An EXAFS study of the cobalt-molybdenum/.gamma.-alumina hydrodesulfurization catalyst

While Mo in the Co-Mo/y-A1203 hydrodesulfurization catalyst is present as a sulfidic species similar to MoS2, Co shows two types of coordination, one with six sulfurs (but not a bulk sulfide) and the other with four oxygens. The significance of such species is discussed. In addition to an additive relation of the EXAFS function and the residual spectra, the ratio of amplitude terms of the catalyst and the model system has been employed in the analysis.

Microemulsion-mediated synthesis of cobalt (pure fcc and hexagonal phases) and cobalt-nickel alloy nanoparticles

By choosing appropriate microemulsion systems, hexagonal cobalt (Co) and cobalt-nickel (1:1) alloy nanoparticles have been obtained with cetyltrimethylammonium bromide as a cationic surfactant at 500 degrees C. This method thus stabilizes the hcp cobalt even at sizes (<10 nm) at which normally fcc cobalt is predicted to be stable. On annealing the hcp cobalt nanoparticles in H-2 at 700 degrees C we could transform them to fcc cobalt nanoparticles. Microscopy studies show the formation of spherical nanoparticles of hexagonal and cubic forms of cobalt and Co-Ni (1:1) alloy nanoparticles with the average size of 4, 8 and 20 nm, respectively. Electrochemical studies show that the catalytic property towards oxygen evolution is dependent on the applied voltage. At low voltage (less than 0.65 V) the Co (hexagonal) nanoparticles are superior to the alloy (Co-Ni) nanoparticles while above this voltage the alloy nanoparticles are more efficient catalysts. The nanoparticles of cobalt (hcp and fcc) and alloy (Co-Ni) nanoparticles show ferromagnetism. The saturation magnetization of Co-Ni nanoparticles is reduced compared to the bulk possibly due to surface oxidation.

Quasi Crystalline A1-Mn Alloys: Pressure Induced Crystallization and Structural Studies

Irreversible, Pressure induced, quasicrystal-to-crystal transitions are observed for the first time in melt spun alloys at 4.9 GPa for Al 78 Mn22 and 9.3 GPa for Al86 Mn14 by monitoring the electrical resistivities of these alloys as a function of pressure. Electron diffraction and x-ray measurements are used to show that these quasicrystalline phases have icosohedral point group symmetry. The crystalline phases which appear at high pressures are identified as h.c.p. for Al78 Mn22 and orthorhombic for Al86 Mn14.

Adsorption Of Methanol On The Surfaces Of Copper-Alloys - Ups And Eels Studies

Methanol adsorbs molecularly on the surfaces of Cu–Pd alloys at low temperatures and transforms to CH3O or CO on warming, depending upon the alloy composition. On oxygen presorbed Cu–Pd alloy surfaces, adsorption of methanol gives rise to H2O and H2CO. CH3OH adsorbed molecularly on the surfaces of Cu–Au alloys and CH3O is formed only at relatively high temperatures.

Role of alloys in the thermal decomposition and combustion of ammonium perchlorate

The participation of aluminum in the decomposition reaction of ammonium perchlorate (AP) is enhanced if magnesium is added—either as a mixture of Al and Mg powders or as an alloy of Mg in Al. The differential thermal analyses of the compositions show a sensitization in the temperatures of decomposition, as well as increase in the heat of reaction. The AP-Mg and Ap-(Mg---Li) alloy pellets also show increased reactivity. The burning rates of AP-(Al-10% Mg) alloy pellets increase with increase in the alloy content, while calorimetric values peak at 40% alloy content. The combustion product gases of AP-40% (Al-10% Mg) alloy contain large quantities of hydrogen.

The effect of rapid solidification on the order-disorder transformation in iron-based alloys

The effect of rapid solidification on the ordering reaction in Fe---Si and Fe---Al alloys has been reported. It is shown that rapid solidification can influence the ordering reaction in alloys with higher critical ordering temperatures. For ordering reactions at lower temperatures, the effect is similar to that of solid-state quenching. Different factors influencing the ordering reactions and domain structures during rapid solidification of iron-based alloys are discussed.

Surface segregation and oxidation studies of Cu-Sn and Cu-Pd alloys by x-ray photoelectron and auger spectroscopy

X-ray photoelectron and Auger spectroscopic techniques have been employed to study surface segregation and oxidation of Cu-1 at%Sn, Cu-9at%Pd and Cu-25at%Pd alloys. Both Cu-Pd(9%) and Cu-Pd(25%) alloys show segregation of Cu when heated above 500 K. The Pd concentration was reduced by 50% at 750 K compared to the bulk composition; the enthalpy of segregation of Cu is around - 6kJ/mol. Sn segregation is seen from 470 to 650 K in the Cu-Sn(1%) alloy, and a saturation plateau of Sn concentration above 650 K is observed. Surface oxidation of Cu-Sn(1%) and Cu-Pd(9%) alloys at 500 K showed the formation of Cu2O on the surface with total suppression of Sn or Pd on the respective alloy surfaces. On vacuum annealing the oxidised Cu-Sn alloy surface at 550 K, a displacement reaction 2Cu2O+Sn→4Cu+SnO2 was observed. However, under similar annealing of the oxidised Cu-Pd(9%) alloy surface at 500 K, oxide oxygen was totally desorbed leaving the Cu-Pd alloy surface clean. In the case of the Cu-Pd(25%) alloy, only dissociatively chemisorbed oxygen was seen at 500 K which desorbed at the same temperature. Oxygen spill-over from copper to palladium is suggested as the mechanism of oxygen desorption from the oxidised Cu-Pd alloy surfaces.

X-ray photoelectron spectra and Auger studies of the surface oxidation of cobalt

Surface oxidation of Co has been investigated at different temperatures in the 300–600 K range at oxygen exposures upto 106 L by XPES and AES techniques. In the XPES, both the valence band and core level bands have been employed to monitor the oxidation while in the AES, metal Auger intensity ratios as well as O(KLL)/Co(L23M45M45) ratios have been examined. Only CoO is formed on the surface at high oxygen exposures at and above 500 K.

Sensing Shape Recovery Using Conductivity Noise in Thin Films of NiTi Shape Memory Alloys

Low frequency fluctuations in the electrical resistivity, or noise, have been used as a sensitive tool to probe into the temperature driven martensite transition in dc magnetron sputtered thin films of nickel titanium shape-memory alloys. Even in the equilibrium or static case, the noise magnitude was more than nine orders of magnitude larger than conventional metallic thin films and had a characteristic dependence on temperature. We observe that the noise while the temperature is being ramped is far larger as compared to the equilibrium noise indicating the sensitivity of electrical resistivity to the nucleation and propagation of domains during the shape recovery. Further, the higher order statistics suggests the existence of long range correlations during the transition. This new characterization is based on the kinetics of disorder in the system and separate from existing techniques and can be integrated to many device applications of shape memory alloys for in-situ shape recovery sensing.

Ternary metal complexes of anionic and neutral pyridoxine (vitamin B6) with 2,2'-bipyridine. Syntheses and x-ray structures of (pyridoxinato)bis(2,2'-bipyridyl)cobalt(III) perchlorate and chloro(2,2'-bipyridyl)(pyridoxine)copper(II) perchlorate hydrate

Ternary metal complexes involving vitamin B6 with formulas [CO",(PN-H)](anCdI [OC)'(bpy)(PN)Cl]C10(.bpHy 0 = 2,2'-bipyridine, PN = neutral pyridoxine, PN-H = anionic pyridoxine) have been prepared for the first time and characterized by means of magnetic and spectroscopic measurements. The crystal structures of the compounds have also been determined. [CO(PN-H)](CcryIsOta,l)lize s in the space group P2,/c with a = 18.900 (3) A, b = 8.764 (1) A, c = 20.041 (2) A,p = 116.05 (l)', and Z = 4 and [Cu(bpy)(PN)C1]C104-H20in the space group Pi with a = 12.136 (5) A, b = 13.283 (4) A,c = 7.195 (2) A, a = 96.91 (Z)', 0 = 91.25 (3)', y = 71.63 (3)', and Z = 2. The structures were solved by the heavy-atom method and refined by least-squares techniques to R values of 0.080 and 0.042 for 3401 and 2094 independent reflections, respectively. Both structures consist of monomeric units. The geometry around Co(II1) is octahedral and around Cu(I1) is distorted square pyramidal. In [CO(PN-H)]t(wCo IoxOy~ge)n~s ,fro m phenolic and 4-(hydroxymethyl) groups of PN-H and two nitrogens from each of two bpy's form the coordination sphere. In [Cu(bpy)(PN)C1]C104.H20o ne PN and one bpy, with the same donor sites, act as bidentate chelates in the basal plane, with a chloride ion occupying the apical position. In both structures PN and PN-H exist in the tautomeric form wherein pyridine N is protonated and phenolic 0 is deprotonated. However, a novel feature of the cobalt compound is that PN-H is anionic due to the deprotonation of the 4-(hydroxymethyl) group. The packing in both structures is governed by hydrogen bonds, and in the copper compound partial stacking of bpy's at a distance of -3.55 also adds to the stability of the system. Infrared, NMR, and ligand field spectroscopic results and magnetic measurements are interpreted in light of the structures.

Mixed ligand complexes in vinyl polymerization-II: [NN-ethylenebis(salicylideneiminato)] (benzoylacetonato)cobalt(III) as an initiator

The polymerization of methyl methacrylate initiated by a mixed ligand complex. [NN-ethylenebis(salicylideneiminato)](benzoylacetonato)cobalt(III) has been studied in bulk and in benzene at 70° and 80°. The rate of polymerization is proportional to (concentration of the chelate)Image and the monomer exponent is close to 1.5. The activation energy and the kinetic and transfer constants are evaluated. A free radical mechanism has been proposed.

Structure-thermal behaviour studies on the salicylato complex of cobalt

The salicylato complex of cobalt was synthesized and its structure established to be [Co(sal)2] · 4 H2O, where, sal =, from elemental analysis, IR spectroscopy, magnetic susceptibility, cryoscopy and conductivity. The X-ray diffractogram of the complex has been given. Thermal decomposition has been studied in air by thermogravimetry (TG), differential thermal analysis and differential scanning calorimetry. TG shows three main steps of decomposition. The intermediates formed at various stages were collected and analysed. From the TG results and chemical analysis of the intermediates, a mechanism has been proposed for the thermal decomposition of the complex, leading to the oxide formation in the final stage.

Interaction of Metal Ions with 2'-Deoxyribonucleotides. Crystal and Molecular Structure of a Cobalt(l1) Complex with 2'-Deoxyinosine 5'-Monophosphate

The crystal structure of the cobalt( 11) complex with 2'-deoxyinosine 5'-monophosphate (5'- dlMP), [Co(5'-dlMP) (H,0),]-2H20, has been analysed by X-ray diffraction. The complex crystallizes in the space group P2,2,2, with a = 6.877(3), b = 10.904(2), c = 25.421 (6) A, and Z = 4. The structure was solved by the heavy-atom method and refined to an R value of 0.043 using 1 776 unique reflections. The cobalt ion binds only to the 6-oxopurine base of the nucleotide at the N(7) position, the octahedral co-ordination of the metal being completed by five water oxygens. The phosphate oxygens are involved in hydrogen bonding with the co-ordinated water molecules. The structure is closely similar to that of the corresponding ribonucleotide complex. The nucleotide has the energetically preferred conformation: an anti base, a C(3') -endo sugar pucker, and a gauche-gauche conformation about the C(4')-C( 5') bond. The significance of sugar puckering in the monomeric complexes of general formula [ M (5'-nucleotide) (H20),] is explained in terms of the structural requirements for metal-water-phosphate bridging interactions.

Ultrasonic velocities and thermal expansion coefficients of amorphous Se80Te20 and Se90Te10 alloys near glass transitions

Precise measurements of the ultrasonic velocities and thermal expansivities of amorphous Se80Te20 and Se90Te10 alloys are reported near the glass transition. The samples are produced by liquid quenching. The longitudinal and transverse velocities are measured at 10 MHz frequency using the McSkimin pulse superposition technique. The thermal expansivities,agr, are measured using a three-terminal capacitance bridge. Theagr-values show a sharp maximum near the glass transition temperature,T g. The ultrasonic velocities also show a large temperature derivative, dV/dT nearT g. The data are discussed in terms of existing theories of the glass transition. The continuous change inagr shows that the glass transition is not a first-order transition, as suggested by some theories. The samples are found to be deformed by small loads nearT g. The ultrasonic velocities and dV/dT have contributions arising from this deformation.