Some mechanisms of tribofilm formation in metal/metal and ceramic/metal sliding interactions

Tribological interaction often generates new structures and materials which form the interface between the sliding pair. The new material designated tribofilm here may be protective or tribologically deleterious. The tribofilm plays a major role in determining the friction and wear of the interaction. Here, we give three examples: mechanically mixed, chemically generated and thermally activated, of tribofilms formed in three different tribological systems and speculate on the mechanism of their formation.

The Role of Tool Design in Influencing the Mechanism for the Formation of Friction Stir Welds in Aluminum Alloy 7020

Design of the required tool is a key and important parameter in the technique of friction stir welding (FSW). This is so because tool design does exert a close control over the quality of the weld. In an attempt to optimize tool design and its selection, it is essential and desirable to understand the mechanisms governing the formation of the weld. In this research study, few experiments were conducted to systematically analyze the intrinsic mechanisms governing the formation of the weld and to effectively utilize the analysis to establish a logical basis for design of the tool. For this purpose, the experiments were conducted using different geometries of the shoulder and pin of the rotating tool in such a way that only tool geometry had an intrinsic influence on formation of the weld. The results revealed that for a particular diameter of the pin there is an optimum diameter of the shoulder. Below this optimum shoulder diameter, the weld does not form while above the optimum diameter the overall symmetry of the weld is lost. Based on experimental results, a mechanism for the formation of friction stir weld is proposed. A synergism of the experimental results with the proposed mechanism is helpful in establishing the set of welding parameters for a given material.

The substrate dependent competitive formation of cyclobutanones and cyclopentanones in an intramolecular rhodium carbenoid CH insertion reaction: enantiospecific total synthesis of silphiperfol-6-ene

The enantiospecific total synthesis of silphiperfol-6-ene has been accomplished starting from the readily available monoterpene (R)-limonene, employing a rhodium carbenoid insertion into the CH bond of a tertiary methyl group. A substrate dependent competitive insertion of the rhodium carbenoid in the gamma- and beta-CH bonds to form cyclopentanone and cyclobutanones, respectively, has been described. (C) 2012 Elsevier Ltd. All rights reserved.

A study on the formation of crystalline phases during solidification and crystallisation in the bulk metallic glass of Zr53Cu21Al10Ni8Ti8 composition

The present paper considers the formation of crystalline phases during solidification and crystallisation of the Zr53Cu21Al10Ni8Ti8 alloy. Solidification was carried out by a copper mould casting technique, which yielded a partially crystalline microstructure comprising a `big cube phase' in a dendritic morphology and a bct Zr2Ni phase. Detailed high-resolution microscopy was carried out to determine possible mechanisms for the formation of the crystalline phases. Based on microstructural examinations, it was established that the dendrites grew by the attachment of atomistic ledges. The bct Zr2Ni phase, formed during solidification and crystallisation, showed various types of faults depending on the crystallite size, and its crystallography was examined in detail. It has been shown that the presence of these faults could be explained by anti-site occupancy in the bct lattice of the Zr2Ni phase.

Dynamics of end-to-end loop formation: A flexible chain in the presence of hydrodynamic interaction

Based on the Wilemski-Fixman approach G. Wilemski, M. Fixman, J. Chem. Phys. 60 (1974) 866], we show that, for a flexible chain in theta solvent, hydrodynamic interaction treated with a pre-averaging approximation makes ring closing faster if the chain is not very short. We also show that the ring closing time for a long chain with hydrodynamic interaction in theta solvent scales with the chain length (N) as N-1.5, in agreement with the previous renormalization group calculation based prediction by Freidman and O'Shaughnessy B. Friedman, B. O'Shaughnessy, Phys. Rev. A 40 (1989) 5950]. (C) 2012 Elsevier B.V. All rights reserved.

Computational investigations on covalent dimerization/oligomerization of polyacenes: Is it relevant to soot formation?

We have postulated a novel pathway that could assist in the nucleation of soot particles through covalent dimerization and oligomerizations of a variety of PAHs. DFT calculations were performed with the objective of obtaining the relative thermal stabilities and formation probabilities of oligomeric species that exploit the facile dimerization that is known to occur in linear oligoacenes. We propose that the presence of small stretches of linear oligoacence (tetracene or longer) in extended PAH, either embedded or tethered, would be adequate for enabling the formation of such dimeric and oligomeric adducts; these could then serve as nuclei for the growth of soot particles. Our studies also reveal the importance of p-stacking interactions between extended aromatic frameworks in governing the relative stabilities of the oligomeric species that are formed. (c) 2012 Wiley Periodicals, Inc.

A touch of history and a peep into the future of the lipid-quinone known as coenzyme Q and ubiquinone

Coenzyme Q (ubiquinone), a fully substituted benzoquinone with polyprenyl side chain, participates in many cellular redox activities. Paradoxically it was discovered only in 1957, albeit being ubiquitous. It required a person, F. L. Crane, a place, Enzyme Institute, Madison, USA, and a time when D. E. Green was directing vigorous research on mitochondria. Located at the transition of 2-electron flavoproteins and 1-electron cytochrome carriers, it facilitates electron transfer through the elegant Q-cycle in mitochondria to reduce O-2 to H2O, and to H2O2, now a significant signal-transducing agent, as a minor activity in shunt pathway (animals) and alternative oxidase (plants). The ability to form Q-radical by losing an electron and a proton was ingeniously used by Mitchell to explain the formation of the proton gradient, considered the core of energy transduction, and also in acidification in vacuoles. Known to be a mobile membrane constituent (microsomes, plasma membrane and Golgi apparatus), allowing it to reach multiple sites, coenzyme Q is expected to have other activities. Coenzyme Q protects circulating lipoproteins being a better lipid antioxidant than even vitamin E. Binding to proteins such as QPS, QPN, QPC and uncoupling protein in mitochondria, QA and QB in the reaction centre in R. sphaeroides, and disulfide bond-forming protein in E. coli (possibly also in Golgi), coenzyme Q acquires selective functions. A characteristic of orally dosed coenzyme Q is its exclusive absorption into the liver, but not the other tissues. This enrichment of Q is accompanied by significant decrease of blood pressure and of serum cholesterol. Inhibition of formation of mevalonate, the common precursor in the branched isoprene pathway, by the minor product, coenzyme Q, decreases the major product, cholesterol. Relaxation of contracted arterial smooth muscle by a side-chain truncated product of coenzyme Q explains its effect of decreasing blood pressure. Extensive clinical studies carried out on oral supplements of coenzyine Q, initially by K. Folkers and Y. Yamamura and followed many others, revealed a large number of beneficial effects, significantly in cardiovascular diseases. Such a variety of effects by this lipid quinone cannot depend on redox activity alone. The fat-soluble vitamins (A, D, E and K) that bear structural relationship with coenzyme Q are known to be active in their polar forms. A vignette of modified forms of coenzyme Q taking active role in its multiple effects is emerging.

Influence of Bottom Bubbling Rate on Formation of Metal Emulsion in Al-Cu Alloy and Molten Salt System

In steel refining process, an increase of interfacial area between the metal and slag through the metal droplets emulsified into the slag, so-called ``metal emulsion'', is one prevailing view for improving the reaction rate. The formation of metal emulsion was experimentally evaluated using Al-Cu alloy as metal phase and chloride salt as slag phase under the bottom bubbling condition. Samples were collected from the center of the salt phase in the container. Large number of metal droplets were separated from the salt by dissolving it into water. The number, surface area, and weight of the droplets increased with the gas flow rate and have local maximum values. The formation and sedimentation rates of metal droplets were estimated using a mathematical model. The formation rate increased with the gas flow rate and has a local maximum value as a function of gas flow rate, while the sedimentation rate is independent of the gas flow rate under the bottom bubbling condition. Three types of formation mode of metal emulsion, which occurred by the rupture of metal film around the bubble, were observed using high speed camera. During the process, an elongated column covered with metal film was observed with the increasing gas flow rate. This elongated column sometimes reached to the top surface of the salt phase. In this case, it is considered that fine droplets were not formed and in consequence, the weight of metal emulsion decreased at higher gas flow rate.

Remarkable photocytotoxicity of curcumin in HeLa cells in visible light and arresting its degradation on oxovanadium(IV) complex formation

Curcumin (Hcur) as a cellular imaging and PDT agent shows remarkable photocytotoxicity in HeLa cells in visible light of 400-700 nm giving IC50 = 8.2 +/- 0.2 mu M and its degradation is arrested on formation of photocytotoxic dipyridophenazine (dppz) complex VO(cur)(dppz)Cl] (IC50 = 3.3 +/- 0.4 mu M), while both are less toxic in the dark.

Potential G-quadruplex formation at breakpoint regions of chromosomal translocations in cancer may explain their fragility

Genetic alterations like point mutations, insertions, deletions, inversions and translocations are frequently found in cancers. Chromosomal translocations are one of the most common genomic aberrations associated with nearly all types of cancers especially leukemia and lymphoma. Recent studies have shown the role of non-B DNA structures in generation of translocations. In the present study, using various bioinformatic tools, we show the propensity of formation of different types of altered DNA structures near translocation breakpoint regions. In particular, we find close association between occurrence of G-quadruplex forming motifs and fragile regions in almost 70% of genes involved in rearrangements in lymphoid cancers. However, such an analysis did not provide any evidence for the occurrence of G-quadruplexes at the close vicinity of translocation breakpoint regions in nonlymphoid cancers. Overall, this study will help in the identification of novel non-B DNA targets that may be responsible for generation of chromosomal translocations in cancer. (C) 2012 Elsevier Inc. All rights reserved.

Gibbs Energy of Formation of Ca3Ti8Al12O37 and Phase Relations and Chemical Potentials in the System Al2O3-TiO2-CaO

The quaternary oxide in the system Al2O3-CaO-TiO2 is found to have the composition Ca3Ti8Al12O37 rather than CaTi3Al8O19 as reported in the literature. The standard Gibbs energy of formation of Ca3Ti8Al12O37 from component binary oxides is measured in the temperature range from 900 to 1250 K using a solid-state electrochemical cell incorporating single crystal CaF2 as the solid electrolyte. The results can be represented by the equation: delta G(f(0x))(0) (+/- 70)/J mol(-1) = -248474 - 15.706(T/K). Combining this information with thermodynamic data on calcium aluminates and titanates available in the literature, subsolidus phase relations in the pseudo-ternary system Al2O3-CaO-TiO2 are computed and presented as isothermal sections. The evolution of phase relations with temperature is highlighted. Chemical potential diagrams are computed at 1200 K, showing the stability domains of the various phases in the chemical potential-composition space. In each chemical potential diagram, chemical potential of one component is plotted against the cationic fraction of the other two components. The diagrams are valid at relatively high oxygen potentials where Ti is present in its four-valent state in all the oxide phases.

Comments on ``Effects of current density on the formation and microstructure of Sn-9Zn, Sn-8Zn-3Bi and Sn-3Ag-0.5Cu solder joints''

Othman et al. (Intermetallics 2012;22:1-6) recently published a manuscript on ``Effects of current density on the formation and microstructure of Sn-9Zn, Sn-8Zn-3Bi and Sn-3Ag-0.5Cu solder joints''. We found problems in calculation of diffusion parameters. Even the comment on the formation of Cu5Zn8 instead of Cu6Sn5 is not correct. In this comment, we have explained the correct procedure to calculate the diffusion coefficients. Further, we have also explained the reason for the formation of Cu5Zn8 instead of Cu6Sn5 in the Cu/Sn-9Zn system. (C) 2012 Elsevier Ltd. All rights reserved.

System Ho-Rh-O: Phase Equilibria, Chemical Potentials and Gibbs Energy of Formation of HoRhO3

The thermodynamic properties of the HoRhO3 were determined in the temperature range from 900 to 1300 K by using a solid-state electrochemical cell incorporating calcia-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of orthorhombic perovskite HoRhO3, from Ho2O3 with C-rare earth structure and Rh2O3 with orthorhombic structure, can be expressed by the equation; Delta G(f)degrees((ox)) (+/- 78)/(J/mol) = -50535 + 3.85(T/K) Using the thermodynamic data of HoRhO3 and auxiliary data for binary oxides from the literature, the phase relations in the Ho-Rh-O system were computed at 1273 K. Thermodynamic data for intermetallic phases in the binary Ho-Rh were estimated from experimental enthalpy of formation for three compositions from the literature and Miedema's model, consistent with the phase diagram. The oxygen potential-composition diagram and three-dimensional chemical potential diagram at 1273 K, and temperature-composition diagrams at constant oxygen partial pressures were computed for the system Ho-Rh-O. The decomposition temperature of HoRhO3 is 1717(+/- 2) K in pure O-2 and 1610(+/- 2) K in air at a total pressure p(o) = 0.1 MPa.

Ex Situ X-ray Diffraction, X-ray Absorption Near Edge Structure, Electron Spin Resonance, and Transmission Electron Microscopy Study of the Hydrothermal Crystallization of Vanadium Oxide Nanotubes: An Insight into the Mechanism of Formation

The nucleation and growth of vanadium oxide nanotubes (VOx-NT) have been followed by a combination of numerous ex situ techniques. long the hydrothermal process. Intermediate solid phases extracted at different reaction times have been characterized by powder X-ray diffraction, scanning and transmission electron microscopy, electron spin resonance, and V-K edge :X-ray absorption near-edge structure spectroscopy. The supernatant vanadate solutions extracted during the hydrothermal treatment have been studied by liquid V-51 NMR and flame. spectroscopy. For short durations of the hydrothermal synthesis, the initial V2O5-surfactant intercalate. is progressively transformed into VOx-NT whose crystallization starts to be detected after a hydrothermal treatment of 24 h. Upon heating from 24 h to 7 days, VOx-NT are obtained in larger amount and with an improved crystallinity. The detection of soluble amines and cyclic metavanadate V4O12](4-) in the supernatant solution along the hydrothermal process suggests that VOx-NT result from a dissolution precipitation mechanism. Metavanadate species V4O12](4-) could behave as molecular precursors in the polymerization reactions leading to VOx-NT.

Mechanistic Aspects for the Formation of Copper Dimer Bridged by Phosphonic Acid and Extending Its Dimensionality by Organic and Inorganic Linkers: Synthesis, Structural Characterization, Magnetic Properties, and Theoretical Studies

Six new copper metal complexes with formulas Cu(H2O)(2,2'-bpy) (H2L)](2) center dot H4L center dot 4 H2O (1), {Cu(H2O)(2,2'-bpy)-(H3L)}(2)(H2L)]center dot 2H(2)O (2), Cu(H2O)(1,10-phen)(H2L)](2)center dot 6H(2)O (3), Cu(2,2'-bpy)(H2L)](n)center dot nH(2)O (4), Cu(1,10-phen)(H2L)](n)center dot 3nH(2)O (5), and {Cu(2,2'-bpy)(MoO3)}(2)(L)](n)center dot 2nH(2)O (6) have been synthesized starting from p-xylylenediphosphonic acid (H4L) and 2,2'-bipyridine (2,2'-bpy) or 1,10-phenanthroline (1,10-phen) as secondary linkers and characterized by single crystal X-ray diffraction analysis, IR spectroscopy, and thermogravimetric (TG) analysis. All the complexes were synthesized by hydrothermal methods. A dinuclear motif (Cu-dimer) bridged by phosphonic acid represents a new class of simple building unit (SBU) in the construction of coordination architectures in metal phosphonate chemistry. The initial pH of the reaction mixture induced by the secondary linker plays an important role in the formation of the molecular phosphonates 1, 2, and 3. Temperature dependent hydrothermal synthesis of the compounds 1, 2, and 3 reveals the mechanism of the self assembly of the compounds based on the solubility of the phosphonic acid H4L. Two-dimensional coordination polymers 4, 5, and 6, which are formed by increasing the pH of the reaction mixture, comprise Cu-dimers as nodes, organic (H2L) and inorganic (Mo4O12) ligands as linkers. The void space-areas, created by the (4,4) connected nets in compounds 4 and 5, are occupied by lattice water molecules. Thus compounds 4 and 5 have the potential to accommodate guest species/molecules. Variable temperature magnetic studies of the compounds 3, 4, 5, and 6 reveal the antiferromagnetic interactions between the two Cu(II) ions in the eight membered ring, observed in their crystal structures. A density functional theory (DFT) calculation correlates the conformation of the Cu-dimer ring with the magnitude of the exchange parameter based on the torsion angle of the conformation.