Deformation and Recrystallization texture evolution in Nano-crystalline Nickel

Deformation and recrystallization textures in nano-crystalline nickel with average grain size of 20 nm were investigated using X-ray diffraction, electron microscopy and differential scanning calorimetry. The deformation behaviour of nano-crystalline nickel is quite complicated due to intervention of other deformation mechanisms like grain boundary sliding and restoration mechanisms like grain growth and grain rotation to dislocation mediated slip. Recrystallization studies carried out on the deformed nano-crystalline nickel showed that the deformation texture was retained during low temperature annealing (300 degrees C), while at higher temperature (1000 degrees C), the texture got randomised. The exact mechanism of texture formation during deformation and recrystallization has been discussed.

Diffusion mechanism in the gold-copper system

Interdiffusion study is conducted in the Au-Cu system, which has complete solid solution in the higher temperature range and ordered phases in the lower temperature range. First experiments are conducted at higher temperatures, where atoms can diffuse randomly. Higher values of interdiffusion coefficients are found in the range of 40-50 at.% Cu. This trend is explained with the help of thermodynamic factor and possible concentration of vacancies. Following an experiment is conducted at 623 K (350 degrees C), where the ordered phases are grown. The interdiffusion coefficients at this temperature are compared after extrapolating the data calculated at higher temperatures.

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.

Oxidative DNA cleavage, cytotoxicity and antimicrobial studies of L-ornithine copper (II) complexes

New ternary copper (II) complexes, Cu(L-orn)(B)(Cl)](Cl center dot 2H(2)O) (1-2) where L-orn is L-ornithine, B is an N,N-donor heterocyclic base, viz. 2,2'-bipyridine (bpy, 1) and 1,10-phenanthroline (phen, 2), were synthesized and characterized by various spectroscopic techniques. Complex 2 is characterized by the X-ray single crystallographic method. The complex shows a distorted square-pyramidal (4 + 1) CuN3OCl coordination sphere. Binding interactions of the complexes with calf thymus DNA (CT-DNA) were investigated by UV-Vis absorption titration, ethidium bromide displacement assay, viscometric titration experiment and DNA melting studies. Complex 2 shows appreciable chemical nuclease activity in the presence of 3-mercaptopropionic acid (MPA). The complexes were subjected to in vitro cytotoxicity studies against carcinomic human alveolar basal epithelial cells (A-549) and human epithelial (HEp-2) cells. The IC50 values of 1 and 2 are less than that of cisplatin against HEp-2 cell lines. MIC values for 1 against the bacterial strains Streptococcus mutans and Pseudomonas aeruginosa are 0.5 mM. (C) 2012 Elsevier Ltd. All rights reserved.

Microstructure and mechanical properties of oxidation resistant suction cast Nb-Si-Al alloy

In this paper, we report a significant improvement in mechanical and oxidation properties of near eutectic Nb-Si alloys by the addition of aluminum (Al) and control of microstructural length scale. A comparative study of two alloys Nb-18.79at%Si and Nb-12.3at%Si-9at%Al were carried out. The processing for microstructure refinements were carried out by vacuum suction casting in water cooled thick copper mould. It is shown that addition of Al suppresses Nb3Si phase and promotes beta Nb5Si3 phase under nonequilibrium solidification condition. The microstructural length scale and in particular eutectic spacing reduces significantly to 50-100 nm in suction cast ternary alloy. A detailed TEM study shows the presence of delta-Nb11Si4 phase in Nb matrix. The hardness of Nb solid solution can be increased as a consequence to a level observed in Nb3Si intermetallic due to the well oriented precipitates. Compression test yields the ultimate strength of 1.8 +/- 0.1 GPa and engineering strain of 2.3 +/- 0.03%. In comparison, the binary Nb-18.79 at% Si alloy possesses an ultimate strength of 1.35 +/- 0.1 GPa and strain of 0.2 +/- 0.01% when processed under identical conditions. The latter exhibits coarser microstructural length scale (300-400 nm) and a brittle behavior. The indentation fracture toughness of Al containing suction cast alloy shows a value of 20.2 +/- 0.5 MPa root m which represents a major improvement over bulk Nb-Si eutectic alloy. The detailed thermal studies confirm a multifold improvement in oxidation resistance up to 1000 degrees C. (C) 2012 Elsevier B.V. All rights reserved.

Synthesis and characterization of nickel/barium hexa-aluminate composite coatings

Electrodeposition of nickel/barium hexa-aluminate (Ni/BHA) composite coatings has been carried out from a Watt's bath on mild steel substrate. BHA powders with plate habit were synthesized by solution combustion synthesis followed by heat treatment to ensure complete conversion to the hexa-aluminate phase. Heat treated material was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) combined with X-ray analysis. The dispersion behaviour and stability of BHA suspensions with cationic and anionic surfactants at room temperature were studied by dynamic light scattering under different pH. The influence of BHA concentration in the electrolytic bath, deposition temperature, pH, current density and duty cycle on particle incorporation in the coatings were studied and conditions for maximum particle incorporation were established. Coatings with a roughness of about 0 center dot 4 mu m were produced by using this technique. Effect of BHA content on microhardness was also investigated. A reasonably good thickness of the coatings was achieved in a given set of conditions.

Microstructural Evolution and Some Unusual Effects During Thermo-Mechanical Cycling of Sn-Ag-Cu Alloys

Sn-Ag-Cu (SAC) solders are susceptible to appreciable microstructural coarsening during storage or service. This results in evolution of joint properties over time, and thereby influences the long-term reliability of microelectronic packages. Accurate prediction of this aging behavior is therefore critical for joint reliability predictions. Here, we study the precipitate coarsening behavior in two Sn-Ag-Cu (SAC) alloys, namely Sn-3.0Ag-0.5Cu and Sn-1.0Cu-0.5Cu, under different thermo-mechanical excursions, including isothermal aging at 150 degrees C for various lengths of time and thermo-mechanical cycling between -25 degrees C and 125 degrees C, with an imposed shear strain of similar to 19.6% per cycle, for different number of cycles. During isothermal aging and the thermo-mechanical cycling up to 200 cycles, Ag3Sn precipitates undergo rapid, monotonous coarsening. However, high number of thermo-mechanical cycling, usually between 200 and 600 cycles, causes dissolution and re-precipitation of precipitates, resulting in a fine and even distribution. Also, recrystallization of Sn-grains near precipitate clusters was observed during severe isothermal aging. Such responses are quite unusual for SAC solder alloys. In the regime of usual precipitate coarsening in these SAC alloys, an explicit parameter, which captures the thermo-mechanical history dependence of Ag3Sn particle size, was defined. Brief mechanistic description for the recrystallization of Sn grains during isothermal aging and reprecipitation of the Ag3Sn due to high number of thermo-mechanical cycles are also presented.

Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(II) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies

Four dinuclear bis(mu-Cl) bridged copper(II) complexes, Cu-2(mu-Cl)(2)(L-X)(2)](ClO4)(2) (L-X = N,N-bis(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper(II) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate L-X ligand, a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu(II) site in its axial position forming an SP-I dinuclear Cu(II) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1-3 exhibit methylmonooxygenase (pMMO) behaviour and oxidise 4-tert-butylcatechol (4-TBCH2) with molecular oxygen in MeOH or MeCN to 4-tert-butyl-benzoquinone (4-TBQ), 5-methoxy-4-tert-butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6'-Bu-t-biphenyl-3,4,3',4'-tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible.

DNA Binding and Oxidative Cleavage Activity of Ternary (alpha-Lipoic Acid) Copper(II) Complex of Heterocyclic Base

Ternary copper(II) complex Cu(a-lipo)(phen)(Cl)](NO3) where a-lipo = a-lipoic acid, phen is N, N-donor heterocyclic base, 1,10-phenanthroline was synthesized, characterized, and its DNA binding and cleavage activity were studied. Binding interactions of the complex with calf thymus (CT) DNA has been investigated by emission, viscosity, and DNA melting studies. The complex shows efficient oxidative cleavage of SC-DNA in the presence of 3-mercaptopropionic acid involving hydroxyl radical species, and results of control experiments exhibit the inhibition of DNA cleavage in the presence of hydroxyl radical scavengers, viz. DMSO and KI.

In Vitro and in Vivo Anticancer Activity of Copper Bis(thiosemicarbazone) Complexes

Neutral and cationic copper bis(thiosemicarbazone) complexes bearing methyl, phenyl, and hydrogen, on the diketo-backbone of the ligand have been synthesized. All of them were characterized by spectroscopic methods and in three cases by X-ray crystallography. In vitro cytotoxicity studies revealed that they are cytotoxic unlike the corresponding zinc complexes. Copper complexes Cu(GTSC) and Cu(GTSCHCl) derived from glyoxal-bis(4-methyl-4-phenyl-3-thiosemicarbazone) (GTSCH(2)) are the most cytotoxic complexes against various human cancer cell lines, with a potency similar to that of the anticancer drug adriamycin and up to 1000 fold higher than that of the corresponding zinc complex. Tritiated thymidine incorporation assay revealed that Cu(GTSC) and Cu(GTSCHCl) inhibit DNA synthesis substantially. Cell cycle analyses showed that Cu(GTSC) and Cu(GTSCHCl) induce apoptosis in HCT116 cells. The Cu(GTSCHCl) complex caused distinct DNA cleavage and Topo II alpha inhibition unlike that for Cu(GTSC). In vivo administration of Cu(GTSC) significantly inhibits tumor growth in HCT116 xenografts in nude mice.

Synthesis, crystal structure, DNA binding and cleavage activities of oximato bridged cationic dinuclear copper(II) complex having labile ligands

Oximato bridged dinuclear copper(II) complex Cu(L)(CH3OH)](2)(ClO4)(2) with an oxime-Schiff base ligand, viz. 3-2-(dimethylamino)ethyl]imino]-2-butanoneoxime (HL), has been synthesized and structurally characterized. The dinuclear copper(II) complex crystallizes in monoclinic space group P2(1)/n with the unit cell parameters, a = 13.3564(9) angstrom, b = 12.0821(8) angstrom, c = 17.5045(11) angstrom, beta = 90.097, V = 2824.8(3) angstrom(3), Z = 4, R = 0.0769. The complex shows quasi-reversible cyclic voltammetric response at 0.844V (Delta E-p = 276 mV) at 100 mVs(-1). The binding studies of the complex with calf thymus DNA has been investigated using absorption spectrophotometry. Cleavage activity of the complex has been carried out on double stranded pBR 322 plasmid DNA by using gel electrophoresis experiments in the absence and in the presence of the oxidant, viz., H2O2.

Mixed-ligand nickel(II) thiosemicarbazone complexes: Synthesis, characterization and biological evaluation

The syntheses and characterization of some new mixed-ligand nickel(II) complexes {Ni(L-1)(PPh3)] (1), Ni(L-1)(Py)] (2), Ni(L-2)(PPh3)]center dot DMSO (3), Ni(L-2)(Imz)] (4), Ni(L-3)(4-pic)] (5) and RNi(L-3))(2)(mu-4,4'-byp)]center dot 2DMSO (6)1 of three selected thiosemicarbazones the 4-(p-X-phenyl)thiosemicarbazones of salicylaldehyde) (H2L1-3) (A, Scheme 1) are described in the present study, differing in the inductive effect of the substituent X (X = F, Br and OCH3), in order to observe its influence, if any, on the redox potentials and biological activity of the complexes. All the synthesized ligands and the metal complexes were successfully characterized by elemental analysis, IR, UV-Vis, NMR spectroscopy and cyclic voltammetry. The molecular structures of four mononuclear (1-3 and 5) and one dinuclear (6) Ni(II) complex have been determined by X-ray crystallography. The complexes have been screened for their antibacterial activity against Escherichia coli and Bacillus. The minimum inhibitory concentrations of these complexes and their antibacterial activities indicate that compound 4 is the potential lead molecule for drug designing. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis, antimicrobial, DNA-binding and photonuclease studies of Cobalt(III) and Nickel(II) Schiff base complexes

New metal complexes of the type M(nih)(L)](PF6)(n)center dot xAH(2)O and M(nih)(2)](PF6)center dot xH(2)O (where M = Co(III) or Ni(II), L = 1,10-phenanthroline (phen)/or 2,2' bipyridine (bpy), nih = 2-hydroxy-1-naphthaldehyde isonicotinoyl hydrazone, n = 2 or 1 and x = 3 or 2) have been synthesized and characterized by elemental analysis, magnetic, IR and H-1 NMR spectral data. The electronic and magnetic moment 2.97-3.07 B.M. data infers octahedral geometry for all the complexes. The IR data reveals that Schiff base (nih) form coordination bond with the metal ion through azomethine-nitrogen, phenolic-oxygen and carbonyl-oxygen in a tridentate fashion. In addition, DNA-binding properties of these six metal complexes were investigated using absorption spectroscopy, viscosity measurements and thermal denaturation methods. The results indicated that the nickel(II) complex strongly bind with calf-thymus DNA with intrinsic DNA binding constant K-b value of 4.9 x 10(4) M-1 for (3), 4.2 x 10(4) M-1 for (4), presumably via an intercalation mechanism compared to cobalt(III) complex with K-b value of 4.6 x 10(4) M-1 (1) and 4.1 x 10(4) M-1 (2). The DNA Photoclevage experiment shows that, the complexes act as effective DNA cleavage agent. (C) 2012 Elsevier B.V. All rights reserved.

The effect of minor addition of Ni on the microstructural evolution and mechanical properties of suction cast Al-0.14 at. pct Sc binary alloy

Aluminum scandium binary alloys represent a promising precipitation-hardening alloy system. However, the hardness of the binary alloys decreases with the rapid coarsening of Al3Sc precipitate during high-temperature aging. In the current study, we report a new approach to compensate for the loss of mechanical properties by combining rapid solidification with very small ternary addition of transition metal Ni. This addition yields dispersion, and at a critical concentration improves the mechanical properties. We explore additions of a maximum of 0.06 at. pct of Nickel to a binary Al-0.14 at. pct Sc alloy, which yield nickel-rich dispersions. We report two kinds of biphasic dispersions containing AlNi2Sc/Al9Ni2 and alpha-Al/Al9Ni2 phase combinations. The maximum improvement in mechanical properties occurs with the addition of 0.045 at. pct Ni with a yield strength of 239 +/- A 7 MPa for an aging treatment at 583 K (310 A degrees C) for 15 hours. DOI: 10.1007/s11661-013-1624-z (C) The Minerals, Metals & Materials Society and ASM International 2013

Photocytotoxic ferrocene-appended (L-tyrosine)copper(II) complexes of phenanthroline bases

Copper(II) complexes of ferrocene(Fc)-conjugated reduced Schiff base of L-tyrosine (Fc-TyrH), viz., Cu(Fc-Tyr)(L)](ClO4), where L is 1,10-phenanthroline (phen, 1), dipyrido3,2-d:2',3'-f]quinoxaline (dpq, 2), dipyrido3,2-a:2',3'-c]phenazine (dppz, 3) and 2-(naphthalen-1-yl)-1H-imidazo4,5-f]1,10]phenanthroline (nip, 4), were prepared and tested for their photocytotoxicity in cancer cells. Cu(Fc-Phe)(phen)](-ClO4) (5) of L-phenylalanine and Cu(Ph-Tyr)(L)(ClO4)] of the reduced Schiff base Ph-TyrH derived from benzaldehyde and L-tyrosine having phen (6) and dppz (7), and Cu(Ph-Phe)(phen)(ClO4)] (8) using L-phenylalanine were prepared and used as controls. Complexes 5 and 6 were structurally characterized by X-ray crystallography. A copper(II)-based d-d band near 600 nm and a ferrocenyl band at similar to 450 nm were observed in DMF-Tris-HCI buffer (1:4 v/v) in respective complexes. The complexes are photocleavers of pUC19 DNA in visible light forming (OH)-O-center dot radicals. They are cytotoxic in HeLa (human cervical cancer) and MCF-7 (human breast cancer) cells showing an enhancement of cytotoxicity in visible light. Fluorescence imaging shows nuclear localization of the complexes.