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Presentation on examination of wave speeds in copper, strength in aluminum, and spall in iron as means to improve input physics models used in large-scale hydrodynamic simulations of complex dynamic events.
A homogeneous catalyst is provided comprising one or more metals; and at least two metal coordinating ligands wherein the homogeneous catalyst is a multi-ligand metal complex adapted for use with an oxidant in an oxidation reaction to catalytically pretreat lignocellulosic biomass. In one embodiment, the homogenous catalyst is copper (II) 2, 2′ bipyridine ethylenediamine (Cu(bpy)en). Related methods are also disclosed.
Electroformed copper and nickel are used in structural applications for advanced propellant combustion chambers. An improved process has been developed by Bell Aerospace Textron, Inc. wherein electroformed nickel-manganese alloy has demonstrated superior mechanical and thermal stability when compared to previously reported deposits from known nickel plating processes. Solution chemistry and parametric operating procedures are now established and material property data is established for deposition of thick, large complex shapes such as the Space Shuttle Main Engine. The critical operating variables are those governing the ratio of codeposited nickel and manganese. The deposition uniformity which in turn affects the manganese concentration distribution is affected by solution resistance and geometric effects as well as solution agitation. The manganese concentration in the deposit must be between 2000 and 3000 ppm for optimum physical properties to be realized. The study also includes data regarding deposition procedures for achieving excellent bond strength at an interface with copper, nickel-manganese or INCONEL 718. Applications for this electroformed material include fabrication of complex or re-entry shapes which would be difficult or impossible to form from high strength alloys such as INCONEL 718.
Developing coordination complexes of earth abundant metals that can perform substrate oxidations under benign conditions is an ongoing challenge. Here, the reactivity of two mononuclear Cu-complexes toward the oxidant H 2 O 2 is reported. Both complexes displayed ligand oxidation upon reaction with the oxidant. Analysis of spectroscopic data established that the respective product complexes contained mononuclear Cu(II) centers. Moreover, treatment of these Cu-complexes with oxidant in the presence of substrate resulted in the interception of ligand oxidation with preferential oxidation of the substrate. Computational studies identified plausible mechanistic pathways, suggesting a copper-oxyl intermediate as the likely reactive intermediate responsible for substrate and ligand oxidation. To our knowledge, this is the first Cu-mediated system that showed ligand oxidation, oxo-transfer capability, and external hydrocarbon oxidation under stoichiometric conditions.
The goal is to achieve a comprehensive understanding of the nature, mechanism of function and biogenesis of c-type cytochromes and their oligomeric complexes. These cytochrome are ubiquitous heme proteins that are required for cellular bioenergetics, including photosynthesis (Ps) and respiration (Res), which are central to chemical energy (ATP) production by oxidative- and photophosphorylation. We contribute to the molecular characterization of individual and membrane-integral cytochromes as parts of Ps and Res electron transport (ET) pathways, using the facultative phototrophic bacteria of as excellent models for multidisciplinary investigations. Supported by this grant we discovered novel membrane-bound cytochromes and cyts c complexes that are important for Ps- and Res-ET. We worked out their biogenesis including maturation (covalent heme addition) and assembly of mature subunits into complexes. These involve fundamental process found virtually in all organisms and are fundamental processes with major significance to the “Photosynthetic Systems” program of DOE-BES, because the cytochromes are integral components of natural energy production systems. Elucidation of basic principles, and the knowledge gained by their study greatly impact on our ability to design, engineer, and create new natural, bio-hybrid, bio-inspired and artificial systems to better capture light, transduce and store its energy with improved efficacy and are of broad significance.
In this work, we demonstrate a two-phase capillary-fed boiling micro-cooler that consists of a ~ 25-..mu..m-thick copper inverse opal (CIO) porous wicking structure for high-heat-flux boiling and a silicon 3D-manifold for distributed liquid delivery and vapor extraction across a 0.5 cm x 0.5 cm heated area. At low inlet water mass flow rates of 1.5 to 1.9 g(min)-1, the micro-cooler displays nearly two-phase boiling with exit vapor quality ~ 1 and a high critical heat flux (CHF) of 253 to 320 W cm-2 with low superheat of ~ 10 degrees C resulting in a thermal resistance of boiling ~ 0.025 cm2 degrees C W-1 or heat transfer coefficient of 0.4 MW m-2 degrees C-1. For higher flow rates of 5, 10, and 15 g(min)-1, the micro-cooler exhibits a hybrid single-phase and two-phase cooling regime where the contribution of the sensible heat (single-phase) cooling is linearly added to that of the two-phase cooling. For the highest flow rate of 15 g(min)-1, the CHF is increased to ~ 500 W cm-2 resulting in an overall thermal resistance of ~ 0.18 cm2 degrees C W-1. However, the two-phase heat transfer effectiveness, which estimates the utilization level of the inlet mass flow rate for two-phase boiling, is reduced to ~ 0.11. To achieve the best cooling system performances, the micro-cooler must operate entirely within the two-phase boiling regime (exit vapor quality or two-phase heat transfer effectiveness ~ 1). Ideally, the "coolant" should be delivered near its saturation temperature (~ 100 degrees C for water), which provides significant advantages for the energy-efficient operation of data centers and power electronics. We present detailed analysis with Infrared and high speed camera images at various inlet flow rates and heat fluxes to understand complex heat transfer in the micro-cooler. Furthermore, a conjugate thermofluidic simulation model, which incorporates the physics of capillary-fed boiling in a porous copper layer, agrees well with the experimental data.
In this paper an investigation into the effect of transition metal ion and selenate/fluorophosphate doping on the structures of Na{sub 2}M(SO{sub 4}){sub 2}·2H{sub 2}O (M=transition metal) materials is reported. In agreement with previous reports, the monoclinic (Kröhnkite) structure is adopted for M=Mn, Fe, Co, Cu, while for the smallest first row divalent transition metal ion, M=Ni, the triclinic (Fairfieldite structure) is adopted. On selenate doping there is a changeover in structure from monoclinic to triclinic for M=Fe, Co, Cu, with the larger Fe{sup 2+} system requiring the highest level of selenate to complete the changeover. Thus the results suggest that the relative stability of the two structure types is influenced by the relative size of the transition metal: oxoanion group, with the triclinic structure favoured for small transition metals/large oxoanions. The successful synthesis of fluorophosphate doped samples, Na{sub 2}M(SO{sub 4}){sub 2−x}(PO{sub 3}F){sub x}·2H{sub 2}O was also obtained for M=Fe, Co, Cu, with the results showing a changeover in structure from monoclinic to triclinic for M=Co, Cu for very low levels (x=0.1) of fluorophosphate. In the case of M=Fe, the successful synthesis of fluorophosphates samples was achieved for x≤0.3, although no change in cell symmetry was observed. Rather in this particular case, the X-ray diffraction patterns showed evidence for selective peak broadening, attributed to local disorder as a result of the fluorophosphate group disrupting the H-bonding network. Overall the work highlights how isovalent doping can be exploited to alter the structures of Na{sub 2}M(SO{sub 4}){sub 2}·2H{sub 2}O systems. - Graphical abstract: Partial substitution of sulfate in Na{sub 2}M(SO{sub 4}){sub 2}0.2H{sub 2}O (M=Co, Cu) by selenate or fluorophosphate leads to a structural change from the monoclinic Kröhnkite to the triclinic Fairfieldite structure. - Highlights: • The successful synthesis of Na{sub 2}M(SO{sub 4}){sub 2}·2H{sub 2}O (M=transition metal) phases doped with selenate and fluorophosphate. • A change in structure is observed on selenate doping for M=Fe, Co, Cu. • This change in structure is also observed on fluorophosphate doping for M=Co, Cu. • The work highlights how isovalent doping can be exploited to alter the structures of Na{sub 2}M(SO{sub 4}){sub 2}·2H{sub 2}O systems.
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MnO 2 is one of the safest and most abundant electrochemical materials available. It exhibits polymorphism, which has been exploited in many applications especially batteries. In alkaline batteries, γ-MnO 2 is widely used because its proton insertion reaction yields one e - (1st) per Mn at high voltages. It also gives a second (2nd) e - during dissolution-precipitation reactions that occur at lower voltages than the proton insertion; however, these 2nd e - reactions are highly irreversible. Here in this communication, here we explore the reversibility of the 2nd e - reactions with bismuth oxide (Bi 2 O 3 ) and copper (Cu) additives, and cycling in specific potential regions where δ-MnO 2 is the polymorph synthesized electrochemically in-situ from γ-MnO 2 . The use of Bi 2 O 3 and Cu add complexation and intercalation reactions, where presence and/or electrochemical activation of both are essential for reversibility and for capacity retention (50–100%). Attaining 300–610Wh kg -1 against a zinc anode is possible for these batteries, which could promote its use for many applications.
Methanobactins (Mbns), copper-binding peptidic compounds produced by some bacteria, are candidate therapeutics for human diseases of copper overload. The paired oxazolone-thioamide bidentate ligands of methanobactins are generated from cysteine residues in a precursor peptide, MbnA, by the MbnBC enzyme complex. MbnBC activity depends on the presence of iron and oxygen, but the catalytically active form has not been identified. Here, we provide evidence that a dinuclear Fe(II)Fe(III) center in MbnB, which is the only representative of a >13,000-member protein family to be characterized, is responsible for this reaction. These findings expand the known roles of diiron enzymes in biology and set the stage for mechanistic understanding, and ultimately engineering, of the MbnBC biosynthetic complex.
The crystalline structure of intermetallic Cu{sub 3}Sn synthesized by successively condensing thin layers of copper and tin on a substrate at 150°C has been studied. Cu{sub 3}Sn compound exists in a very narrow homogeneity range and has a long-period close-packed ordered D0{sub 19} superstructure. It has been found that the crystal lattice exhibits many slip traces associated with dislocation motion. The dislocation motion is due to the stressed state of the crystal, which can be characterized as uniform extension. Electron micrographs show that slip traces in the Cu{sub 3}Sn crystal are parallel to the ( 1-bar 1-bar 21) and (11 2-bar 1) planes belonging to pyramidal slip system II, which is a main slip system along with pyramidal and basal ones. Slip traces result from the motion of partial dislocations, as indicated by the amount of slip, which is equal to half the interplanar distance. Since the crystal is ordered, slip is accomplished by a pair of superpartial dislocations and a slip trace may be a superstructural or complex stacking fault.
Microparticle hydrodynamic penetration (HDP) may be associated with the erosion regime in cold spray processing and other high-velocity impact events. Here, in an experimental approach where we can individually launch particles and study the impact sites, we explore copper microparticles impacted on copper substrates at velocities above 900 m/s where HDP begins. We lift cross-sectional lamellae from the impact sites with a focused-ion beam for further microstructural characterization using electron backscatter diffraction and scanning transmission electron microscopy. Due to the gradients of strain, strain rate, and temperature associated with HDP, heterogeneous microstructures result. The structural evolution processes observed include deformation twinning and multiple dislocation-mediated grain recrystallization mechanisms—geometric dynamic recrystallization (gDRX), discontinuous DRX (dDRX), and meta DRX (mDRX). The higher strains at the interface lead to the most significant structural changes and complex mechanisms. In contrast, there is a gradient to more conventional dislocation plasticity away from the interface (on either the particle or substrate side). Here, these microstructural observations are consistent with the deformation map for copper and extend the observations of impact-induced recrystallization across new regimes of behavior.
The practical implementation of Li metal batteries is hindered by difficulties in controlling the Li metal plating microstructure. While previous atomic layer deposition (ALD) studies have focused on directly coating Li metal with thin films for the passivation of the electrode–electrolyte interface, a different approach is adopted, situating the ALD film beneath Li metal and directly on the copper current collector. Here, a mechanistic explanation for this simple strategy of controlling the Li metal plating microstructure using TiO 2 grown on copper foil by ALD is presented. In contrast to previous studies where ALD-grown layers act as artificial interphases, this TiO 2 layer resides at the copper–Li metal interface, acting as a nucleation layer to improve the Li metal plating morphology. Upon lithiation of TiO 2 , a Li x TiO 2 complex forms; this alloy provides a lithiophilic surface layer that enables uniform and reversible Li plating. The reversibility of lithium deposition is evident from the champion cell (5 nm TiO 2 ), which displays an average Coulombic efficiency (CE) of 96% after 150 cycles at a moderate current density of 1 mA cm –2 . This simple approach provides the first account of the mechanism of ALD-derived Li nucleation control and suggests new possibilities for future ALD-synthesized nucleation layers.
The author has identified the following significant results. Three major tectonic provinces have been mapped by geologic photointerpretation of ERTS-1 imagery over the Ok Tedi test site. These areas can be characterized as follows: (1) A broad area of low relief and mature topography suggesting a history of relative tectonic stability. (2) A narrow belt of moderate to high relief, broad open folds and prominent linear features. The Mount Fubilan-type porphyry copper deposits and recent volcanic effusive centers occur in this province. (3) A heterogeneous zone of high relief and high drainage density suggestive of relative structural complexity.
High pressure can profoundly affect the electronic structure and reactivity, creating compounds between elements that do not react at ambient conditions. Lithium is known to react with gold and silver; however, no copper compounds are known to date. Here, by compressing mixtures of the elements in diamond-anvil cells, compounds of lithium and copper have been synthesized and characterized by X-ray diffraction for the first time. Pressures as low as 1 GPa lead to the formation of a complex layered phase LiCu, displaying two-dimensional kagomé lattice layers of Cu atoms. With increasing pressure, the layered Cu–Cu bonding is replaced by linear chains of Cu atoms in the high-pressure phase Li 2 Cu. Here we show the powerful effects of even modest pressures on the reactivity of lithium, leading to structures of remarkable complexity and low-dimensional transition metal bonding.
Recent experimental studies in the ZnO-“FeO”-SiO{sub 2} system in reducing atmosphere demonstrated significant discrepancies with the current FactSage thermodynamic model developed using previous experimental data in this system in equilibrium with metallic iron and air. The present experimental study on phase equilibria in the ZnO-“FeO”-SiO{sub 2}-“Cu{sub 2}O” system in equilibrium with liquid copper at 1250 °C (1523 K) at low copper oxide concentrations in slag was initiated and undertaken to resolve these discrepancies. A high-temperature equilibration–rapid quenching–electron-probe X-ray microanalysis (EPMA) technique using a primary phase substrate support and closed system approach with Cu metal introduced to determine effective equilibrium oxygen partial pressure from the Cu{sub metal}/Cu{sub 2}O{sub slag} equilibria was applied to provide accurate information on the liquidus and corresponding solid compositions in the spinel, willemite, and tridymite primary phase fields. The present results confirmed the accuracy of the FactSage model, resolved discrepancies, and demonstrated significant uncertainties in the recent studies by other authors on the system in the open reducing atmosphere. The present study shows how this closed system approach can be used to obtain key thermodynamic data on phase equilibria in systems containing volatile metal species, overcoming the limitations and uncertainties encountered in conventional open gas/condensed phase equilibration with these systems. The study highlights the importance of the focus on obtaining accurate experimental data and the risks of misleading information from inadequate experimental control and analysis. The study also demonstrates that continuing in-depth critical review and analysis of the elemental reactions taking place in complex systems is an essential step in phase equilibrium research.
Lubricating materials for use in a vacuum environment have been the subject of a series of experimental investigations. Evaporation properties were evaluated for solid polymeric compositions. Friction and wear studies explored the behavior during sliding contact for series of polymeric compositions, binary alloys containing soft film-forming phases, complex alloys with film-forming materials, and a burnished MoS2 film. Friction and wear experiments were conducted at 10(exp-9)mm Hg with a 3/16-inch-radius-hemisphere rider specimen sliding on the flat surface of a rotating 2-1/2-inch-diameter disk specimen with materials that had low rates of evaporation. The influence of fillers in polytetrafluoroethylene (PTFE) on decomposition during vacuum friction studies was determined with a mass spectrometer. A real advantage in reducing decomposition and improving friction wear properties is gained by adding fillers (e.g., copper) that improve thermal conductivity through the composite materials. A polyimide and an epoxy-MoS2 composition material were found to have better friction and wear properties than PTFE compositions. A series of alloys (cast binary as well as more complex alloys) that contained microinclusions of potential film-forming material was studied. These materials replaced the normal surface oxides as they were worn away on sliding contact. Iron sulfide, nickel oxide, and tin are typical film-forming materials employed and were demonstrated to be effective in inhibiting surface welding and reducing friction. A burnished MoS2 film applied to type 440-C stainless steel in argon with a rotating soft wire brush had good endurance properties but somewhat higher friction than commercially available bonded films. An oil film applied to the burnished MoS2 markedly reduced its endurance life.
Targeted radionuclide therapy generally relies on the chelation of select short-lived isotopes such as 177 Lu and 67 Cu. The majority of Lu(III) and Cu(II) chelate structural information is derived from solid state diffraction data. Herein, the complexes Lu(DOTA) - , Cu(NOTA) - were examined in solution using EXAFS for the first time. Both ligands were fully deprotonated and coordinated to the metal with four and three carboxylic sites for Lu(DOTA) - and Cu(NOTA) - , respectively. Near-neighbor correlations from nitrogen atoms on the macrocyclic cages were also visible in the spectra in addition to the adjacent carbon backbones. Coordination numbers, bond distances, and Debye-Waller factors are reported and discussed alongside differences with known crystal structures.