Nanocrystalline materials are being explored as potential off-chip interconnects materials for next generation microelectronics packaging. Mechanical behavior and deformation mechanisms in nanocrystalline copper and nickel have been explored. Nanostructured copper interconnections exhibit better fatigue life as compared to microcrystalline copper interconnects at a pitch of 100 and #956;m and lower. Nanocrystalline copper is quite stable upto 100 oC whereas nickel is stable even up to 400 oC. Grain boundary (GB) diffusion along with grain rotation and coalescence has been identified as the grain growth mechanism. Ultimate tensile and yield strength of nanocrystalline (nc) Cu and Ni are atleast 5 times higher than microcrystalline counterparts. Considerable amount of plastic deformation has been observed and the fracture is ductile in nature. Fracture surfaces show dimples much larger than grain size and stretching between dimples indicates localized plastic deformation. Activation energies for creep are close to GB diffusion activation energies indicating GB diffusion creep. Creep rupture at 45o to the loading axis and fracture surface shows lot of voiding and ductile kind of fracture. Grain rotation and coalescence along direction of maximum resolved shear stress plays an important role during creep. Grain refinement enhances the endurance limit and hence high cycle fatigue life. However, a deteriorating effect of grain refinement has been observed on low cycle fatigue life. This is because of the ease of crack initiation in nanomaterials. Persistent slip bands (PSBs) at an angle of 45o to loading axis are observed at higher strain ranges (> 1% for nc- Cu) with a width of about 50 nm. No relationship has been observed between PSBs and crack initiation. A non-recrystallization annealing treatment, 100 oC/ 2 hrs for nc- Cu and 250 oC/ 2 hrs for nc- Ni has been shown to improve the LCF life without lowering the strength much. Fatigue crack growth resistance is higher in nc- Cu and Ni compared to their microcrystalline counterparts. This is due to crack deflection at GBs leading to a tortuous crack path. Nanomaterials exhibit higher threshold stress intensity factors and effective threshold stress intensity is proportional to the elastic modulus of the material.

The design of non-classical materials, such as multifunctional energetic materials and/or the synthesis of high pressure phases rely on the understanding of the mechanisms responsible for shock-induced reactions in powder mixtures. The critical reactant powder configurational changes and mechanical mixing processes necessary for reaction initiation have yet to be determined. Consequently, shock-induced reactions have only been observed in select material systems under certain conditions, and remain an uncontrolled phenomenon. Shock-induced reactions in nickel and aluminum powder mixtures are investigated in this work through the use of instrumented gas-gun experiments performing time-resolved pressure and shock velocity measurements to determine the pressure-volume (P-V) shock compressibility (Hugoniot) of the mixture, from which evidence of reaction is inferred through deviations from the inert shock response calculated on the basis of mixture theory. The role of particle size and morphology on non-diffusional mixing and chemical reactivity is explored by conducting similar tests on micron-scale powders of spherical and plate-like (flake) shape. Recovery experiments performed just below the reaction threshold provide information about the densification and mixing behavior between reactants. Discrete-component numerical simulations of the shock-compression of powder mixtures are performed to reveal the micromechanics of particle deformation, and mechanisms of mass-flow and mixing that can lead to the formation of reaction products. The results obtained from time-resolved measurements, recovery experiments, and numerical simulations are coupled to model the linkages between starting powder configuration, mechanically-driven mixing, and chemical reactivity. The knowledge gained from this investigation will lead to understanding of reaction mechanisms, and the control over reaction initiation threshold, time and exothermicity, in addition to characteristics of reaction products formed. The scientific understanding attained will advance the design and application of multifunctional materials for next generation energetic applications, and/or the synthesis of novel materials.

In this study, we used different ways to synthetize four-coordinate zinc(II) and nickel(II) complexes with optically active Schiff base offering N2S2 coordination, i.e. N,N'-Bis(2-thiobenzylidene)-l,2-(R,R)cycholhexyl- enediaminatozinc(II) (1) and N,N'-Bis(2-thiobenzylidene)-l,2-(R,R)cychol- hexylenediaminatonickel(II) (2). We obtained the crystal structure of 2 and the pyridine adduct of 1, N,N'-Bis(2-thiobenzylidene)-l,2-(R,R)cycholhexylenediaminopyridylzinc(II) (1¡DPy). Coordination geometry around Zn atom in 1¡DPy is a distorted trigonal bipyramid. These structures were compared with the N2O2 stuctural analogues reported in the literature. We hope these chiral complexes can make contribution to the enzyme model studies in the future.

In this study, the carbon electrode of supercapacitor was fabricated by using mesocarbon microbeads. For finding the optimal processing parameters of carbon electrode, the effects of specific surface area of activated carbon, the amount of carbon black and binder, and various electrolytes on the capacitative properties of supercapacitor are investigated. To fabricate the composite electrode of supercapacitor, NiO and WO3 thin films were deposited respectively on the carbon electrode by electron beam evaporation. The influences of various scan rates of cyclic voltammograms (CV) on the characteristic of capacitance are studied. The charge-discharge efficiency and life time of the composite electrode are also discussed. Experimental results reveal that the optimum carbon electrode can be obtained using mesocarbon microbeads with high specific surface area (2685 m2/g) and larger pore volume (0.6 cm3/g) and adding 10 wt.% carbon black and 2wt.% binder. The specific capacitances of carbon electrodes in 1 M KOH and 1 M Et4NBF4 are 230.8 F/g and 221.5 F/g, respectively. Besides, the XRD and SEM results showed that NiO and WO3 thin films on composite electrode are sheet-liked crystal structure and stone-liked amorphous structure, respectively. The composite electrode exhibits better capacitance properties than those of carbon electrode at high scan rate by CV analysis. It reveals the promotion of the capacitative property of supercapacitor at higher power density and the improving of the decay property in capacitance at high scan rate. Finally, in the test of charge-discharge efficiency and life time, the charge-discharge efficiency is near 100% after 5000 cycles and it still retains good adhesion between electrode material and substrate.

Nickel Nanostrands (NiNS) are nano-particles that are highly branched and have a high aspect ratio. These particles show promise as excellent additives to composites when electrical conductivity is desired. Unfortunately, there is very little research done on dispersing powdered NiNS in various polymer matrices. This thesis covers the research in dispersing NiNS in three separate polymer systems, and related composite processing and characterization. An aromatic polyimide (CP2) is first used as a thermoplastic matrix and attempts to incorporate NiNS via an in-situ processing technique concurrent with in-situ polymerization are detailed. Epoxy is then used as a representative thermoset where the NiNS are dispersed in the resin before a hardener is added. The last polymer tested is thermoplastic Polyvinylidene Fluoride (PVDF). NiNS are introduced to this polymer in a solution mixture. Once dispersed, the PVDF solution is heated until the solvent evaporates leaving a PVDF melt containing NiNS, which is subsequently cooled. Samples of all three polymer nano-composites are created and dispersion is observed with an optical microscope. Using DSC, DMA and dielectric spectroscopy, thermal, mechanical and electrical properties are measured and analyzed. Results for the CP2 nano-composites showed that during the cure phase, the NiNS settled to the bottom of the films resulting in a non-dispersed composite. This result highlighted the difference between NiNS and other more conventional nano-particles, namely that the NiNS are larger and heavier, therefore are not 'locked into' a dispersed state by the polymer chains. Several techniques were investigated for dispersing NiNS in the epoxy matrix. A method without solvent was shown to be the most effective and resulted in a well-dispersed nano-composite that showed increases in electrical conductivity and dielectric constant as NiNS concentration increases. Enhancement in storage modulus was observed above the composite's Tg as well. PVDF nano-composites also showed good dispersion and a general increase in electrical properties. Below Tg, storage modulus decreases at first before a slight recovery with increasing NiNS. Beyond Tg, the opposite effect is observed. FTIR measurements for the PVDF were also taken and showed no significant changes in the polymer morphology with additions of NINS.

Late transition metal complexes bearing nitrogen-containing ligands have many applications in biotechnology or industrial catalysis. In this thesis, we react two nitrogen-containing tridentate ligands with some late transition metal salts to yield complexes (1)-(18). Besides spectroscopic characterization, complexes (3), (5)-(7), (8), (10), (12)-(16) yielded crystal structures analyzed using X-ray single crystal diffraction. From crystal structure of complexes (3), (5)- (7), we concluded that the reaction of ligand and Cu(£L£L) salts always gave the CuLX2 products. In Ni series, structures of different coordination types were obtained by using different crystal-growing methods. Crystals obtained using diffusion method take on the form of MLX2 while different structures of complexes (8), (10) were obtained using double layer method. Judging from the result of ESI-Mass analyses, complexes (8) and (10) were both of the dimeric form[NiL1Cl(£g-Cl)]2. However complex (10) was shown by X-ray single crystal to be [NiL 2(H2O)2 Cl]Cl. This could be the hydration product from [NiL1Cl(£g-Cl)]2.

Leaching is the most widely used process for extraction of nickel metal from lateritic ores. In this study, nickel extraction from Manisa-G&ouml / rdes region laterites by hydrochloric acid leaching is aimed. The mineralogical analysis of sample showed that hematite, goethite, dolomite, quartz and smectite are the main minerals in the ore. Attrition scrubbing, cycloning and magnetic separation with permroll were used as preconcentration processes but results were unsatisfactory. HCl leaching experiments were conducted both at room temperature and at elevated temperatures. The effects of various parameters such as leaching duration, particle size, concentration of HCl, pulp density, Cl- concentration and temperature on nickel recovery were examined. The results showed that under the optimised leaching conditions (particle size: 100 % -1 mm, HCl concentration: 3 N, leaching duration: 3 hours, leaching temperature: 100 oC, pulp density: 1/30 solid to liquid ratio by volume) it was possible to extract 87.26 % of nickel in the ore.

The A-cluster of acetyl-CoA synthase (ACS) catalyzes the formation of acetyl- CoA from CO, coenzyme-A, and a methyl group donated by a corrinoid iron-sulfur protein. Recent crystal structures have exhibited three different metals, Zn, Cu, and Ni, in the proximal site, which bridges a square-planar nickel site and a [Fe4S4] cubane. Contradicting reports supported both the nickel and copper containing forms as representing active enzyme. The results presented here indicate that copper is not necessary or sufficient for catalysis and that copper addition to ACS is deleterious. Several proposed mechanisms exist for the synthesis of acetyl-CoA, the two most prominent are the ‘paramagnetic’ and ‘diamagnetic’ mechanisms. The ‘diamagnetic’ mechanism proposes a two electron activation that precedes methylation to produce an EPR silent Ni2+-CH3 species. This then reacts with CO and coenzyme-A to form acetyl- CoA and regenerate the starting species. The ‘paramagnetic’ mechanism assumes a one electron activation prior to the methylation of the paramagnetic Ni1+-CO state to form an unstable Ni3+-acetyl species. This is immediately reduced by an electron shuttle. Results are presented here that no shuttle or external redox mediator is necessary for catalysis. This supports the ‘diamagnetic’ mechanism, specifically that a two-electron reductive activation is necessary and that the Ni1+-CO species is not an intermediate. The two-electron reductive activation required by the ‘diamagnetic’ mechanism results in an unknown electronic state. Two proposals have been made to describe this form of the A-cluster. The first hypothesis from Brunold et al involves a one-electron reduction of the [Fe4S4]2+ cube and a one-electron reduction of the Nip 2+. This should result in a spin-coupled state that is S = integer. The Ni0 hypothesis requires both electrons to localize on the Nip 2+ forming a zero-valent proximal nickel. Mössbauer spectroscopy has been used to probe the oxidation state and spin state of the [Fe4S4] cube in the reduced active form. No integer spin system is found and this is interpreted as supporting the Ni0 hypothesis. Additionally, spectra are presented that indicate the heterogeneous nature of the A-cluster is not caused by the occupancy of the proximal site.

Nitrogen ligands with bulky substituents are currently attracting interest as tools for controlling the coordination gap aperture. Bis(imino)pyridines and a-diimines are particularly noteworthy in this context. It has been shown that bulky derivatives of N-ligands are highly sensitive to the rates of both chain propagation and of termination processes in polymerization, leading to high molecular weight polyolefins while sterically less demanding analogues produce oligomers. These results underline the importance of steric factors in designing the structure of ligands. Coordination chemistry with the tridentate hybrid ligand containing soft and hard backbone, such as P/N, N/N, etc, has been drawing an intensive research. We have endeavored to prepare a series of amido phosphinimine derivatives containing bulky substituents on both P- and N- atoms and their metal complexes. These complexes which have been well-characterized by solution multi nuclei NMR spectroscopic data and single crystal X-Ray diffractometer are potentially more rigid and robust to conquer the flexibility of the backbone.

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