison of the ground state results with the fcc-based portions of the experimentally-determined phase diagrams under consideration.

  11. HIGHLY SENSITIVE ASSAY FOR ANTICHOLINESTERASE COMPOUNDS USING 96 WELL PLATE FORMAT

    EPA Science Inventory

    The rapid and sensitive detection of organophosphate insecticides using a 96 well plate format is reported. Several features of this assay make it attractive for development as a laboratory-based or field screening assay. Acetylcholinesterase (AChE) was stabilized in a gelati...

  12. Formation of Toxic Iodinated Disinfection By-Products from Compounds Used in Medical Imaging

    EPA Science Inventory

    Iodinated X-ray contrast media (ICM) were investigated as a source of iodine in the formation of iodo-trihalomethane (iodo-THM) and iodo-acid disinfection byproducts (DBPs), both of which are highly genotoxic and/or cytotoxic in mammalian cells. ICM are widely used at medical cen...

  13. Some Contributions of Resistant Compounds to Soil Organic Matter Formation and Nutrient Cycling

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Some biomolecules in soil organic matter (SOM) are intrinsically more resistant to microbial decomposition than are other SOM components. Their resistance can be altered by soil properties and by land management, which can affect the formation and stability of SOM and in turn soil processes. Selecte...

  14. Enzymatic formation of compound-K from ginsenoside Rb1 by enzyme preparation from cultured mycelia of Armillaria mellea

    PubMed Central

    Upadhyaya, Jitendra; Kim, Min-Ji; Kim, Young-Hoi; Ko, Sung-Ryong; Park, Hee-Won; Kim, Myung-Kon

    2015-01-01

    Background Minor saponins or human intestinal bacterial metabolites, such as ginsenosides Rg3, F2, Rh2, and compound K, are more pharmacologically active than major saponins, such as ginsenosides Rb1, Rb2, and Rc. In this work, enzymatic hydrolysis of ginsenoside Rb1 was studied using enzyme preparations from cultured mycelia of mushrooms. Methods Mycelia of Armillaria mellea, Ganoderma lucidum, Phellinus linteus, Elfvingia applanata, and Pleurotus ostreatus were cultivated in liquid media at 25°C for 2 wk. Enzyme preparations from cultured mycelia of five mushrooms were obtained by mycelia separation from cultured broth, enzyme extraction, ammonium sulfate (30–80%) precipitation, dialysis, and freeze drying, respectively. The enzyme preparations were used for enzymatic hydrolysis of ginsenoside Rb1. Results Among the mushrooms used in this study, the enzyme preparation from cultured mycelia of A. mellea (AMMEP) was found to convert ginsenoside Rb1 into compound K with a high yield, while those from G. lucidum, P. linteus, E. applanata, and P. ostreatus produced remarkable amounts of ginsenoside Rd from ginsenoside Rb1. The enzymatic hydrolysis pathway of ginsenoside Rb1 by AMMEP was Rb1 → Rd → F2 → compound K. The optimum reaction conditions for compound K formation from ginsenoside Rb1 were as follows: reaction time 72–96 h, pH 4.0–4.5, and temperature 45–55°C. Conclusion AMMEP can be used to produce the human intestinal bacterial metabolite, compound K, from ginsenoside Rb1 with a high yield and without food safety issues. PMID:27158230

  15. Deposition of Functional Coatings Based on Intermetallic Systems TiAl on the Steel Surface by Vacuum Arc Plasma

    NASA Astrophysics Data System (ADS)

    Budilov, V.; Vardanyan, E.; Ramazanov, K.

    2015-11-01

    Laws governing the formation of intermetallic phase by sequential deposition of nano-sized layers coatings from vacuum arc plasma were studied. Mathematical modeling process of deposition by vacuum arc plasma was performed. In order to identify the structural and phase composition of coatings and to explain their physical and chemical behaviour XRD studies were carried out. Production tests of the hardened punching tools were performed.

  16. Redox effect on volatile compound formation in wine during fermentation by Saccharomyces cerevisiae.

    PubMed

    Fariña, Laura; Medina, Karina; Urruty, Maia; Boido, Eduardo; Dellacassa, Eduardo; Carrau, Francisco

    2012-09-15

    Although redox state is a well-known key process parameter in microbial activity, its impact on wine volatile aroma compounds produced during fermentation has not been studied in detail. In this study we report the effect of reductive and microaerobic conditions on wine aroma compound production using different initial amounts of yeast assimilable nitrogen (YAN: 180 and 400 mg N/l) in a simil grape must defined medium and two S. cerevisiae strains commonly used in wine-making. In batch fermentation culture conditions, reductive conditions were obtained using flasks plugged with Muller valves filled with sulphuric acid; while microaerobic conditions were attained with defined cotton plugs. It was found that significant differences in redox potential were obtained using the different plugs, and with variation of over 100 mV during the main fermentation period. Significant differences in the final concentration of higher alcohols, esters and fatty acids were attributed to differences in the redox state in the medium in both strains. A consistent increase in esters and medium chain fatty acids, as well as a decrease of higher alcohols and isoacids, was seen under reductive fermentation conditions. Interestingly, 1-propanol, δ-butyrolactone and ethyl lactate concentrations, showed no significant variation under the different redox conditions. A better understanding of the influence of redox state of the fermentation medium on the composition of volatile compounds in wine could enable improvement of vinification management. From a microbiological standpoint results presented here will contribute to the standardization of data models for the application of metabolic footprinting methods for wine yeast strain phenotyping and characterization.

  17. Photoassisted carbon dioxide reduction and formation of twoand three-carbon compounds. [prebiological photosynthesis

    NASA Technical Reports Server (NTRS)

    Halmann, M.; Aurian-Blajeni, B.; Bloch, S.

    1981-01-01

    The photoassisted reduction of aqueous carbon dioxide in the presence of naturally occurring minerals is investigated as a possible abiotic precursor of photosynthesis. Aqueous carbon dioxide saturated suspensions or surfaces of the minerals nontronite, bentonite, anatase, wolframite, molybdenite, minium, cinnabar and hematite were irradiated with high-pressure mercury lamps or sunlight. Chemical analyses reveal the production of formic acid, formaldehyde, methanol and methane, and the two and three-carbon compounds glyoxal (CHOCHO) and malonaldehyde (CH2(CHO)2). It is suggested that such photosynthetic reactions with visible light in the presence of semiconducting minerals may provide models for prebiological carbon and nitrogen fixation in both oxidized and reduced atmospheres.

  18. Synthesis of superheavy elements and dinuclear-system concept of compound-nucleus formation

    SciTech Connect

    Antonenko, N.V.; Adamian, G.G.; Cherepanov, E.A.

    1996-12-31

    Dinuclear system concept is applied to the analysis of reactions used for the synthesis of elements with Z = 110, 112, 114, and 116. The inner fusion barriers obtained for these reactions are in good agreement with the experimental estimations resulted from the excitation energies of compound nuclei. A model is suggested for the calculation of the competition between complete fusion and quasifission in reactions with heavy nuclei. The fusion rate through the inner fusion barrier in mass asymmetry is found by using the multidimensional Kramers-type stationary solution of the Fokker-Planck equation. The influence of dissipative effects on the dynamics of nuclear fusion is considered.

  19. DFT studies on Schiff base formation of vitamin B6 analogues. Reaction between a pyridoxamine-analogue and carbonyl compounds.

    PubMed

    Ortega-Castro, J; Adrover, M; Frau, J; Salvà, A; Donoso, J; Muñoz, F

    2010-04-08

    A comprehensive theoretical study based on density functional theory calculations (B3LYP and M06-2X functionals) of the formation of Schiff bases of pyridoxamine analogues with two different aldehydes was conducted. The reaction mechanism was found to involve two steps, namely: (1) formation of a carbinolamine and (2) dehydration of the carbinolamine to give the final imine. Also, consistent with available experimental evidence, the carbinolamine dehydration was the rate-determining step of the process determined by means of M06-2X functional. Using an appropriate solvation method and reactant conformation ensures that all proton transfers involved will be intramolecular, which substantially reduces energy barriers and facilitates reaction in all cases. The formation of a Schiff base between pyridoxal 5-phosphate (PLP) and an amine or amino acid requires the contribution of an external water molecule in order to facilitate proton transfers. On the other hand, the formation of a Schiff base between pyridoxamine 5-phosphate (PMP) and a carbonyl compound requires no external aid since the spatial arrangement of the functional groups in PMP ensures that all proton transfers will be intramolecular.

  20. Different formats of imprinted polymers for determining organotin compounds in environmental samples.

    PubMed

    Gallego-Gallegos, Mercedes; Muñoz-Olivas, Riansares; Cámara, Carmen

    2009-02-01

    Organotin compounds and their degradation products enter the environment mainly as a result of their use as biocides and antifouling paints. Analysis of these compounds in environmental samples has to be very sensitive and selective so that their concentrations corresponding to the low environmental target values can also be detected. Generally, analysis of a complex matrix leads to high interferences during the different process steps; clean-up procedures are recommended to overcome this problem. For the past many years, solid phase extraction by employing imprinted materials has been extensively used for many organic substances that are used for pre-concentration and clean-up purposes with excellent results. Here, we present three different imprinted polymers prepared via bulk, precipitation, and emulsion polymerization methods that use similar compositions. The synthesized polymer particles were characterized morphologically by employing scanning electron microscopy and Brunauer-Emmett-Teller analysis. Binding properties were calculated using the Langmuir-Freundlich isotherm. Depending on the properties of the materials, different analytical applications for complex matrices are proposed. These applications are mainly used on tributyltin and its degradation products for environmental analysis.

  1. Formation of biomineral iron oxides compounds in a Fe hyperaccumulator plant: Imperata cylindrica (L.) P. Beauv.

    PubMed

    Fuente, V; Rufo, L; Juárez, B H; Menéndez, N; García-Hernández, M; Salas-Colera, E; Espinosa, A

    2016-01-01

    We report a detailed work of composition and location of naturally formed iron biominerals in plant cells tissues grown in iron rich environments as Imperata cylindrica. This perennial grass grows on the Tinto River banks (Iberian Pyritic Belt) in an extreme acidic ecosystem (pH∼2.3) with high concentration of dissolved iron, sulphate and heavy metals. Iron biominerals were found at the cellular level in tissues of root, stem and leaf both in collected and laboratory-cultivated plants. Iron accumulated in this plant as a mix of iron compounds (mainly as jarosite, ferrihydrite, hematite and spinel phases) was characterized by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), Mössbauer spectroscopy (MS), magnetometry (SQUID), electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX; TEM-EDX; HRSTEM). A low fraction of phosphorous was detected in this iron hyperaccumulator plant. Root and rhizomes tissues present a high proportion of ferromagnetic iron oxide compounds. Iron oxides-rich zones are localized in electron dense intra and inter-cellular aggregates that appear as dark deposits covering the inner membrane and organelles of the cell. This study aims to contribute to a better understanding of the mechanisms of accumulation, transport, distribution of iron in Imperata cylindrica.

  2. Antioxidant Compounds in Traditional Indian Pickles May Prevent the Process-Induced Formation of Benzene.

    PubMed

    Kharat, Mahesh M; Adiani, Vanshika; Variyar, Prasad; Sharma, Arun; Singhal, Rekha S

    2016-01-01

    Pickles in the Indian market contain ascorbic acid from the raw material used and benzoate as an added preservative that are involved in the formation of benzene in soft drinks. In this work, 24 market pickle samples were surveyed for benzene content, as well as its precursors and other constituents that influence its formation. The analysis showed that pickle samples were high in acid content (low pH) and showed significant amount of ascorbic acid, minerals (Cu and Fe), and benzoic acid present in them. Also, most samples exhibited high antioxidant activity that might be attributed to the ingredients used, such as fruits and spices. The solid-phase microextraction headspace gas chromatography-mass spectrometry method was developed in-house for benzene analysis. Eleven of 24 samples had benzene, with the highest concentration of 4.36 ± 0.82 μg of benzene per kg of pickle for a lime pickle that was also reported to have highest benzoic acid and considerably less hydroxyl radical ((•)OH) scavenging activity. However, benzene levels for all 11 samples were considerably below the World Health Organization regulatory limit of 10 μg/kg for benzene in mineral water. Studies on model systems revealed that the high antioxidant activity of Indian pickles may have had a strong inhibitory effect on benzene formation.

  3. Organic aerosol formation from biogenic compounds over the Ponderosa pine forest in Colorado

    NASA Astrophysics Data System (ADS)

    Roux, Alma Hodzic; Lee-Taylor, Julia; Cui, Yuyan; Madronich, Sasha

    2013-05-01

    The secondary organic aerosol (SOA) formation and regional growth from biogenic precursors is of particular interest given their abundance in the atmosphere, and has been investigated during the Rocky Mountain Biogenic Aerosol field Study in 2011 in the pine forest canopy (dominated by terpene emissions) using both WRF/Chem 4km simulations and the GECKO-A explicit chemistry box-model runs. We have quantified the relative contribution of different biogenic precursors to SOA levels that were measured by the aerosol mass spectrometer at the site, and investigated the relative contribution of OH, O3 and NO3 chemistry to the formed SOA mass during day-and nighttime. Although, the local production and mass concentrations of submicron organic aerosols at the site seem relatively modest ˜1-2 ug/m3, we show that the optically active regional mass is increased as the SOA formation continues for several days in the background forest air. We investigate whether the simplified SOA parameterizations used in 3D models can capture this growth. In addition, preliminary comparisons of the number concentrations and the composition of ultrafine particles (8 - 30nm) from WRF/Chem simulations and TD-CIMS measurements are also discussed, and the contribution of organic aerosols to CCN formation is quantified.

  4. Entrance-channel mass-asymmetry dependence of compound nucleus formation time in light heavy-ion reactions

    SciTech Connect

    Szanto de Toledo, A.; Carlson, B.V.; Beck, C.

    1996-12-01

    The entrance-channel mass-asymmetry dependence of the compound nucleus formation time in light heavy-ion reactions has been investigated within the framework of semiclassical dissipative collision models. The model calculations have been applied successfully to the formation of the {sup 38}Ar compound nucleus as populated via the {sup 9}Be+{sup 29}Si, {sup 11}B+{sup 27}Al, {sup 12}C+{sup 26}Mg, and {sup 19}F+{sup 19}F entrance channels. The shape evolution of several other light composite systems appears to be consistent with the so-called {open_quote}{open_quote}Fusion Inhibition Factor{close_quote}{close_quote} which has been observed experimentally. As found previously in more massive systems for the fusion-evaporation process, the entrance-channel mass-asymmetry degree of freedom appears to determine the competition between the different mechanisms as well as the time scales involved. {copyright} {ital 1996 The American Physical Society.}

  5. Formation pathways and opioid activity data for 3-hydroxypyridinium compounds derived from glucuronic acid and opioid peptides by Maillard processes.

    PubMed

    Horvat, Stefica; Roscić, Maja; Lemieux, Carole; Nguyen, Thi M-D; Schiller, Peter W

    2007-07-01

    The kinetics of formation and identity of the reaction products of the glucuronic acid with three representative opioid peptides were investigated in vitro. Peptides were conjugated with glucuronic acid either in solution or under dry-heating conditions. From the incubations performed in solution N-(1-deoxy-D-fructofuranos-1-yluronic acid)-peptide derivatives (Amadori compounds) were isolated, whereas from the dry-heated reactions products containing the 3-hydroxypyridinium moiety at the N-terminal of the peptide chain were obtained. Experiments performed under mild dry-heating conditions (40 degrees C) in model systems based on Leu-enkephalin and glucuronic acid, and in environment of either 40% or 75% relative humidity, revealed that the higher level of humidity promoted a process that enhanced 3-hydroxypyridinium compound generation. The mechanism of 3-hydroxypyridinium formation is discussed. In comparison with their respective parent peptides, the N-(1-deoxy-D-fructofuranosyl-uronic acid) derivatives of the opioid peptides showed three- to 11-fold lower mu- and delta-receptor-binding affinities and agonist potencies in the functional assays, likely as a consequence of the steric bulk introduced at the N-terminal amino group. The further decrease in opioid activity observed with the 3-hydroxypyridinium-containing peptides may be due to the lower pK(a) of the 3-hydroxypyridinium moiety and to delocalization of the positive charge in the pyridinium ring system.

  6. Reduction of nitrogen compounds in oceanic basement and its implications for HCN formation and abiotic organic synthesis

    PubMed Central

    2009-01-01

    Hydrogen cyanide is an excellent organic reagent and is central to most of the reaction pathways leading to abiotic formation of simple organic compounds containing nitrogen, such as amino acids, purines and pyrimidines. Reduced carbon and nitrogen precursor compounds for the synthesis of HCN may be formed under off-axis hydrothermal conditions in oceanic lithosphere in the presence of native Fe and Ni and are adsorbed on authigenic layer silicates and zeolites. The native metals as well as the molecular hydrogen reducing CO2 to CO/CH4 and NO3-/NO2- to NH3/NH4+ are a result of serpentinization of mafic rocks. Oceanic plates are conveyor belts of reduced carbon and nitrogen compounds from the off-axis hydrothermal environments to the subduction zones, where compaction, dehydration, desiccation and diagenetic reactions affect the organic precursors. CO/CH4 and NH3/NH4+ in fluids distilled out of layer silicates and zeolites in the subducting plate at an early stage of subduction will react upon heating and form HCN, which is then available for further organic reactions to, for instance, carbohydrates, nucleosides or even nucleotides, under alkaline conditions in hydrated mantle rocks of the overriding plate. Convergent margins in the initial phase of subduction must, therefore, be considered the most potent sites for prebiotic reactions on Earth. This means that origin of life processes are, perhaps, only possible on planets where some kind of plate tectonics occur. PMID:19849830

  7. Reduction of nitrogen compounds in oceanic basement and its implications for HCN formation and abiotic organic synthesis.

    PubMed

    Holm, Nils G; Neubeck, Anna

    2009-10-22

    Hydrogen cyanide is an excellent organic reagent and is central to most of the reaction pathways leading to abiotic formation of simple organic compounds containing nitrogen, such as amino acids, purines and pyrimidines. Reduced carbon and nitrogen precursor compounds for the synthesis of HCN may be formed under off-axis hydrothermal conditions in oceanic lithosphere in the presence of native Fe and Ni and are adsorbed on authigenic layer silicates and zeolites. The native metals as well as the molecular hydrogen reducing CO2 to CO/CH4 and NO3-/NO2- to NH3/NH4+ are a result of serpentinization of mafic rocks. Oceanic plates are conveyor belts of reduced carbon and nitrogen compounds from the off-axis hydrothermal environments to the subduction zones, where compaction, dehydration, desiccation and diagenetic reactions affect the organic precursors. CO/CH4 and NH3/NH4+ in fluids distilled out of layer silicates and zeolites in the subducting plate at an early stage of subduction will react upon heating and form HCN, which is then available for further organic reactions to, for instance, carbohydrates, nucleosides or even nucleotides, under alkaline conditions in hydrated mantle rocks of the overriding plate. Convergent margins in the initial phase of subduction must, therefore, be considered the most potent sites for prebiotic reactions on Earth. This means that origin of life processes are, perhaps, only possible on planets where some kind of plate tectonics occur.

  8. First-principles study of Al-Cu energetics and consequences on athermal formation of Cu-rich compounds

    NASA Astrophysics Data System (ADS)

    Besson, R.; Kwon, J.; Thuinet, L.; Avettand-Fènoël, M.-N.; Legris, A.

    2014-12-01

    In spite of its practical interest, the Al-Cu system remains largely unexplored, especially on its Cu-rich side. In order to improve the knowledge of this system, we perform a thorough ab initio study of fcc-based Al-Cu energetics, using the recently proposed M2BCE reciprocal-space cluster expansion approach. We demonstrate the existence of two clearly distinct composition domains, revealing complex ground-state properties. Below 50% Cu, the GP 2 -A l3Cu compound appears as highly favored, in agreement with the well-documented transformation sequence in Al-based alloys. Conversely, the domain between 50% and 80% Cu displays a much shallower landscape, characterized by the existence of a wealth of compounds undergoing fcc →bcc structural instabilities. While such "Bain paths" have been identified for a long time in iron-based alloys, our work gives evidence for their existence in the Al-Cu system. As a striking application, these instabilities provide plausible athermal mechanisms for the formation of Cu-rich phases, in particular for the unexpected emergence of γ1-A l4C u9 , a Hume-Rothery compound observed in various nonequilibrium conditions.

  9. SOA Formation form the NO3 radicals Chemistry of Isoprene, Monoterpenes, Sesquiterpenes, Biogenic Oxygenated Compounds, and Aromatics

    NASA Astrophysics Data System (ADS)

    Kleindienst, T. E.; Jaoui, M.; Docherty, K.; Corse, E.; Offenberg, J. H.; Lewandowski, M.

    2011-12-01

    Volatile organic compounds (VOCs) are oxidized in the atmosphere primarily by hydroxyl radicals (OH) during daylight hours but also by nitrate radicals (NO3) during overnight, photochemically inactive periods. While reactions with OH have received considerable attention with regard to gas-phase reaction products and secondary organic aerosol (SOA) formation, less is known about the mechanisms and products resulting from nighttime NO3 reactions despite their potential for SOA formation. To date, there have been limited studies on the chemical characteristics of aerosol reaction products formed from VOCs oxidation with NO3, and few SOA reaction products have been identified. Nighttime reactions have nevertheless been incorporated into some air quality models despite the limited information available and substantial uncertainties which still exist. The National Exposure Research Laboratory of the U.S. Environmental Protection Agency recently undertook an integrated laboratory research effort to better understand the contribution of NO3 reactions to nighttime SOA formation. Isoprene, methacrolein, a-pinene, b-pinene, d-limonene, b-caryophyllene, farnesene, a-humulene, 2-methyl-3-buten-2-ol, toluene, m-xylene, and naphthalene were reacted with NO3 under a wide range of conditions in a series of separate photochemical reaction chamber experiments. These hydrocarbons are thought to contribute to ambient SOA formation. NO3 was formed through thermal decomposition of N2O5. The yield, physical characteristics, and composition of SOA formed in each experiment was analyzed by a suite of instruments including a scanning mobility particle sizer, a Sunset Labs semi continuous EC-OC monitor, a volatility differential mobility analyzer, a direct insertion probe-mass spectrometer, a high resolution time-of-flight aerosol mass spectrometer, and a gas-chromatography-mass spectrometer. To understand the relative contributions of nighttime versus daytime VOCs reactions, a similar

  10. Comets and the formation of biochemical compounds on the primitive earth - A review

    NASA Technical Reports Server (NTRS)

    Oro, J.; Mills, T.; Lazcano, A.

    1992-01-01

    Thirty years ago it was suggested that comets impacting on the primitive earth may have represented a significant source of terrestrial volatiles, including some important precursors for prebiotic synthesis (Oro, 1961). This possibility is strongly supported not only by models of the collisional history of the early earth, but also by astronomical evidence that suggests that frequent collisions of cometlike bodies from the circumstellar disk around the star Beta Pictoris are taking place. Although a significant fraction of the complex organic compounds that appear to be present in cometary nuclei were probably destroyed during impact, it is argued that cometary collisions with the primitive earth represented an important source of both free-energy and volatiles, and may have created transient, gaseous environments in which prebiotic synthesis may have taken place.

  11. Reactions of SIV species with organic compounds: formation mechanisms of organo-sulfur derivatives in atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Passananti, Monica; Shang, Jing; Dupart, Yoan; Perrier, Sébastien; George, Christian

    2015-04-01

    Secondary organic aerosol (SOA) have an important impact on climate, air quality and human health. However the chemical reactions involved in their formation and growth are not fully understood or well-constrained in climate models. It is well known that inorganic sulfur (mainly in oxidation states (+IV) and (+VI)) plays a key role in aerosol formation, for instance sulfuric acid is known to be a good nucleating gas. In addition, acid-catalyzed heterogeneous reactions of organic compounds has shown to produce new particles, with a clear enhancement in the presence of ozone (Iinuma 2013). Organosulfates have been detected in tropospheric particles and aqueous phases, which suggests they are products of secondary organic aerosol formation process (Tolocka 2012). Originally, the production of organosulfates was explained by the esterification reaction of alcohols, but this reaction in atmosphere is kinetically negligible. Other formation pathways have been suggested such as hydrolysis of peroxides and reaction of organic matter with sulfite and sulfate radical anions (SO3-, SO4-) (Nozière 2010), but it remains unclear if these can completely explain atmospheric organo-sulfur aerosol loading. To better understand the formation of organo-sulfur compounds, we started to investigate the reactivity of SIV species (SO2 and SO32-) with respect to specific functional groups (organic acids and double bonds) on atmospherically relevant carboxylic acids and alkenes. The experiments were carried out in the homogeneous aqueous phase and at the solid-gas interface. A custom built coated-wall flow tube reactor was developed to control relativity humidity, SO2 concentration, temperature and gas flow rate. Homogeneous and heterogeneous reaction kinetics were measured and resulting products were identified using liquid chromatography coupled with an orbitrap mass spectrometer (LC-HR-MS). The experiments were performed with and without the presence of ozone in order to evaluate any

  12. Stereoselective formation of the varietal aroma compound rose oxide during alcoholic fermentation.

    PubMed

    Koslitz, Stephan; Renaud, Lauren; Kohler, Marcel; Wüst, Matthias

    2008-02-27

    The potent aroma compound rose oxide was quantified in several white wines by a headspace solid-phase microextration stable isotope dilution assay (HS-SPME-SIDA) and the enantiomeric ratios of the cis diastereomers were determined by enantioselective capillary GC. The most odor-active stereoisomer (23)-cis-rose oxide was detectable in all investigated white wines ranging from 0.2 to 12 microg/L. However, its contribution to the overall aroma in some white wine varieties can be neglected as indicated by a low odor activity value (OAV). The highest concentrations were found in Gewürztraminer wines, confirming the importance of rose oxide as a varietal aroma compound in this variety. Surprisingly, the enantiomeric ratio of cis-rose oxide in all investigated wines was substantially lower than in nonfermented musts and in some wines almost racemic cis-rose oxide was detected. Fermentation studies with a model must that contained deuterated water revealed that yeast is capable of reducing the precursor 3,7-dimethyl octa-2,5-dien-1,7-diol (geranyl diol I) yielding 3,7-dimethyl-5-octen-1,7-diol (citronellyl diol I) that gives rise to cis- and trans-rose oxide after acid catalyzed cylization. The deuterium labeling pattern of the resulting rose oxide stereoisomers and a clearly detectable kinetic isotope effect indicate that at least two different reductive pathways in yeast exist that yield cis-rose oxide with different enantiomeric ratios altering the genuine enantiomeric ratio in grape musts. The presence of (+)-cis-rose oxides in wines can therefore be attributed to the reductive yeast metabolism during fermentation. This observation corroborates recent findings that the modification of terpene derived varietal aroma is an integral part of yeast metabolism and not only a simple hydrolytical process.

  13. Influence of PDO Ragusano cheese biofilm microbiota on flavour compounds formation.

    PubMed

    Carpino, Stefania; Randazzo, Cinzia L; Pino, Alessandra; Russo, Nunziatina; Rapisarda, Teresa; Belvedere, Gianni; Caggia, Cinzia

    2017-02-01

    The objectives of the present study were to characterize the biofilm microbiota of 11 different farms (from A to K), producing PDO Ragusano cheese, and to investigate on its ability to generate volatile organic compounds (VOCs) in milk samples inoculated with biofilm and incubated under Ragusano cheese making conditions. The biofilms were subjected to plate counting and PCR/T/DGGE analysis and the VOCs generated in incubated milk samples were evaluated through SmartNose, GC/O, and GC/MS. Streptococcus thermophilus was the dominant species both in biofilms and in incubated milks. Lactobacillus, Lactococcus, Enterococcus and Leuconostoc were also identified. Low levels of Pseudomonas spp. and yeasts counts were detected, whereas coliforms, Listeria monocytogenes and Salmonella spp., were never found. SmartNose and GC/O analyses were able to differentiate incubated milk samples on the basis of the odour compounds, highlighting that samples E and F overlapped and sample C was clearly separated from the others. These results complied with those acquired by GC/MS analysis, that detected in total 20 VOCs. Principal component analysis showed positive correlations (r > 0.6; P < 0.05) between some lactic acid bacteria (LAB) and VOCs: such as Enterococcus hirae with alcohols, Lactococcus lactis, Lactobacillus plantarum, Lactobacillus casei and Lactobacillus delbrueckii with aldehydes, and Lactobacillus fermentum, Lactobacillus helveticus and Lactobacillus hilgardii with ketones. This work demonstrates that biofilm represents an excellent source of LAB biodiversity, which contribute to generate VOCs during the production of PDO Ragusano cheese.

  14. Numerical study of the effect of oxygenated blending compounds on soot formation in shock tubes

    SciTech Connect

    Boehm, H.; Braun-Unkhoff, M.

    2008-04-15

    This numerical study deals with the influence of blends on the amount of soot formed in shock tubes, which were simulated by assuming a homogeneous plug flow reactor model. For this purpose, first, the reaction model used here was validated against experimental results previously obtained in the literature. Then, the soot volume fractions of various mixtures of methyl tert-butyl ether (MTBE)-benzene, isobutene-benzene, methanol-benzene, and ethanol-benzene diluted in argon were simulated and compared to the results of benzene-argon pyrolysis at 1721 K and 5.4 MPa. For MTBE, isobutene, methanol, and ethanol, small amounts of additives to benzene-argon mixtures promoted soot formation, for the shock tube model assumed, while higher concentrations of these additives led to smaller soot volume fractions in comparison to pure benzene-argon pyrolysis. The most significant soot promotion effect was found for the additives MTBE and isobutene. The channel for MTBE decomposition producing isobutene and methanol is very effective at temperatures beyond 1200 K. Thus, both MTBE-benzene and isobutene-benzene mixtures diluted in argon showed rather similar behavior in regard to soot formation. Special emphasis was directed toward the causes for the concentration-dependent influence of the blends on the amount of soot formed. Aromatic hydrocarbons and acetylene were identified as key gas-phase species that determine the trends in the formation of soot of various mixtures. From reaction flux analysis for phenanthrene, it was deduced that the combinative routes including phenyl species play a major role in forming PAHs, especially at early reaction times. It is found that the additives play an important role in providing material to grow side chains, such as by reaction channels including phenylacetylene or benzyl, which are confirmed to form aromatic hydrocarbons and thus to influence the amount of soot formed, particularly when the concentrations of the blends are increased

  15. Investigation of formation of nitrogen compounds in coal combustion. Final report

    SciTech Connect

    Blair, D.W.; Crane, I.D.; Wendt, J.O.L.

    1983-10-01

    This is the final report on DOE contract number DE-AC21-80MC14061. It concerns the formation of nitrogen oxide from fuel-bound nitrogen during coal combustion. The work reported was divided into three tasks. They addressed problems of time-resolving pyrolysis rates of coal under simulated combustion conditions, the combustion of the tar that results from such pyrolysis, and theoretical modeling of the pyrolysis process. In all of these tasks, special attention was devoted to the fate of coal nitrogen. The first two tasks were performed by Exxon Research and Engineering Company. 49 references.

  16. The effect of pH on polymorph formation of the pharmaceutically active compound tianeptine.

    PubMed

    Orola, Liana; Veidis, Mikelis V; Sarcevica, Inese; Actins, Andris; Belyakov, Sergey; Platonenko, Aleksandrs

    2012-08-01

    The anti-depressant pharmaceutical tianeptine has been investigated to determine the dynamics of polymorph formation under various pH conditions. By varying the pH two crystalline polymorphs were isolated. The molecular and crystal structures have been determined to identify the two polymorphs. One polymorph is an amino carboxylic acid and the other polymorph is a zwitterion. In the solid state the tianeptine moieties are bonded through hydrogen bonds. The zwitterion was found to be less stable and transformed to the acid form. During this investigation an amorphous form was identified.

  17. Corrosion behavior of binary titanium aluminide intermetallics

    SciTech Connect

    Saffarian, H.M.; Gan, Q.; Hadkar, R.; Warren, G.W.

    1996-08-01

    The corrosion behavior of arc-melted binary titanium aluminide intermetallics TiAl, Ti{sub 2}Al, and TiAl{sub 3} in aqueous sodium sulfate and sodium chloride solutions was measured and compared to that of pure Ti and Al. Effects of electrolyte composition (e.g., sulfate [0.25 M SO{sub 4}{sup 2}{sup {minus}}], chloride [0.1 to 1.0 M Cl{sup {minus}}], and pH [3 to 10]) were examined. Anodic polarization of titanium aluminides in aqueous SO{sub 4}{sup 2}{sup {minus}} solutions was similar (showing passive behavior), but no pitting or pitting potential (E{sub pit}) was observed. In aqueous NaCl, however, titanium aluminides were susceptible to pitting, and E{sub pit} decreased with increasing Al content (i.e., Ti{sub 3}Al had the highest E{sub pit} and, therefore, a greater resistance to pitting, followed by TiAl and TiAl{sub 3}). For TiAl, E{sub pit} was slightly dependent upon pH or Cl{sup {minus}} concentration. Pit morphology and E{sub pit} values were quite different for TiAl compared to Ti{sub 3}Al. TiAl showed numerous small pits, whereas Ti{sub 3}Al exhibited fewer but larger and deeper pits. The larger pit density for TiAl was associated with Al-rich interdendrite regions. One interesting feature of the anodic polarization curves for Ti{sub 3}Al was a small anodic peak frequently observed at {approximately}1.4 V{sub SCE} to 1.8 V{sub SCE}. Results suggested this peak was associated with pit initiation, since pitting initiated concurrently with the peak or immediately afterward.

  18. Establishment of an in silico phospholipidosis prediction method using descriptors related to molecular interactions causing phospholipid-compound complex formation.

    PubMed

    Haranosono, Yu; Nemoto, Shingo; Kurata, Masaaki; Sakaki, Hideyuki

    2016-04-01

    Although phospholipidosis (PLD) often affects drug development, there is no convenient in vitro or in vivo test system for PLD detection. In this study, we developed an in silico PLD prediction method based on the PLD-inducing mechanism. We focused on phospholipid (PL)-compound complex formation, which inhibits PL degradation by phospholipase. Thus, we used some molecular interactions, such as electrostatic interactions, hydrophobic interactions, and intermolecular forces, between PL and compounds as descriptors. First, we performed descriptor screening for intermolecular force and then developed a new in silico PLD prediction using descriptors related to molecular interactions. Based on the screening, we identified molecular refraction (MR) as a descriptor of intermolecular force. It is known that ClogP and most-basic pKa can be used for PLD prediction. Thereby, we developed an in silico prediction method using ClogP, most-basic pKa, and MR, which were related to hydrophobic interactions, electrostatic interactions, and intermolecular forces. In addition, a resampling method was used to determine the cut-off values for each descriptor. We obtained good results for 77 compounds as follows: sensitivity = 95.8%, specificity = 75.9%, and concordance = 88.3%. Although there is a concern regarding false-negative compounds for pKa calculations, this predictive ability will be adequate for PLD screening. In conclusion, the mechanism-based in silico PLD prediction method provided good prediction ability, and this method will be useful for evaluating the potential of drugs to cause PLD, particularly in the early stage of drug development, because this method only requires knowledge of the chemical structure.

  19. Effects of sulfhydryl compounds, carbohydrates, organic acids, and sodium sulfite on the formation of lysinoalanine in preserved egg.

    PubMed

    Luo, Xu-Ying; Tu, Yong-Gang; Zhao, Yan; Li, Jian-Ke; Wang, Jun-Jie

    2014-08-01

    To identify inhibitors for lysinoalanine formation in preserved egg, sulfhydryl compounds (glutathione, L-cysteine), carbohydrates (sucrose, D-glucose, maltose), organic acids (L-ascorbic acid, citric acid, DL-malic acid, lactic acid), and sodium sulfite were individually added at different concentrations to a pickling solution to prepare preserved eggs. Lysinoalanine formation as an index of these 10 substances was determined. Results indicate that glutathione, D-glucose, maltose, L-ascorbic acid, citric acid, lactic acid, and sodium sulfite all effectively diminished lysinoalanine formation in preserved egg albumen and yolk. When 40 and 80 mmol/L of sodium sulfite, citric acid, L-ascorbic acid, and D-glucose were individually added into the pickling solution, the inhibition rates of lysinoalanine in the produced preserved egg albumen and yolk were higher. However, the attempt of minimizing lysinoalanine formation was combined with the premise of ensuring preserved eggs quality. Moreover, the addition of 40 and 80 mmol/L of sodium sulfite, 40 and 80 mmol/L of D-glucose, 40 mmol/L of citric acid, and 40 mmol/L of L-ascorbic acid was optimal to produce preserved eggs. The corresponding inhibition rates of lysinoalanine in the albumen were approximately 76.3% to 76.5%, 67.6% to 67.8%, 74.6%, and 74.6%, and the corresponding inhibition rates of lysinoalanine in the yolk were about 68.7% to 69.7%, 50.6% to 51.8%, 70.4%, and 57.8%. It was concluded that sodium sulfite, D-glucose, L-ascorbic, and citric acid at suitable concentrations can be used to control the formation of lysinoalanine during preserved egg processing.

  20. The natural chlorine cycle - Formation of the carcinogenic and greenhouse gas compound chloroform in drinking water reservoirs.

    PubMed

    Forczek, Sándor T; Pavlík, Milan; Holík, Josef; Rederer, Luděk; Ferenčík, Martin

    2016-08-01

    Chlorine cycle in natural ecosystems involves formation of low and high molecular weight organic compounds of living organisms, soil organic matter and atmospherically deposited chloride. Chloroform (CHCl3) and adsorbable organohalogens (AOX) are part of the chlorine cycle. We attempted to characterize the dynamical changes in the levels of total organic carbon (TOC), AOX, chlorine and CHCl3 in a drinking water reservoir and in its tributaries, mainly at its spring, and attempt to relate the presence of AOX and CHCl3 with meteorological, chemical or biological factors. Water temperature and pH influence the formation and accumulation of CHCl3 and affect the conditions for biological processes, which are demonstrated by the correlation between CHCl3 and ΣAOX/Cl(-) ratio, and also by CHCl3/ΣAOX, CHCl3/AOXLMW, CHCl3/ΣTOC, CHCl3/TOCLMW and CHCl3/Cl(-) ratios in different microecosystems (e.g. old spruce forest, stagnant acidic water, humid and warm conditions with high biological activity). These processes start with the biotransformation of AOX from TOC, continue via degradation of AOX to smaller molecules and further chlorination, and finish with the formation of small chlorinated molecules, and their subsequent volatilization and mineralization. The determined concentrations of chloroform result from a dynamic equilibrium between its formation and degradation in the water; in the Hamry water reservoir, this results in a total amount of 0.1-0.7 kg chloroform and 5.2-15.4 t chloride. The formation of chloroform is affected by Cl(-) concentration, by concentrations and ratios of biogenic substrates (TOC and AOX), and by the ratios of the substrates and the product (feedback control by chloroform itself).

  1. Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics

    PubMed Central

    Booth, C.H.; Jiang, Yu; Wang, D.L.; Mitchell, J.N.; Tobash, P.H.; Bauer, E.D.; Wall, M.A.; Allen, P.G.; Sokaras, D.; Nordlund, D.; Weng, T.-C.; Torrez, M.A.; Sarrao, J.L.

    2012-01-01

    Uranium and plutonium’s 5f electrons are tenuously poised between strongly bonding with ligand spd-states and residing close to the nucleus. The unusual properties of these elements and their compounds (e.g., the six different allotropes of elemental plutonium) are widely believed to depend on the related attributes of f-orbital occupancy and delocalization for which a quantitative measure is lacking. By employing resonant X-ray emission spectroscopy (RXES) and X-ray absorption near-edge structure (XANES) spectroscopy and making comparisons to specific heat measurements, we demonstrate the presence of multiconfigurational f-orbital states in the actinide elements U and Pu and in a wide range of uranium and plutonium intermetallic compounds. These results provide a robust experimental basis for a new framework toward understanding the strongly-correlated behavior of actinide materials. PMID:22706643

  2. Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics.

    PubMed

    Booth, C H; Jiang, Yu; Wang, D L; Mitchell, J N; Tobash, P H; Bauer, E D; Wall, M A; Allen, P G; Sokaras, D; Nordlund, D; Weng, T-C; Torrez, M A; Sarrao, J L

    2012-06-26

    Uranium and plutonium's 5f electrons are tenuously poised between strongly bonding with ligand spd-states and residing close to the nucleus. The unusual properties of these elements and their compounds (e.g., the six different allotropes of elemental plutonium) are widely believed to depend on the related attributes of f-orbital occupancy and delocalization for which a quantitative measure is lacking. By employing resonant X-ray emission spectroscopy (RXES) and X-ray absorption near-edge structure (XANES) spectroscopy and making comparisons to specific heat measurements, we demonstrate the presence of multiconfigurational f-orbital states in the actinide elements U and Pu and in a wide range of uranium and plutonium intermetallic compounds. These results provide a robust experimental basis for a new framework toward understanding the strongly-correlated behavior of actinide materials.

  3. Intermetallic alloy welding wires and method for fabricating the same

    DOEpatents

    Santella, M.L.; Sikka, V.K.

    1996-06-11

    Welding wires for welding together intermetallic alloys of nickel aluminides, nickel-iron aluminides, iron aluminides, or titanium aluminides, and preferably including additional alloying constituents are fabricated as two-component, clad structures in which one component contains the primary alloying constituent(s) except for aluminum and the other component contains the aluminum constituent. This two-component approach for fabricating the welding wire overcomes the difficulties associated with mechanically forming welding wires from intermetallic alloys which possess high strength and limited ductilities at elevated temperatures normally employed in conventional metal working processes. The composition of the clad welding wires is readily tailored so that the welding wire composition when melted will form an alloy defined by the weld deposit which substantially corresponds to the composition of the intermetallic alloy being joined. 4 figs.

  4. Intermetallic alloy welding wires and method for fabricating the same

    DOEpatents

    Santella, Michael L.; Sikka, Vinod K.

    1996-01-01

    Welding wires for welding together intermetallic alloys of nickel aluminides, nickel-iron aluminides, iron aluminides, or titanium aluminides, and preferably including additional alloying constituents are fabricated as two-component, clad structures in which one component contains the primary alloying constituent(s) except for aluminum and the other component contains the aluminum constituent. This two-component approach for fabricating the welding wire overcomes the difficulties associated with mechanically forming welding wires from intermetallic alloys which possess high strength and limited ductilities at elevated temperatures normally employed in conventional metal working processes. The composition of the clad welding wires is readily tailored so that the welding wire composition when melted will form an alloy defined by the weld deposit which substantially corresponds to the composition of the intermetallic alloy being joined.

  5. Formation of toxic iodinated disinfection by-products from compounds used in medical imaging.

    PubMed

    Duirk, Stephen E; Lindell, Cristal; Cornelison, Christopher C; Kormos, Jennifer; Ternes, Thomas A; Attene-Ramos, Matias; Osiol, Jennifer; Wagner, Elizabeth D; Plewa, Michael J; Richardson, Susan D

    2011-08-15

    Iodinated X-ray contrast media (ICM) were investigated as a source of iodine in the formation of iodo-trihalomethane (iodo-THM) and iodo-acid disinfection byproducts (DBPs), both of which are highly genotoxic and/or cytotoxic in mammalian cells. ICM are widely used at medical centers to enable imaging of soft tissues (e.g., organs, veins, blood vessels) and are designed to be inert substances, with 95% eliminated in urine and feces unmetabolized within 24 h. ICM are not well removed in wastewater treatment plants, such that they have been found at elevated concentrations in rivers and streams (up to 100 μg/L). Naturally occurring iodide in source waters is believed to be a primary source of iodine in the formation of iodo-DBPs, but a previous 23-city iodo-DBP occurrence study also revealed appreciable levels of iodo-DBPs in some drinking waters that had very low or no detectable iodide in their source waters. When 10 of the original 23 cities' source waters were resampled, four ICM were found--iopamidol, iopromide, iohexol, and diatrizoate--with iopamidol most frequently detected, in 6 of the 10 plants sampled, with concentrations up to 2700 ng/L. Subsequent controlled laboratory reactions of iopamidol with aqueous chlorine and monochloramine in the absence of natural organic matter (NOM) produced only trace levels of iodo-DBPs; however, when reacted in real source waters (containing NOM), chlorine and monochloramine produced significant levels of iodo-THMs and iodo-acids, up to 212 nM for dichloroiodomethane and 3.0 nM for iodoacetic acid, respectively, for chlorination. The pH behavior was different for chlorine and monochloramine, such that iodo-DBP concentrations maximized at higher pH (8.5) for chlorine, but at lower pH (6.5) for monochloramine. Extracts from chloraminated source waters with and without iopamidol, as well as from chlorinated source waters with iopamidol, were the most cytotoxic samples in mammalian cells. Source waters with iopamidol but no

  6. Insights into secondary organic aerosol formation mechanisms from measured gas/particle partitioning of specific organic tracer compounds.

    PubMed

    Zhao, Yunliang; Kreisberg, Nathan M; Worton, David R; Isaacman, Gabriel; Weber, Robin J; Liu, Shang; Day, Douglas A; Russell, Lynn M; Markovic, Milos Z; VandenBoer, Trevor C; Murphy, Jennifer G; Hering, Susanne V; Goldstein, Allen H

    2013-04-16

    In situ measurements of organic compounds in both gas and particle phases were made with a thermal desorption aerosol gas chromatography (TAG) instrument. The gas/particle partitioning of phthalic acid, pinonaldehyde, and 6,10,14-trimethyl-2-pentadecanone is discussed in detail to explore secondary organic aerosol (SOA) formation mechanisms. Measured fractions in the particle phase (f(part)) of 6,10,14-trimethyl-2-pentadecanone were similar to those expected from the absorptive gas/particle partitioning theory, suggesting that its partitioning is dominated by absorption processes. However, f(part) of phthalic acid and pinonaldehyde were substantially higher than predicted. The formation of low-volatility products from reactions of phthalic acid with ammonia is proposed as one possible mechanism to explain the high f(part) of phthalic acid. The observations of particle-phase pinonaldehyde when inorganic acids were fully neutralized indicate that inorganic acids are not required for the occurrence of reactive uptake of pinonaldehyde on particles. The observed relationship between f(part) of pinonaldehyde and relative humidity suggests that the aerosol water plays a significant role in the formation of particle-phase pinonaldehyde. Our results clearly show it is necessary to include multiple gas/particle partitioning pathways in models to predict SOA and multiple SOA tracers in source apportionment models to reconstruct SOA.

  7. Catalytic conversion of lignin pyrolysis model compound- guaiacol and its kinetic model including coke formation

    PubMed Central

    Zhang, Huiyan; Wang, Yun; Shao, Shanshan; Xiao, Rui

    2016-01-01

    Lignin is the most difficult to be converted and most easy coking component in biomass catalytic pyrolysis to high-value liquid fuels and chemicals. Catalytic conversion of guaiacol as a lignin model compound was conducted in a fixed-bed reactor over ZSM-5 to investigate its conversion and coking behaviors. The effects of temperature, weight hourly space velocity (WHSV) and partial pressure on product distribution were studied. The results show the maximum aromatic carbon yield of 28.55% was obtained at temperature of 650 °C, WHSV of 8 h−1 and partial pressure of 2.38 kPa, while the coke carbon yield was 19.55%. The reaction pathway was speculated to be removing methoxy group to form phenols with further aromatization to form aromatics. The amount of coke increased with increasing reaction time. The surface area and acidity of catalysts declined as coke formed on the acid sites and blocked the pore channels, which led to the decrease of aromatic yields. Finally, a kinetic model of guaiacol catalytic conversion considering coke deposition was built based on the above reaction pathway to properly predict product distribution. The experimental and model predicting data agreed well. The correlation coefficient of all equations were all higher than 0.90. PMID:27869228

  8. Neutrophil myeloperoxidase and its substrates: formation of specific markers and reactive compounds during inflammation

    PubMed Central

    Kato, Yoji

    2016-01-01

    Myeloperoxidase is an inflammatory enzyme that generates reactive hypochlorous acid in the presence of hydrogen peroxide and chloride ion. However, this enzyme also uses bromide ion or thiocyanate as a substrate to form hypobromous or hypothiocyanous acid, respectively. These species play important roles in host defense against the invasion of microorganisms. In contrast, these enzyme products modify biomolecules in hosts during excess inflammation, indicating that the action of myeloperoxidase is both beneficial and harmful. Myeloperoxidase uses other endogenous compounds, such as serotonin, urate, and l-tyrosine, as substrates. This broad-range specificity may have some biological implications. Target molecules of this enzyme and its products vary, including low-molecular weight thiols, proteins, nucleic acids, and lipids. The modified products represent biomarkers of myeloperoxidase action. Moderate inhibition of this enzyme might be critical for the prevention/modulation of excess, uncontrolled inflammatory events. Some phytochemicals inhibit myeloperoxidase, which might explain the reductive effect caused by the intake of vegetables and fruits on cardiovascular diseases. PMID:27013775

  9. Catalytic conversion of lignin pyrolysis model compound- guaiacol and its kinetic model including coke formation

    NASA Astrophysics Data System (ADS)

    Zhang, Huiyan; Wang, Yun; Shao, Shanshan; Xiao, Rui

    2016-11-01

    Lignin is the most difficult to be converted and most easy coking component in biomass catalytic pyrolysis to high-value liquid fuels and chemicals. Catalytic conversion of guaiacol as a lignin model compound was conducted in a fixed-bed reactor over ZSM-5 to investigate its conversion and coking behaviors. The effects of temperature, weight hourly space velocity (WHSV) and partial pressure on product distribution were studied. The results show the maximum aromatic carbon yield of 28.55% was obtained at temperature of 650 °C, WHSV of 8 h‑1 and partial pressure of 2.38 kPa, while the coke carbon yield was 19.55%. The reaction pathway was speculated to be removing methoxy group to form phenols with further aromatization to form aromatics. The amount of coke increased with increasing reaction time. The surface area and acidity of catalysts declined as coke formed on the acid sites and blocked the pore channels, which led to the decrease of aromatic yields. Finally, a kinetic model of guaiacol catalytic conversion considering coke deposition was built based on the above reaction pathway to properly predict product distribution. The experimental and model predicting data agreed well. The correlation coefficient of all equations were all higher than 0.90.

  10. Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides.

    PubMed

    Zhang, Qingnan; Hu, Shu-Xian; Qu, Hui; Su, Jing; Wang, Guanjun; Lu, Jun-Bo; Chen, Mohua; Zhou, Mingfei; Li, Jun

    2016-06-06

    The chemistry of lanthanides (Ln=La-Lu) is dominated by the low-valent +3 or +2 oxidation state because of the chemical inertness of the valence 4f electrons. The highest known oxidation state of the whole lanthanide series is +4 for Ce, Pr, Nd, Tb, and Dy. We report the formation of the lanthanide oxide species PrO4 and PrO2 (+) complexes in the gas phase and in a solid noble-gas matrix. Combined infrared spectroscopic and advanced quantum chemistry studies show that these species have the unprecedented Pr(V) oxidation state, thus demonstrating that the pentavalent state is viable for lanthanide elements in a suitable coordination environment.

  11. Formation of N-nitroso compounds during cooking of Japanese food.

    PubMed

    Kawabata, T; Matsui, M; Ishibashi, T; Hamano, M; Ino, M

    1982-01-01

    N-Nitrosamines in several traditional Japanese meals, such as 'Nebemono', 'Ten-pura' and Kara-age', were analysed. No appreciable amount, or only trace quantities, of NDMA and NPYR could be detected in these meals. The effects of various gases on nitrosamine formation in dried squid have been examined at higher cooking temperatures and the highest yield of NDMA was observed by exposure to the gas produced by the combustion of kerosene, followed by that of city gas, while very low levels of NDMA were formed when samples were wrapped in aluminium foil or broiled in air or argon atmospheres. The principal precursor of NDMA in dried squid was found to be TMAO, which is abundant in the squid muscle and from which nitrosatable DMA can be produced during broiling at higher temperatures.

  12. Formation of nanostructured Group IIA metal activated sensors: The transformation of Group IIA metal compound sites

    NASA Astrophysics Data System (ADS)

    Tune, Travis C.; Baker, Caitlin; Hardy, Neil; Lin, Arthur; Widing, Timothy J.; Gole, James L.

    2015-05-01

    Trends in the Group IIA metal oxides and hydroxides of magnesium, calcium, and barium are unique in the periodic table. In this study we find that they display novel trends as decorating nanostructures for extrinsic semiconductor interfaces. The Group IIA metal ions are strong Lewis acids. We form these M2+ ions in aqueous solution and bring these solutions in contact with a porous silicon interface to form interfaces for conductometric measurements. Observed responses are consistent with the formation of MgO whereas the heavier elements display behaviors which suggest the effect of their more basic nature. Mg(OH)2, when formed, represents a weak base whereas the heavier metal hydroxides of Ca, Sr, and Ba are strong bases. However, the hydroxides tend to give up hydrogen and act as Brönsted acids. For the latter elements, the reversible interaction response of nanostructures deposited to the porous silicon (PS) interface is modified, as the formation of more basic sites appears to compete with M2+ Lewis acidity and hydroxide Brönsted acidity. Mg2+ forms an interface whose response to the analytes NH3 and NO is consistent with MgO and well explained by the recently developing Inverse Hard/Soft Acid/Base model. The behavior of the Ca2+ and Ba2+ decorated interfaces as they interact with the hard base NH3 follows a reversal of the model, indicating a decrease in acidic character as the observed conductometric response suggests the interaction with hydroxyl groups. A change from oxide-like to hydroxide-like constituents is supported by XPS studies. The changes in conductometric response is easily monitored in contrast to changes associated with the Group IIA oxides and hydroxides observed in XPS, EDAX, IR, and NMR measurements.

  13. Mechanical properties and electronic structures of Fe-Al intermetallic

    NASA Astrophysics Data System (ADS)

    Liu, YaHui; Chong, XiaoYu; Jiang, YeHua; Zhou, Rong; Feng, Jing

    2017-02-01

    Using the first-principles calculations, the elastic properties, anisotropy properties, electronic structures, Debye temperature and stability of Fe-Al (Fe3Al, FeAl, FeAl2, Fe2Al5 and FeAl3) binary compounds were calculated. The formation enthalpy and cohesive energy of these Fe-Al compounds are negative, and show they are thermodynamically stable structures. Fe2Al5 has the lowest formation enthalpy, which shows the Fe2Al5 is the most stable of Fe-Al binary compounds. These Fe-Al compounds display disparate anisotropy due to the calculated different shape of the 3D curved surface of the Young's modulus and anisotropic index. Fe3Al has the biggest bulk modulus with the value 233.2 GPa. FeAl has the biggest Yong's modulus and shear modulus with the value 296.2 GPa and 119.8 GPa, respectively. The partial density of states, total density of states and electron density distribution maps of the binary Fe-Al binary compounds are analyzed. The bonding characteristics of these Fe-Al binary compounds are mainly combination by covalent bond and metallic bonds. Meanwhile, also exist anti-bond effect. Moreover, the Debye temperatures and sound velocity of these Fe-Al compounds are explored.

  14. Volatile and intermediate-volatility organic compounds in sub-urban Paris: variability, origin and importance for SOA formation

    NASA Astrophysics Data System (ADS)

    Ait-Helal, W.; Borbon, A.; Sauvage, S.; de Gouw, J. A.; Colomb, A.; Gros, V.; Freutel, F.; Crippa, M.; Afif, C.; Baltensperger, U.; Beekmann, M.; Doussin, J.-F.; Durand-Jolibois, R.; Fronval, I.; Grand, N.; Leonardis, T.; Lopez, M.; Michoud, V.; Miet, K.; Perrier, S.; Prévôt, A. S. H.; Schneider, J.; Siour, G.; Zapf, P.; Locoge, N.

    2014-02-01

    Measurements of gaseous and particulate organic carbon were performed during the MEGAPOLI experiments, in July 2009 and January-February 2010, at the SIRTA observatory in sub-urban Paris. Measurements of primary and secondary volatile organic compounds (VOCs), of both anthropogenic and biogenic origins, including for the first time C12-C16 n-alkanes of intermediate volatility (IVOCs), suspected to be efficient precursors of secondary organic aerosol (SOA). The time series of gaseous carbon are generally consistent with times series of particulate organic carbon at regional scales and are clearly affected by meteorology and air mass origin. Concentration levels of anthropogenic VOCs in urban and sub-urban Paris were surprisingly low (2-963 ppt) compared to other megacities worldwide and to rural continental sites. Urban enhancement ratios of anthropogenic VOC pairs agree well between the urban and sub-urban Paris sites, showing the regional extent of anthropogenic sources of similar composition. Contrary to other primary anthropogenic VOCs (aromatics and alkanes), IVOCs showed lower concentrations in winter (< 5 ppt) compared to summer (13-27 ppt) in agreement with a gas-particle partitioning in favor of their transfer to the particle phase in winter. Higher concentrations of most oxygenated VOCs in winter (18-5984 ppt) suggest their dominant primary anthropogenic origin. The respective role of primary anthropogenic gaseous compounds in regional SOA formation was investigated by estimating the SOA mass concentration expected from the anthropogenic VOCs and IVOCs (I / VOCs) measured at SIRTA. From an approach based on emissions inferred from the I / VOC concentrations times the SOA formation yields', the so-called integrated approach conducted in this study, 46% of the SOA measured at SIRTA is explained by our measured concentrations of I / VOC, with 10% explained by only C12-C16 IVOCs. From results of an alternative time-resolved approach, the explained variability

  15. Dissolution of Cu/Mg Bearing Intermetallics in Al-Si Foundry Alloys

    NASA Astrophysics Data System (ADS)

    Javidani, Mousa; Larouche, Daniel; Grant Chen, X.

    2016-10-01

    Evolutions of the Cu/Mg bearing intermetallics were thoroughly investigated in four Al-Si hypoeutectic alloys containing various Cu (1 and 1.6 wt pct) and Mg (0.4 and 0.8 wt pct) contents. The area fractions of Cu/Mg bearing phases before and after solution heat treatment (SHT) were quantified to evaluate the solubility/stability of the phases. Two Mg-bearing intermetallics (Q-Al5Cu2Mg8Si6, π-Al8FeMg3Si6) which appear as gray color under optical microscope were discriminated by the developed etchant. Moreover, the concentrations of the elements (Cu, Mg, and Si) in α-Al were analyzed. The results illustrated that in the alloys containing ~0.4 pct Mg, Q-Al5Cu2Mg8Si6 phase was dissolved after 6 hours of SHT at 778 K (505 °C); but containing in the alloys ~0.8 pct Mg, it was insoluble/ partially soluble. Furthermore, after SHT at 778 K (505 °C), Mg2Si was partially substituted by Q-phase. Applying a two-step SHT [6 hours@778 K (505 °C) + 8 hours@798 K (525 °C)] in the alloys containing ~0.4 pct Mg helped to further dissolve the remaining Mg bearing intermetallics and further modified the microstructure, but in the alloys containing ~0.8 pct Mg, it caused partial melting of Q-phase. Thermodynamic calculations were carried out to assess the phase formation in equilibrium and in non-equilibrium conditions. There was an excellent agreement between the experimental results and the predicted results.

  16. Formation of alpha-dicarbonyl compounds in beer during storage of Pilsner.

    PubMed

    Bravo, Adriana; Herrera, Julio C; Scherer, Erika; Ju-Nam, Yon; Rübsam, Heinrich; Madrid, Jorge; Zufall, Carsten; Rangel-Aldao, Rafael

    2008-06-11

    With the aim of determining the formation of alpha-dicarbonyl intermediates during beer aging on the shelf, alpha-dicarbonyls were identified and quantified after derivatization with 1,2-diaminobenze to generate quinoxalines. The sensory effects of alpha-dicarbonyls were evaluated by the quantification of key Strecker aldehydes and by GC-olfactometry (GCO)analysis of beer headspace using solid phase microextraction. Four alpha-dicarbonyls, reported here for the first time, were detected in fresh and aged beers, three were derived from the 2,3-enolization pathway of mono- and disaccharides, and the fourth was derived from the epimerization of 3-deoxy-2-hexosulose. Ten alpha-dicarbonyls were quantified during beer processing and during different periods of beer aging at 28 degrees C. The aging periods were from 15 to 105 days. During beer aging, 1-deoxydiuloses were produced and degraded, while 1,4-dideoxydiuloses were produced at the highest rates. The GCO analysis indicated that forced beer aging increased the amounts of furaneol, trans-2-nonenal, and phenylacetaldehyde. The blockage of alpha-dicarbonyls inhibited the accumulation of sensory-active aldehydes in the beer headspace.

  17. Synthesis and chemistry of organoimidovanadium(V) compounds and their role in the formation of vanadium nitrides

    NASA Astrophysics Data System (ADS)

    Gipson, Rocky Dean

    A series of vanadium(V) compounds of the formula (eta5-C 5Me5)V(NR)Cl2 (R = 1-adamantyl, tert-butyl, para-tolyl) have been prepared by the reaction of (eta5 -C5Me5)V(O)Cl2 with RNCO or by oxidation of [(eta5-C5Me5)VCl2] 3 with azide. The para-tolylimido compound undergoes chloride metathesis with monoanionic reagents NaOtBu, LiNEt 2, and Mg(CH2SiMe3)2 to produce mono- and disubstituted products. A discussion of ligand strength in this system using 51V NMR is presented. Ammonolysis of the dichloro compounds produces the symmetrically-bridged [(eta5-C5Me5)V(mu-N)Cl]2, in yields consistent with the basicity of the organoimido ligand. A comparison of this reactivity with that of (eta5-C5Me 5)V(NSiMe3)Cl2 is presented. An X-ray structural study of (eta5-C5Me5)V(NtBu)Cl 2 exhibits a 173° V-N-C imido linkage and V-N triple bond. Synthesis of (eta5-tBuC5H 4)V(NR)Cl2 compounds was performed utilizing (t-Bu)C 5H4SiMe3 as the cyclopentadiene reagent with V(NR)Cl 3. In contrast to the metathesis of V(NR)Cl3 compounds with Li(tBu)C5H4, reduction of the vanadium(V) is not observed. An X-ray crystal structure of (eta5- tBuC5H4)V(N-ptol)Cl2 reveals linear V-N-C bonding, and a short N-C bond of 139 pm. This is explained by delocalized bonding, which incorporates the imido carbon atoms as well as nitrogen and vanadium. Details of the structure and valence-bond descriptions are of this compound are presented. Organoimidotrichlorovanadium(V) compounds bind ligands L2 (L2 = 1,2-dimethoxyethane; N,N,N,N-tetramethylethylenediamine) to produce adducts V(NR)Cl3L2. The V(NR)Cl3L 2 compounds thermally react to form terminal nitrides V(N)Cl2L 2 via an unprecedented cleavage of the N-C bond of the organoimido ligand, with reactivity following the order t-butyl > 1-adamantyl > p-tolyl. The downfield 51V NMR shifts of the adducts relative to starting materials is discussed using crystal-field models. X-ray crystal structures of V(NAd)Cl3(DME) and V(N ptol)Cl3(TMEDA) are presented, and details

  18. Impact of molecular weight on the formation of electrosprayed chitosan microcapsules as delivery vehicles for bioactive compounds.

    PubMed

    Gómez-Mascaraque, Laura G; Sanchez, Gloria; López-Rubio, Amparo

    2016-10-05

    The molecular weight of chitosan is one of its most determinant characteristics, which affects its processability and its performance as a biomaterial. However, information about the effect of this parameter on the formation of electrosprayed chitosan microcapsules is scarce. In this work, the impact of chitosan molecular weight on its electrosprayability was studied and correlated with its effect on the viscosity, surface tension and electrical conductivity of solutions. A Discriminant Function Analysis revealed that the morphology of the electrosprayed chitosan materials could be correctly predicted using these three parameters for almost 85% of the samples. The suitability of using electrosprayed chitosan capsules as carriers for bioactive agents was also assessed by loading them with a model active compound, (-)-epigallocatechin gallate (EGCG). This encapsulation, with an estimated efficiency of around 80% in terms of preserved antioxidant activity, showed the potential to prolong the antiviral activity of EGCG against murine norovirus via gradual bioactive release combined with its protection against degradation in simulated physiological conditions.

  19. Na@SiO2-Mediated Addition of Organohalides to Carbonyl Compounds for the Formation of Alcohols and Epoxides

    NASA Astrophysics Data System (ADS)

    Kapoor, Mohit; Hwu, Jih Ru

    2016-11-01

    Alcohols and epoxides were generated by the addition of organohalides to carbonyl compounds in the presence of sodium metal impregnated with silica gel (Na@SiO2) in THF at 25 °C through a radical pathway. Under the same conditions, Schiff bases were also successfully converted to the corresponding amines. Furthermore, the reaction of aldehydes with α-haloesters or 4-(chloromethyl)-coumarin with the aid of Na@SiO2 generated trans epoxides. An unprecedented mechanism is proposed for their formation. The advantages associated with these new reactions include: (1) products are obtained in good-to-excellent yields, (2) reactions are completed at room temperatures in a short period of time (<2.0 h), (3) it is unnecessary to perform the reactions under anhydrous conditions, and (4) the entire process requires only simple manipulations.

  20. Compounds of tin(IV) - catalysts of amide formation. Effect of temperature and nature of leaving group

    SciTech Connect

    Oleinik, N.M.; Garkusha-Bozhko, I.P.; Usanova, I.V.

    1988-09-20

    The effect of substitution of the ester oxygen atom by sulfur in p-nitrophenyl acetate on its aminolysis rate with benzylamine in beneze at 25/degree/C in the presence of dibutyltin dibenzoate as catalyst was studied. Such substitution leads to a decrease in the catalytic activity by approximately a half, and this is explained by the smaller capacity of the sulfur atom for the formation of hydrogen bonds. The effect of temperature on the rate of the reaction of N-benzyl-oxycarbonylglycine p-nitrophenyl ester with glycine tert-butyl ester in benzene in the presence of dibutyltin dibenzoate was also investigated in the range of 10-50/degree/C. The Arrhenius equation is not fulfilled in this case. The obtained facts demonstrate the multistage character of the catalytic reaction and do not contradict the authors previously proposed bifunctional mechanism of catalysis by tin(IV) compounds.

  1. Vibrational spectral investigation and natural bond orbital analysis of pharmaceutical compound 7-Amino-2,4-dimethylquinolinium formate - DFT approach

    NASA Astrophysics Data System (ADS)

    Suresh, D. M.; Amalanathan, M.; Sebastian, S.; Sajan, D.; Hubert Joe, I.; Bena Jothy, V.; Nemec, Ivan

    2013-11-01

    The molecular geometry, the normal mode frequencies and corresponding vibrational assignments, natural bond orbital analysis and the HOMO-LUMO analysis of 7-Amino-2,4-dimethylquinolinium formate in the ground state were performed by B3LYP levels of theory using the 6-31G(d) basis set. The optimised bond lengths and bond angles are in good agreement with the X-ray data. The vibrational spectra of the title compound which is calculated by DFT method, reproduces vibrational wave numbers and intensities with an accuracy which allows reliable vibrational assignments. The possibility of N-H⋯O hydrogen bonding was identified using NBO analysis. Natural bond orbital analysis confirms the presence of intramolecular charge transfer and the hydrogen bonding interaction.

  2. Vibrational spectral investigation and natural bond orbital analysis of pharmaceutical compound 7-Amino-2,4-dimethylquinolinium formate - DFT approach.

    PubMed

    Suresh, D M; Amalanathan, M; Sebastian, S; Sajan, D; Hubert Joe, I; Bena Jothy, V; Nemec, Ivan

    2013-11-01

    The molecular geometry, the normal mode frequencies and corresponding vibrational assignments, natural bond orbital analysis and the HOMO-LUMO analysis of 7-Amino-2,4-dimethylquinolinium formate in the ground state were performed by B3LYP levels of theory using the 6-31G(d) basis set. The optimised bond lengths and bond angles are in good agreement with the X-ray data. The vibrational spectra of the title compound which is calculated by DFT method, reproduces vibrational wave numbers and intensities with an accuracy which allows reliable vibrational assignments. The possibility of N-H⋯O hydrogen bonding was identified using NBO analysis. Natural bond orbital analysis confirms the presence of intramolecular charge transfer and the hydrogen bonding interaction.

  3. [Studies by means of 1H NMR spectroscopy of complex formation of aromatic biologically active compounds with antibiotic topotecan].

    PubMed

    Mosunov, A A; Kostiukov, V V; Evstigneev, M P

    2012-01-01

    The analysis of heteroassociation of antibiotic topotecan (TPT) with aromatic biologically active compounds (BAC): caffeine, mutagens ethidium bromide and proflavine, antibiotic daunomycin, vitamins flavin-mononucleotide and nicotinamide, has been carried out in the work using 1H NMR spectroscopy data. The equilibrium constants of heteroassociation and induced chemical shifts of the protons have been obtained in the complexes with BAC. It is found that the complex formation TPT-BAC has the nature of stacking of the chromophores, additionally stabilized in the case of proflavine by intermolecular hydrogen bond. Calculation of the basic components of the Gibbs free energy of the complexation reactions is carried out, and the factors which stabilize and destabilize the heterocomplexes of molecules are revealed.

  4. Na@SiO2-Mediated Addition of Organohalides to Carbonyl Compounds for the Formation of Alcohols and Epoxides

    PubMed Central

    Kapoor, Mohit; Hwu, Jih Ru

    2016-01-01

    Alcohols and epoxides were generated by the addition of organohalides to carbonyl compounds in the presence of sodium metal impregnated with silica gel (Na@SiO2) in THF at 25 °C through a radical pathway. Under the same conditions, Schiff bases were also successfully converted to the corresponding amines. Furthermore, the reaction of aldehydes with α-haloesters or 4-(chloromethyl)-coumarin with the aid of Na@SiO2 generated trans epoxides. An unprecedented mechanism is proposed for their formation. The advantages associated with these new reactions include: (1) products are obtained in good-to-excellent yields, (2) reactions are completed at room temperatures in a short period of time (<2.0 h), (3) it is unnecessary to perform the reactions under anhydrous conditions, and (4) the entire process requires only simple manipulations. PMID:27853277

  5. Observations of a dynamical-to-kinematic diffraction transition in plastically deformed polycrystalline intermetallic YCu

    SciTech Connect

    Williams, Scott H.; Brown, Donald W.; Clausen, Bjorn; Russell, Alan; Gschneidner Jr., Karl A.

    2014-03-01

    Unlike most intermetallic compounds, polycrystalline YCu, a B2 (CsCl-type) intermetallic, is ductile at room temperature. The mechanisms for this behavior are not fully understood. In situ neutron diffraction was used to investigate whether a stress-induced phase transformation or twinning contribute to the ductility; however, neither mechanism was found to be active in YCu. Surprisingly, this study revealed that the intensities of the diffraction peaks increased after plastic deformation. It is thought that annealing the samples created nearly perfect crystallinity, and subsequent deformation reduced this high degree of lattice coherency, resulting in a modified mosaic structure that decreased or eliminated the extinction effect. Analysis of changes in diffraction peak intensity showed a region of primary plasticity that exhibits significant changes in diffraction behavior. Fully annealed samples initially contain diffracting volumes large enough to follow the dynamical theory of diffraction. When loaded beyond the yield point, dislocation motion disrupts the lattice perfection, and the diffracting volume is reduced to the point that diffraction follows the kinematic theory of diffraction. Since the sample preparation and deformation mechanisms present in this study are common in numerous material systems, this dynamical to kinematic diffraction transition should also be considered in other diffraction experiments. These measurements also suggest the possibility of a new method of investigating structural characteristics. (C) 2014 Published by Elsevier Ltd. on behalf of Acta Materialia Inc.

  6. Volatile organic compounds measured in summer in Beijing and their role in ground-level ozone formation

    NASA Astrophysics Data System (ADS)

    Shao, Min; Lu, Sihua; Liu, Ying; Xie, Xin; Chang, Chichung; Huang, Shan; Chen, Zhongmin

    2009-01-01

    Beijing has long suffered from serious ground-level ozone pollution, and volatile organic compounds (VOCs) play a key role in ozone formation. To understand the chemical speciation of VOCs in Beijing, nonmethane hydrocarbons (NMHCs) and oxygenated VOCs (OVOCs) were measured in summer in Beijing and nearby provinces (VOCs in this work means NMHCs+OVOCs). A variation of VOC mixing ratios and chemical speciation from 2004 to 2006 was observed at an urban site in Beijing. The typical VOC species, e.g., propane, propene, and toluene, had comparable or lower mixing ratios than levels found in other cities that previously hosted the Olympic Games, while the mixing ratios for isoprene were higher. The chemical compositions of VOCs within Beijing were heavily influenced by vehicular emissions and differed from those obtained in Tianjin and Hebei Province. OVOCs were an important component, accounting for 54% and 37% in the VOC mixing ratio in 2005 and 2006, respectively, and about 40% of the OH loss rates. The main reactive VOC compounds were aldehydes and alkenes. By using isoprene chemistry and the ratio of ethylbenzene to mp-xylene, the initial mixing ratios of VOCs were estimated. The VOCs had similar variation patterns to ambient ozone and peroxyacetyl nitrate (PAN) concentrations. The correlation between daily maximum ozone concentrations and initial VOCs revealed that ozone formation was sensitive to VOCs for both urban (Peking University, PKU) and rural (Yufa) sites. A reduction in NOx would lead to a decrease in ozone at Yufa, but would cause increased ozone at the PKU site.

  7. Fluorimetric determination of some sulfur containing compounds through complex formation with terbium (Tb+3) and uranium (U+3).

    PubMed

    Taha, Elham Anwer; Hassan, Nagiba Yehya; Aal, Fahima Abdel; Fattah, Laila El-Sayed Abdel

    2007-05-01

    Two simple, sensitive and specific fluorimetric methods have been developed for the determination of some sulphur containing compounds namely, Acetylcysteine (Ac), Carbocisteine (Cc) and Thioctic acid (Th) using terbium Tb+3 and uranium U+3 ions as fluorescent probes. The proposed methods involve the formation of a ternary complex with Tb+3 in presence of Tris-buffer method (I) and a binary complex with aqueous uranyl acetate solution method (II). The fluorescence quenching of Tb+3 at 510, 488 and 540 nm (lambda(ex) 250, 241 and 268 nm) and of uranyl acetate at 512 nm (lambda(ex) 240 nm) due to the complex formation was quantitatively measured for Ac, Cc and Th, respectively. The reaction conditions and the fluorescence spectral properties of the complexes have been investigated. Under the described conditions, the proposed methods were applicable over the concentration range (0.2-2.5 microg ml(-1)), (1-4 microg ml(-1)) and (0.5-3.5 microg ml(-1)) with mean percentage recoveries 99.74+/-0.36, 99.70+/-0.52 and 99.43+/-0.23 for method (I) and (0.5-6 microg ml(-1)), (0.5-5 microg ml(-1)), and (1-6 microg ml(-1)) with mean percentage recoveries 99.38+/-0.20, 99.82+/-0.28 and 99.93+/-0.32 for method (II), for the three cited drugs, respectively. The proposed methods were successfully applied for the determination of the studied compounds in bulk powders and in pharmaceutical formulations, as well as in presence of their related substances. The results obtained were found to be in agree statistically with those obtained by official and reported ones. The two methods were validated according to USP guidelines and also assessed by applying the standard addition technique.

  8. Formation of nitrogen- and sulfur-containing light-absorbing compounds accelerated by evaporation of water from secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Nguyen, Tran B.; Lee, Paula B.; Updyke, Katelyn M.; Bones, David L.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey A.

    2012-01-01

    Aqueous extracts of secondary organic aerosols (SOA) generated from the ozonolysis of d-limonene were subjected to dissolution, evaporation, and re-dissolution in the presence and absence of ammonium sulfate (AS). Evaporation with AS at pH 4-9 produced chromophores that were stable with respect to hydrolysis and had a distinctive absorption band at 500 nm. Evaporation accelerated the rate of chromophore formation by at least three orders of magnitude compared to the reaction in aqueous solution, which produced similar compounds. Absorption spectroscopy and high-resolution nanospray desorption electrospray ionization (nano-DESI) mass spectrometry experiments suggested that the molar fraction of the chromophores was small (<2%), and that they contained nitrogen atoms. Although the colored products represented only a small fraction of SOA, their large extinction coefficients (>105 L mol-1 cm-1 at 500 nm) increased the effective mass absorption coefficient of the residual organics in excess of 103 cm2 g-1 - a dramatic effect on the optical properties from minor constituents. Evaporation of SOA extracts in the absence of AS resulted in the production of colored compounds only when the SOA extract was acidified to pH ˜ 2 with sulfuric acid. These chromophores were produced by acid-catalyzed aldol condensation, followed by a conversion into organosulfates. The presence of organosulfates was confirmed by high resolution mass spectrometry experiments. Results of this study suggest that evaporation of cloud or fog droplets containing dissolved organics leads to significant modification of the molecular composition and serves as a potentially important source of light-absorbing compounds.

  9. Formation of Nitrogen- and Sulfur-Containing Light-Absorbing Compounds Accelerated by Evaporation of Water from Secondary Organic Aerosols

    SciTech Connect

    Nguyen, Tran B.; Lee, Paula B.; Updyke, Katelyn M.; Bones, David L.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey

    2012-01-14

    Aqueous extracts of secondary organic aerosols (SOA) generated from the ozonolysis of dlimonene were subjected to dissolution, evaporation, and re-dissolution in the presence and absence of ammonium sulfate (AS). Evaporation with AS at pH 4-9 produced chromophores that were stable with respect to hydrolysis and had a distinctive absorption band at 500 nm. Evaporation accelerated the rate of chromophore formation by at least three orders of magnitude compared to the reaction in aqueous solution, which produced similar compounds. Absorption spectroscopy and high-resolution nanospray desorption electrospray ionization (nano-DESI) mass spectrometry experiments suggested that the molar fraction of the chromophores was small (< 2%), and that they contained nitrogen atoms. Although the colored products represented only a small fraction of SOA, their large extinction coefficients (>10{sup 5} L mol{sup -1} cm{sup -1} at 500 nm) increased the effective mass absorption coefficient of the residual organics in excess of 10{sup 3} cm{sup 2} g{sup -1} - a dramatic effect on the optical properties from minor constituents. Evaporation of SOA extracts in the absence of AS resulted in the production of colored compounds only when the SOA extract was acidified to pH {approx} 2 with sulfuric acid. These chromophores were produced by acid-catalyzed aldol condensation, followed by a conversion into organosulfates. The presence of organosulfates was confirmed by high resolution mass spectrometry experiments. Results of this study suggest that evaporation of cloud or fog droplets containing dissolved organics leads to significant modification of the molecular composition and serves as a potentially important source of light-absorbing compounds.

  10. Predicting density functional theory total energies and enthalpies of formation of metal-nonmetal compounds by linear regression

    NASA Astrophysics Data System (ADS)

    Deml, Ann M.; O'Hayre, Ryan; Wolverton, Chris; Stevanović, Vladan

    2016-02-01

    The availability of quantitatively accurate total energies (Etot) of atoms, molecules, and solids, enabled by the development of density functional theory (DFT), has transformed solid state physics, quantum chemistry, and materials science by allowing direct calculations of measureable quantities, such as enthalpies of formation (Δ Hf ). Still, the ability to compute Etot and Δ Hf values does not, necessarily, provide insights into the physical mechanisms behind their magnitudes or chemical trends. Here, we examine a large set of calculated Etot and Δ Hf values obtained from the DFT+U -based fitted elemental-phase reference energies (FERE) approach [V. Stevanović, S. Lany, X. Zhang, and A. Zunger, Phys. Rev. B 85, 115104 (2012), 10.1103/PhysRevB.85.115104] to probe relationships between the Etot/Δ Hf of metal-nonmetal compounds in their ground-state crystal structures and properties describing the compound compositions and their elemental constituents. From a stepwise linear regression, we develop a linear model for Etot, and consequently Δ Hf , that reproduces calculated FERE values with a mean absolute error of ˜80 meV/atom. The most significant contributions to the model include calculated total energies of the constituent elements in their reference phases (e.g., metallic iron or gas phase O2), atomic ionization energies and electron affinities, Pauling electronegativity differences, and atomic electric polarizabilities. These contributions are discussed in the context of their connection to the underlying physics. We also demonstrate that our Etot/Δ Hf model can be directly extended to predict the Etot and Δ Hf of compounds outside the set used to develop the model.

  11. Formation of volatile compounds in kefir made of goat and sheep milk with high polyunsaturated fatty acid content.

    PubMed

    Cais-Sokolińska, D; Wójtowski, J; Pikul, J; Danków, R; Majcher, M; Teichert, J; Bagnicka, E

    2015-10-01

    This article explored the formation of volatile compounds during the production of kefir from goat and sheep milks with high polyunsaturated fatty acids (PUFA) as a result of feeding animals forage supplemented with maize dried distillers grains with solubles (DDGS). The increased PUFA content of the goat and sheep milks resulted in significant changes to the fermentation process. In particular, apart from an increase in the time taken to ferment sheep milk, fermentation yielded less 2,3-butanedione. The highest quantities of this compound were assayed in kefir produced from goat milk with an increased content of PUFA. An increase of PUFA significantly elevated ethanal synthesis during lactose-alcohol fermentation of sheep milk. Neither the origin of milk (sheep or goat) nor the level of PUFA had any statistical effect on the amount of ethanal assayed during the fermentation of milk and within the finished product. The proportion of l(+)-lactic acid was higher in kefirs produced using goat milk compared with sheep milk and did not depend on the content of PUFA in milk fat. The content of PUFA had a significant effect on the aroma profile of the resulting kefirs. An increase in PUFA content resulted in the loss of whey aroma in goat milk kefirs and the animal odor in sheep milk kefirs, and a creamy aroma became more prevalent in kefirs made from sheep milk.

  12. Formation of combustible hydrocarbons and H2 during photocatalytic decomposition of various organic compounds under aerated and deaerated conditions.

    PubMed

    Mozia, Sylwia; Kułagowska, Aleksandra; Morawski, Antoni W

    2014-11-26

    A possibility of photocatalytic production of useful aliphatic hydrocarbons and H2 from various organic compounds, including acetic acid, methanol, ethanol and glucose, over Fe-modified TiO2 is discussed. In particular, the influence of the reaction atmosphere (N2, air) was investigated. Different gases were identified in the headspace volume of the reactor depending on the substrate. In general, the evolution of the gases was more effective in air compared to a N2 atmosphere. In the presence of air, the gaseous phase contained CO2, CH4 and H2, regardless of the substrate used. Moreover, formation of C2H6 and C3H8 in the case of acetic acid and C2H6 in the case of ethanol was observed. In case of acetic acid and methanol an increase in H2 evolution under aerated conditions was observed. It was concluded that the photocatalytic decomposition of organic compounds with simultaneous generation of combustible hydrocarbons and hydrogen could be a promising method of "green energy" production.

  13. Photo-oxidation of 6-thioguanine by UVA: the formation of addition products with low molecular weight thiol compounds.

    PubMed

    Ren, Xiaolin; Xu, Yao-Zhong; Karran, Peter

    2010-01-01

    The thiopurine, 6-thioguanine (6-TG) is present in the DNA of patients treated with the immunosuppressant and anticancer drugs azathioprine or mercaptopurine. The skin of these patients is selectively sensitive to UVA radiation-which comprises >90% of the UV light in incident sunlight-and they suffer high rates of skin cancer. UVA irradiation of DNA 6-TG produces DNA lesions that may contribute to the development of cancer. Antioxidants can protect 6-TG against UVA but 6-TG oxidation products may undergo further reactions. We characterize some of these reactions and show that addition products are formed between UVA-irradiated 6-TG and N-acetylcysteine and other low molecular weight thiol compounds including β-mercaptoethanol, cysteine and the cysteine-containing tripeptide glutathione (GSH). GSH is also adducted to 6-TG-containing oligodeoxynucleotides in an oxygen- and UVA-dependent nucleophilic displacement reaction that involves an intermediate oxidized 6-TG, guanine sulfonate (G(SO3) ). These photochemical reactions of 6-TG, particularly the formation of a covalent oligodeoxynucleotide-GSH complex, suggest that crosslinking of proteins or low molecular weight thiol compounds to DNA may be a previously unrecognized hazard in sunlight-exposed cells of thiopurine-treated patients.

  14. Volatile organic compounds speciation and their influence on ozone formation potential in an industrialized urban area in Brazil.

    PubMed

    Galvão, Elson Silva; Santos, Jane Meri; Reis Junior, Neyval Costa; Stuetz, Richard Michael

    2016-09-01

    Speciation and the influence on the ozone formation potential (OFP) from volatile organic compounds (VOCs) have been studied between February June 2013 in Vitória, ES, Brazil. Passive samplers were installed at three air-quality monitoring stations and a total of 96 samplings were collected. A total of 78 VOCs were characterized by gas chromatograph-mass spectrometer. The predominant group was organic acids, followed by alcohols and substituted aromatics and 14 precursor species were quantified. An analysis correlating concentrations with wind direction was conducted to identify possible sources. The OFP was calculated applying the scale of maximum incremental reactivity proposed by Carter.[ 23 ] Ozone precursors with the greatest OFP such as undecane, toluene, ethylbenzene and m, p-xylene compounds were the most abundant with means of 0.855, 0.365, 0.259 and 0.289 µg m(-3), respectively. The benzene, toluene, ethylbenzene and xylene (BTEX) group was found below the limits considered harmful to the health of the population living in Vitória. The OFP calculated for the precursors group was 22.55 µg m(-3) for the rainy season and 32.11 µg m(-3) for the dry season. The VOC/NOx ratio in Vitória is approximately 1.71, indicating that the region has a VOC-limiting condition for the production of ozone.

  15. Process for synthesizing compounds from elemental powders and product

    DOEpatents

    Rabin, B.H.; Wright, R.N.

    1993-12-14

    A process for synthesizing intermetallic compounds from elemental powders is described. The elemental powders are initially combined in a ratio which approximates the stoichiometric composition of the intermetallic compound. The mixed powders are then formed into a compact which is heat treated at a controlled rate of heating such that an exothermic reaction between the elements is initiated. The heat treatment may be performed under controlled conditions ranging from a vacuum (pressureless sintering) to compression (hot pressing) to produce a desired densification of the intermetallic compound. In a preferred form of the invention, elemental powders of Fe and Al are combined to form aluminide compounds of Fe[sub 3] Al and FeAl. 25 figures.

  16. A prebiotic fiber increases the formation and subsequent absorption of compound K following oral administration of ginseng in rats

    PubMed Central

    Kim, Kyung-Ah; Yoo, Hye Hyun; Gu, Wan; Yu, Dae-Hyung; Jin, Ming Ji; Choi, Hae-Lim; Yuan, Kathy; Guerin-Deremaux, Laetitia; Kim, Dong-Hyun

    2014-01-01

    Background Gut microflora play a crucial role in the biotransformation of ginsenosides to compound K (CK), which may affect the pharmacological effects of ginseng. Prebiotics, such as NUTRIOSE, could enhance the formation and consequent absorption of CK through the modulation of gut microbial metabolic activities. In this study, the effect of a prebiotic fiber (NUTRIOSE) on the pharmacokinetics of ginsenoside CK, a bioactive metabolite of ginsenosides, and its mechanism of action were investigated. Methods Male Sprague–Dawley rats were given control or NUTRIOSE-containing diets (control diet + NUTRIOSE) for 2 wk, and ginseng extract or vehicle was then orally administered. Blood samples were collected to investigate the pharmacokinetics of CK using liquid chromatography–tandem mass spectrometry. Fecal activities that metabolize ginsenoside Rb1 to CK were assayed with fecal specimens or bacteria cultures. Results When ginseng extract was orally administered to rats fed with 2.5%, 5%, or 10% NUTRIOSE containing diets, the maximum plasma concentration (Cmax) and area under the plasma concentration–time curve values of CK significantly increased in a NUTRIOSE content-dependent manner. NUTRIOSE intake increased glycosidase activity and CK formation in rat intestinal contents. The CK-forming activities of intestinal microbiota cultured in vitro were significantly induced by NUTRIOSE. Conclusion These results show that prebiotic diets, such as NUTRIOSE, may promote the metabolic conversion of ginsenosides to CK and the subsequent absorption of CK in the gastrointestinal tract and may potentiate the pharmacological effects of ginseng. PMID:26045693

  17. Flavoring agents present in a dentifrice can modify volatile sulphur compounds (VSCs) formation in morning bad breath.

    PubMed

    Peruzzo, Daiane Cristina; Salvador, Sérgio Luis; Sallum, Antonio Wilson; Nogueira-Filho, Getúlio da Rocha

    2008-01-01

    This study aimed to evaluate the effects of a flavor-containing dentifrice on the formation of volatile sulphur compounds (VSCs) in morning bad breath. A two-step, blinded, crossover, randomized study was carried out in 50 dental students with a healthy periodontium divided into two experimental groups: flavor-containing dentifrice (test) and non-flavor-containing dentifrice (control). The volunteers received the designated dentifrice and a new toothbrush for a 3 X/day brushing regimen for 2 periods of 30 days. A seven-day washout interval was used between the periods. The assessed parameters were: plaque index (PI), gingival index (GI), organoleptic breath scores (ORG), VSC levels (as measured by a portable sulphide monitor) before (H1) and after (H2) cleaning of the tongue, tongue coating (TC) wet weight and BANA test from TC samples. The intra-group analysis showed a decrease in ORG, from 3 to 2, after 30 days for the test group (p < 0.05). The inter-group analysis showed lower values in ORG, H1 and H2 for the test group (p < 0.05). There was no difference between the amount of TC between groups and the presence of flavor also did not interfere in the BANA results between groups (p > 0.05). These findings suggest that a flavor-containing dentifrice seems to prevent VSCs formation in morning bad breath regardless of the amount of TC in periodontally healthy subjects.

  18. Formation of Low Volatility Organic Compounds and Secondary Organic Aerosol from Isoprene Hydroxyhydroperoxide Low-NO Oxidation.

    PubMed

    Krechmer, Jordan E; Coggon, Matthew M; Massoli, Paola; Nguyen, Tran B; Crounse, John D; Hu, Weiwei; Day, Douglas A; Tyndall, Geoffrey S; Henze, Daven K; Rivera-Rios, Jean C; Nowak, John B; Kimmel, Joel R; Mauldin, Roy L; Stark, Harald; Jayne, John T; Sipilä, Mikko; Junninen, Heikki; Clair, Jason M St; Zhang, Xuan; Feiner, Philip A; Zhang, Li; Miller, David O; Brune, William H; Keutsch, Frank N; Wennberg, Paul O; Seinfeld, John H; Worsnop, Douglas R; Jimenez, Jose L; Canagaratna, Manjula R

    2015-09-01

    Gas-phase low volatility organic compounds (LVOC), produced from oxidation of isoprene 4-hydroxy-3-hydroperoxide (4,3-ISOPOOH) under low-NO conditions, were observed during the FIXCIT chamber study. Decreases in LVOC directly correspond to appearance and growth in secondary organic aerosol (SOA) of consistent elemental composition, indicating that LVOC condense (at OA below 1 μg m(-3)). This represents the first simultaneous measurement of condensing low volatility species from isoprene oxidation in both the gas and particle phases. The SOA formation in this study is separate from previously described isoprene epoxydiol (IEPOX) uptake. Assigning all condensing LVOC signals to 4,3-ISOPOOH oxidation in the chamber study implies a wall-loss corrected non-IEPOX SOA mass yield of ∼4%. By contrast to monoterpene oxidation, in which extremely low volatility VOC (ELVOC) constitute the organic aerosol, in the isoprene system LVOC with saturation concentrations from 10(-2) to 10 μg m(-3) are the main constituents. These LVOC may be important for the growth of nanoparticles in environments with low OA concentrations. LVOC observed in the chamber were also observed in the atmosphere during SOAS-2013 in the Southeastern United States, with the expected diurnal cycle. This previously uncharacterized aerosol formation pathway could account for ∼5.0 Tg yr(-1) of SOA production, or 3.3% of global SOA.

  19. Materials Processing and Microstructure Control in High Temperature Ordered Intermetallics.

    DTIC Science & Technology

    2007-11-02

    an integrated approach that couples processing with microstructure control as guided by the operative phase equilibria has been used to identify...several promising intermetallic alloys. The experimental efforts have focused on three areas involving a coordination of phase equilibria information with

  20. Structural and Mössbauer spectroscopy characterization of bulk and nanostructured TiFe0.5 Ni0.5/graphite compounds and their hydrides

    NASA Astrophysics Data System (ADS)

    Martínez, M. A. R.; André-Filho, J.; Félix, L. L.; Coaquira, J. A. H.; Garg, V. K.; Oliveira, A. C.; Mestnik-Filho, J.

    2015-06-01

    The structural and hyperfine properties of bulk TiFe0.5Ni0.5 intermetallic and ball-milled TiFe0.5Ni0.5/graphite compounds and their hydrides have been studied. The bulk and nanostructured TiFe0.5Ni0.5 compounds crystallize in the cubic crystal structure of CsCl (B2). After hydrogenation, the formation of hydrogen-poor phase (∝-phase) and hydride phase ( β-phase) have been determined for the bulk compound. However, the formation of the ∝-phase and the hydrogen-richest phase ( γ-phase) and other secondary phases have been determined for the ball-milled TiFe0.5Ni0.5/graphite sample. It has been determined that the ball-milled TiFe0.5Ni0.5/graphite sample presents a large amount of the γ-phase which indicates that the presence of graphite nearby nanostructured intermetallic grains enhances the absorption of hydrogen. Mossbauer results are consistent with the structural results. Meanwhile, no significant changes in the isomer shift (IS) value has been determined for the α-phase with respect to the intermetallic compound, a strong increase in the IS value has been determined for the β- and γ-phases with respect to the ∝-phase. That increase indicates a decrease of the s-electron density at the Fe nuclei due to the charge transfer from the metal to the nearby hydrogen atoms.