The syntheses and characterization of nickel complexes; investigation of Ni(dppp)2 and [NiX(dppp)n]x, potentially catalytically active nickel(0)/(I) species for cross-coupling reactions

This thesis describes an investigation in which we compare Ni(0), Ni(I) and Ni(II) complexes containing 1,3-bis(diphenylphosphino)propane (dppp) as a phosphine ligand for their abilities to effect three types of cross-coupling reactions: Buchwald-Hartwig Amination, Heck-Mizoroki, and Suzuki-Miyaura cross-coupling reactions with different types of substrates. The Ni(0) complex Ni(dppp)2 is known and we have synthesized it via a new procedure involving zinc reduction of the known NiCl2(dppp) in the presence of an excess of dppp. The Ni(0) complex was characterized by NMR spectroscopy and X-ray crystallography. Since Ni(I) complexes of dppp seem unknown, we have synthesized what at this stage appear to be NiXdpppn/[NiX(dppp)n]x (X = Cl, Br, I; n = 1,2, x = 1, 2) by comproportionation of molar equivalents of Ni(dppp)2 and NiX2dppp, X= Cl, Br, I.

The Effect of Foam Core Density on the Flexural and Axial Behaviour of Sandwich Panels of Varying Slenderness with Natural Flax-FRP and Glass-FRP Composite Skins

This study investigates the effect of foam core density and skin type on the behaviour of sandwich panels as structural beams tested in four-point bending and axially compressed columns of varying slenderness and skin thickness. Bio-composite unidirectional flax fibre-reinforced polymer (FFRP) is compared to conventional glass-FRP (GFRP) as the skin material used in conjunction with three polyisocyanurate (PIR) foam cores with densities of 32, 64 and 96 kg/m3. Eighteen 1000 mm long flexural specimens were fabricated and tested to failure comparing the effects of foam core density between three-layer FFRP skinned and single-layer GFRP skinned panels. A total of 132 columns with slenderness ratios (kLe/r) ranging from 22 to 62 were fabricated with single-layer GFRP skins, and one-, three-, and five-layer FFRP skins for each of the three foam core densities. The columns were tested to failure in concentric axial compression using pinned-end conditions to compare the effects of each material type and panel height. All specimens had a foam core cross-section of 100x50 mm with 100 mm wide skins of equal thickness. In both flexural and axial loading, panels with skins comprised of three FFRP layers showed equivalent strength to those with a single GFRP layer for all slenderness ratios and core densities examined. Doubling the core density from 32 to 64 kg/m3 and tripling the density to 96 kg/m3 led to flexural strength increases of 82 and 213%, respectively. Both FFRP and GFRP columns showed a similar variety of failure modes related to slenderness. Low slenderness of 22-25 failed largely due to localized single skin buckling, while those with high slenderness of 51-61 failed primarily by global buckling followed by secondary skin buckling. Columns with intermediate slenderness experienced both localized and global failure modes. High density foam cores more commonly exhibited core shear failure. Doubling the core density of the columns resulted in peak axial load increases, across all slenderness ratios, of 73, 56, 72 and 71% for skins with one, three and five FFRP layers, and one GFRP layer, respectively. Tripling the core density resulted in respective peak load increases of 116, 130, 176 and 170%.