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The objectives of this work were to measure the superconductivity and critical fields of (Cu1.5Mo4.5), (SmMo5S6), and (Pb0.9Mo5.1S6) in order to reproduce the published results, and by introduction of magnetic impurities into these semiconductors, observe the compensation effect.
The cyclopentadienyl molybdenum hydride compounds, Cp R Mo(PMe 3 ) 3-x (CO) x H (Cp R = Cp, Cp*; x = 0, 1, 2 or 3), are catalysts for the dehydrogenation of formic acid, with the most active catalysts having the composition Cp R Mo(PMe 3 ) 2 (CO)H. The mechanism of the catalytic cycle is proposed to involve (i) protonation of the molybdenum hydride complex, (ii) elimination of H 2 and coordination of formate, and (iii) decarboxylation of the formate ligand to regenerate the hydride species. NMR spectroscopy indicates that the nature of the resting state depends on the composition of the catalyst. For example, (i) the resting states for the CpMo(CO) 3 H and CpMo(PMe 3 )(CO) 2 H systems are the hydride complexes themselves, (ii) the resting state for the CpMo(PMe 3 ) 3 H system is the protonated species [CpMo(PMe 3 ) 3 H 2 ] + , and (iii) the resting state for the CpMo(PMe 3 ) 2 (CO)H system is the formate complex, CpMo(PMe 3 ) 2 (CO)(κ 1 -O 2 CH), in the presence of a high concentration of formic acid, but CpMo(PMe 3 ) 2 (CO)H when the concentration of acid is low. While CO 2 and H 2 are the principal products of the catalytic reaction induced by Cp R Mo(PMe 3 ) 3-x (CO) x H, methanol and methyl formate are also observed. The generation of methanol is a consequence of disproportionation of formic acid, while methyl formate is a product of subsequent esterification. The disproportionation of formic acid is a manifestation of a transfer hydrogenation reaction, which may also be applied to the reduction of aldehydes and ketones. Thus, CpMo(CO) 3 H also catalyzes the reduction of a variety of ketones and aldehydes to alcohols by formic acid, via a mechanism that involves ionic hydrogenation.
The radionuclide {sup 99}Mo was produced and separated in the process of irradiating powdered mixtures of molybdenum compounds and buffer particles by 30 MeV protons. The separation is based on the Szilard–Chalmers effect wherein {sup 99}Mo recoil particles are fixed in inert buffer particles. Two types of targets were investigated by using mixtures: soluble molybdenum compound–insoluble buffer and insoluble molybdenum compound–soluble buffer. {sup 99}Mo yield equal to 20% with enrichment coefficient 18.3 was obtained by using a target consisting of a mixture of submicron {sup 100}MoO{sub 3} and Al{sub 2}O{sub 3} particles; the {sup 99}Mo yield was equal to 20% and the enrichment coefficient 18.3. For a target with the composition {sup 100}MoS{sub 2} + KCl, making it possible to separate {sup 99}Mo recoil atoms directly into solution, the {sup 99}Mo yield was equal to 8.7% and the enrichment coefficient 30.7.
Process impregnates polytetrafluoroethylene /PTFE/ with rhenium or molybdenum compounds. The refractory metals impregnated PTFE combines chemical inertness with electrical conductivity. They are useful for electro-chemical cells, chemical processing equipment, catalysts, electrostatic charge removal, RF gasketing, and cable shielding.
In this study, non-fluorescent cationic extreme pressure lubricant JDLUB-1 was prepared to improve the lubricity for extended reach well drilling. The lubricant was mainly composed of synthetic base oil, oil-soluble and spherical nano-silica, sulfur-phosphorus-molybdenum anti-friction and anti-extreme pressure additives. The mixture was emulsified with primary emulsifier cycloalkane group condensed fatty amines and a fatty alcohol polyoxyethylene ether co-emulsifier. The fluorescence level did not exceed 4, satisfying the standard requirements. The properties including extreme pressure lubrication, temperature resistance and compatibility with conventional drilling fluid additives were evaluated. The results indicated that the extreme pressure lubricity coefficient could reach 0.0283 after addition of JDLUB-1. Meanwhile, the product was stable at high temperature of 130 °C, and compatible with common additives. The lubricity mechanism of JDLUB-1 was investigated by measuring the zeta potential, particle size distribution, adsorption, and anti-wear evaluation at extreme pressure. The results indicated that the positively charged lubricant oil droplets could be actively adsorbed onto the surface of N80 steel casing coupon. An adsorption film composed of oil soluble and spherical nano-silica and sulfur-phosphorus-molybdenum compounds was formed with a low melting point and low shear strength. During friction, the formation of molybdenum disulfide film leads to repair of the metal surface and formation of a stable sliding friction between the drill string and the wellbore with a low friction coefficient. The JDLUB-1 lubricant was successfully applied in several high-angle deviated wells and extended reach wells in Jidong oilfield (China). The results demonstrated that JDLUB-1 could effectively reduce torque and drag and show potential field application in the future.
A practical two-stage reactive grinding-assisted pathway waste-free and cost-effective for the synthesis of NiMoO{sub 4} has been successfully developed. It was demonstrated that proper design in synthetic strategy for grinding plays a crucial role in determining the ultimate polymorph of NiMoO{sub 4}. Specifically, direct grinding (DG) of MoO{sub 3} and NiO rendered {alpha}-NiMoO{sub 4} after annealing, whereas sequential grinding (SG) of the two independently pre-ground oxides followed by annealing generated {beta}-NiMoO{sub 4} solid solution. Characterizations in terms of Raman and X-ray diffraction suggest the creation of {beta}-NiMoO{sub 4} precursor in the latter alternative is the key aspect for the formation of {beta}-NiMoO{sub 4}. The DG-derived {alpha}-NiMoO{sub 4} tested by oxidative dehydrogenation of propane exhibited superior activity in contrast to its analog synthesized via conventional coprecipitation. It is suggested that the favorable chemical composition facilely obtained via grinding in contrast to that by coprecipitation was essential for achieving a more selective production of propylene. - Graphical Abstract: Grinding-assisted synthesis of NiMoO{sub 4} offers higher and more reproducible activities in contrast to coprecipitation for oxidative dehydrogenation of propane, and both {alpha}- and {beta}-NiMoO{sub 4} can be synthesized. Highlights: Black-Right-Pointing-Pointer NiMoO{sub 4} was prepared through grinding-assisted pathway. Black-Right-Pointing-Pointer Direct/sequential grinding rendered {alpha}-, {beta}-NiMoO{sub 4}, respectively. Black-Right-Pointing-Pointer Grinding-derived {alpha}-NiMoO{sub 4} showed high and reproducible activity for oxidative dehydrogenation of propane.
The electronic structures at the MoO{sub 3}/Co interface were investigated using synchrotron-based ultraviolet and x-ray photoelectron spectroscopy. It was found that interfacial chemical reactions lead to the reduction of Mo oxidation states and the formation of Co-O bonds. These interfacial chemical reactions also induce a large interface dipole, which significantly increases the work function of the cobalt substrate. In addition, two interface states located at 1.0 and 2.0 eV below the Fermi level are identified. These two states overlap at film thickness of between 2-4 nm, which suggests the MoO{sub 3} intermediate layer may facilitate ohmic charge transport.
Recent searches of gravitational-wave data raise the question of what maximum gravitational-wave energies could be emitted during gamma-ray flares of highly magnetized neutron stars (magnetars). The highest energies ({approx}10{sup 49} erg) predicted so far come from a model [K. Ioka, Mon. Not. R. Astron. Soc. 327, 639 (2001), http://adsabs.harvard.edu/abs/2001MNRAS.327..639I] in which the internal magnetic field of a magnetar experiences a global reconfiguration, changing the hydromagnetic equilibrium structure of the star and tapping the gravitational potential energy without changing the magnetic potential energy. The largest energies in this model assume very special conditions, including a large change in moment of inertia (which was observed in at most one flare), a very high internal magnetic field, and a very soft equation of state. Here we show that energies of 10{sup 48}-10{sup 49} erg are possible under more generic conditions by tapping the magnetic energy, and we note that similar energies may also be available through cracking of exotic solid cores. Current observational limits on gravitational waves from magnetar fundamental modes are just reaching these energies and will beat them in the era of advanced interferometers.
(1− x) Cr{sub 2}O{sub 3}/x MoS{sub 2} (x = 0.25, 0.5, 0.75) were synthesized using the powder solid-state route. The structural, morphological, vibrational, and magnetic properties of the as-prepared MoS{sub 2}/Cr{sub 2}O{sub 3} samples with different Cr{sub 2}O{sub 3} contents have been studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy, Raman spectroscopy, and vibrating sample magnetometry (VSM), respectively. The X-ray diffraction results show the presence of the parent compounds (molybdenum disulfide (MoS{sub 2}) and chromium oxide (Cr{sub 2}O{sub 3})) in addition to a secondary phase corresponding to chromium molybdenite Cr{sub 2}Mo{sub 3}O{sub 12}. Raman and IR spectra were recorded, and the observed modes were analyzed and assigned to different normal modes of vibration. Magnetic characterizations revealed that all the series MoS{sub 2}/Cr{sub 2}O{sub 3} composites possess paramagnetic characteristics both at room temperature and at 30 K. Further, the maximum of magnetization increased with the increase of Cr{sub 2}O{sub 3} content.
As magnetic cooling refrigerant, Ni–Mn–Sn Heusler alloys have gained significant potentials for a wide range of practical applications as compared with other expensive Ga-doped Ni–Mn based Heusler alloys, toxic As and P doped Mn-based alloys and rare-earth elements like Gd-based alloys. Consequently, an inclusive investigation on magnetostructural transition and magnetocaloric features of Ni{sub 43}Mn{sub 47−x}Mo{sub x}Sn{sub 10} alloys is carried out. The alloys are assembled through arc-melting technique and their X-ray diffraction analysis confirms their B{sub 2}-type crystal structure at room temperature. As the Mo contents are increased, the magnetostructural transition temperature increases for a temperature range between Curie temperature of austenite and martensite phases. Obvious metamagnetic behavior and magnetic hysteresis are observed in isothermal magnetization curves, suggesting that the temperature and magnetic field can be used as robust tools for tuning the structural transformation in Heusler alloys. The noticeable magnetocaloric effect suggests that the prepared alloys can be an attractive choice for magnetic refrigeration applications.
Nickel based alloys of the type Hastelloy-N™ are ideal candidate materials for molten salt reactors, as well as for applications such as pressure vessels, due to their excellent resistance to creep, oxidation and corrosion. In this work, the authors have attempted to understand the effects of welding on the morphology, chemistry and crystal structure of the precipitates in the heat affected zone (HAZ) and the weld zone of a Ni–Cr–Mo–Fe–Si alloy similar to Hastelloy-N™ in composition, by using characterization techniques such as scanning and transmission electron microscopy. Two plates of a Ni–Cr–Mo–Fe–Si alloy GH-3535 were welded together using a TiG welding process without filler material to achieve a joint with a curved molten zone with dendritic structure. It is evident that the primary precipitates have melted in the HAZ and re-solidified in a eutectic-like morphology, with a chemistry and crystal structure only slightly different from the pre-existing precipitates, while the surrounding matrix grains remained unmelted, except for the zones immediately adjacent to the precipitates. In the molten zone, the primary precipitates were fully melted and dissolved in the matrix, and there was enrichment of Mo and Si in the dendrite boundaries after solidification, and re-precipitation of the complex carbides/silicides at some grain boundaries and triple points. The nature of the precipitates in the molten zone varied according to the local chemical composition. - Graphical abstract: Display Omitted - Highlights: • Ni-based alloy with Cr, Mo, Si, Fe and C was welded, examined with SEM, EBSD, and TEM. • Original Ni{sub 2}(Mo,Cr){sub 4}(Si,C) carbides changed from equiaxed to lamellar shape in HAZ. • Composition and crystal structure remained almost unchanged in HAZ. • Original carbides changed to lamellar Ni{sub 3}(Mo,Cr){sub 3}(Si,C) in some cases in weld metal. • Precipitates were mostly incoherent, but semi-coherent in some cases in weld metal.
A simple expression is proposed for the band gap narrowing (or shrinkage) in semiconductors using optical absorption measurements of spin coated 1 at. % Ga-doped ZnO (with additional 0–1.5 at. % zinc species) thin films as ΔE{sub BGN} = Bn{sup 1/3} [1 − (n{sub c}/n){sup 1/3}], where B is the fitting parameter, n is carrier concentration, and n{sub c} is the critical density required for shrinkage onset. Its uniqueness lies in not only describing variation of ΔE{sub BGN} correctly but also allowing deduction of n{sub c} automatically for several M-doped ZnO (M: Ga, Al, In, B, Mo) systems. The physical significance of the term [1 − (n{sub c}/n){sup 1/3}] is discussed in terms of carrier separation.
We present the characteristics of superconducting nanowire single photon detectors (SNSPDs) fabricated from amorphous Mo{sub 0.75}Ge{sub 0.25} thin-films. Fabricated devices show a saturation of the internal detection efficiency at temperatures below 1 K, with system dark count rates below 500 cps. Operation in a closed-cycle cryocooler at 2.5 K is possible with system detection efficiencies exceeding 20% for SNSPDs which have not been optimized for high detection efficiency. Jitter is observed to vary between 69 ps at 250 mK and 187 ps at 2.5 K using room temperature amplifiers.
The intermetallics compound molybdenum disilicide (MoSi2) is an attractive high-temperature structural material for advanced engine applications. It has excellent oxidation resistance, a high melting point, relatively low density, and high thermal conductivity, and it is easily machined. Past research'at the NASA Lewis Research Center has resulted in the development of a hybrid composite consisting of a MoSi2 matrix reinforced with silicon nitride (Si3N4) Particulate and silicon carbide (SiC) fibers. This composite has demonstrated attractive strength, toughness, thermal fatigue, and oxidation resistance, including resistance to "pest" oxidation. These properties attracted the interest of the Office of Naval Research and Pratt & Whitney, and a joint NASA/Navy/Pratt & Whitney effort was developed to continue to mature the MoSi2 Composite technology. A turbine blade outer air seal, which was part of the Integrated High Performance Turbine Engine Technology (IHPTET) program, was chosen as a first component on which to focus. The first tasks of the materials development effort were to develop improved processing methods to reduce costs and to use fine-diameter fibers that enable the manufacturing of complex shapes. Tape-casting methods were developed to fully infiltrate the fine SiC fibers with matrix powders. The resulting composites were hot pressed to 100-percent density. Composites with cross-plied fiber architectures with 30 vol. % hi-nicalon SiC fibers and 30 vol. % nitride particles are now made routinely and demonstrate a good balance of properties. The next task entailed the measurement of a wide variety of mechanical properties to confirm the suitability of this composite in engines. In particular, participants in this effort demonstrated that composites made with Hi-Nicalon fibers had strength and toughness properties equal to or better than those of the composites made with the large-diameter fibers that had been used previously. Another critically important property measured was impact resistance. Aircraft engine components require sufficient toughness to resist manufacturing defects, assembly damage, stress concentrations at notches, and foreign object damage. Engine company designers indicated that impact resistance would have to be measured before they would seriously consider these types of composites. The Charpy V-notch test was chosen to assess impact resistance, and both monolithic and composite versions Of MOSi2 were tested from -300 to 1400 C. The results (see the following graphs) show that nitride-particulate-reinforced MoSi2 exhibited impact resistance higher than that of many monolithic ceramics and intermetallics, and that the fiber-reinforced composites had even higher values, approaching that of cast superalloys.
The intermetallic compound molybdenum disilicide (MoSi2) is an attractive high-temperature structural material for advanced engine applications. It has excellent oxidation resistance, a high melting point, relatively low density, and high thermal conductivity; and it is easily machined. Past research at the NASA Lewis Research Center has resulted in the development of a hybrid composite consisting of a MoSi2 matrix reinforced with silicon nitride (Si3N4) particulate and silicon carbide (SiC) fibers. This composite has demonstrated attractive strength, toughness, thermal fatigue, and oxidation resistance, including resistance to "pest" oxidation. These properties attracted the interest of the Office of Naval Research and Pratt & Whitney, and a joint NASA/Navy/Pratt & Whitney effort was developed to continue to mature the MoSi2 composite technology. A turbine blade outer air seal, which was part of the Integrated High Performance Turbine Engine Technology (IHPTET) program, was chosen as a first component on which to focus.
The overall objectives the research performed have been to advance the mission of the U. S. Department of Energy, with specific emphasis concerned with the conversion and use of fossil and renewable energy resources, and the synthesis of advanced chemicals. Achieving this objective requires improvements in rational catalyst design by establishing details of reaction mechanisms and their kinetics. Therefore, over the course of this award, emphasis has been directed towards obtaining detailed information concerned with fundamental transformations that occur at metal centers, with particular attention given towards reactions such as (i) hydrodesulfurization (HDS) and hydrodenitrogenation (HDN), (ii) the use of carbon dioxide as a renewable C1 feedstock, (iii) the generation of hydrogen on demand, and (iv) transformations that involve the cleavage of H–H, C–H and C–C bonds. HDS and HDN are the essential processes for removing sulfur- and nitrogen-containing impurities from crude oil in order to obtain (i) cleaner fuels that minimize environmental pollution and (ii) cleaner chemical feedstocks that are less likely to poison the catalysts that are used for subsequent transformations. The catalysts employed for HDS and HDN are typically molybdenum and tungsten sulfides and, to gain insight into these transformations at the molecular level, we have focused on developing the coordination chemistry of heterocyclic sulfur and nitrogen compounds with molybdenum and tungsten. For example, we obtained the first examples of the cleavage of thiophene C–S bonds by employing molecular molybdenum compounds. The efficient utilization of carbon dioxide as a renewable C 1 source for the synthesis of value added organic chemicals and fuels has prompted much effort towards developing catalytic reactions to functionalize CO 2 . One such approach is hydrosilylation, which can proceed in a stepwise manner to afford a series of products with different levels of reduction, namely silyl formates, silyl acetals, methoxy silanes and methane. Despite the utility of these transformations, however, most catalysts employ precious metals, which operate at elevated temperatures, and control of the level of reduction is challenging. Therefore, it is significant that we have developed zinc and magnesium systems that can achieve hydrosilylation of CO 2 and which may be modified to control the level of reduction. The growing demand for energy requires the development of alternative energy sources that are more sustainable than fossil fuels and have a reduced impact on the environment. In this regard, an attractive energy storage medium is provided by hydrogen, which can, for example, be consumed in a fuel cell with only water as a byproduct. Unfortunately, a problem with using hydrogen in this manner is that present storage and transportation techniques are inadequate. For example, not only does storing liquid hydrogen present a safety risk, considerable energy is also required to liquefy the hydrogen and maintain it in this form. Therefore, we have focused on the application of chemical methods to provide hydrogen on demand. One such method utilizes formic acid as a storage medium and we reported the first examples of molybdenum compounds that serve as catalysts for releasing H 2 from formic acid. The nature of the interaction of a C–H bond with a metal center is of pivotal importance in many transformations of organic molecules, and we have examined several systems to probe how the interaction varies according to whether the metal is molybdenum or tungsten. These studies demonstrate that tungsten exhibits a greater propensity to cleave a C–H bond. While the oxidative addition of C–H bonds to a metal center is well precedented, transformations that feature oxidative addition of C–C bonds are uncommon and so it is noteworthy that we have observed the cleavage of a strong C–C bond that is a component of an unstrained 6-membered aromatic ring. The oxidative addition of dihydrogen to a metal center, and its microscopic reverse, reductive elimination, are two of the simplest yet most important transformations in organometallic chemistry. For example, oxidative addition of dihydrogen is a key step in many transition metal-catalyzed reactions involving H 2 . However, relatively few studies have established in detail the factors that influence the thermodynamics of this transformation. Therefore, it is significant that we demonstrated experimentally that that the energetics of the oxidative addition of H 2 to the six coordinate molybdenum and tungsten halide complexes depends very strongly on the nature of both the metal and the halogen. Deuterium kinetic isotope effects (KIEs) and equilibrium isotope effects (EIEs) serve as versatile tools to infer details about reaction mechanisms. In this regard, primary deuterium isotope effects are often interpreted by using two simple guidelines: (i) the KIE for an elementary reaction is normal (k H /k D > 1) and (ii) the EIE is dictated by deuterium preferring to be located in the site corresponding to the highest frequency oscillator. We have evaluated the applicability of these rules to the interactions of H–H and C–H bonds with a transition metal center and our results question the ability to predict primary EIEs in these systems based on the simple notion that deuterium prefers to occupy the highest frequency oscillator. The key findings are that the EIEs for (i) formation of σ–complexes by coordination of H–H and C–H bonds and (ii) oxidative addition of dihydrogen exhibit unusual temperature dependencies, such that the same system may exhibit both normal (i.e. K H /K D > 1) and inverse (i.e. K H /K D < 1) values.
Impregnation of polytetrafluoroethylene with hexaflourides of rhenium, molybdenum, and tungsten