Three-Chromophore Compounds I. Reductive Transformations of the 3,5-diaryl-2-cyclohexen-1-ones

The preparation of three 3,5-diarylcyclohexanones by rhodiumchlorotris(triphenyl-phosphine)—catalyzed reduction of the parent olefines (IIa—IIc) is described. Other reducing agents produced several intermediate products of the total hydrogenolysis.     

Function of sulfur dioxide in the kinetic mechanism of oxidation of carbon

Retardation of the gasification reaction of carbon with oxygen by SO₂ was observed. Rates of oxidation were determined by thermal gravimetric analysis (TGA) of a nuclear graphite in the temperature range of 550–700°C, and of a coconut charcoal in the temperature range of 400–505°C. The oxidant gases were dry air containing 0–6% SO₂. Reduction of the rate by SO₂ varied with burn-off. Differential thermal analysis (DTA) was also applied to detect the retardation effect of SO₂. The technique of infrared internal reflection spectroscopy (IRS) was used to examine the surface species of reacted charcoal samples. Absorption bands were assigned to surface carbonyls, lactones, and a chemisorbed SO₂ in the form of sulfate. Chemisorption of SO₂ was attributed to cause the retardation of the oxidation reaction.     

On the mechanical performance of closed cell Al alloy foams

The mechanical properties of three different commercially available closed cell Al alloys all made by foam casting are examined. The objective is to assess the roles of cell morphology and of imperfections in governing the basic properties: stiffness, yield strength and fracture resistance. This assessment provides goals for manufacturing strategies that enable attainment of good mechanical performance with affordable process technologies. A prevalent role of curves and wiggles in the cell walls on stiffness and strength (anticipated by models) is affirmed by the present measurements. Systematically larger stiffnesses and yield strengths found in tension than in compression are consistent with a prominent role exerted by such imperfections. Moreover, foam casting is apparently capable of cell morphologies that impart properties approaching the best achievable values for an isotropic closed cell solid, devoid of imperfections. There are associated implications for performance and affordability. Fracture measurements indicate crack growth occurring along the cell walls by a mechanism analogous to the plastic tearing of thin sheets. The crack growth resistances are in the range of 1 kJm⁻². This mechanism infers a toughness that scales with the cell wall thickness and its yield strength.     

Superconductivity,structural disorder,and phase transitions in ion-irradiated Nb3Al films

Thin films of single-phase A15 Nb₃Al were irradiated with protons and nitrogen ions. X-ray intensity analysis revealed a decrease of the Bragg-Williams long-range order parameterS and an increase of the average displacement amplitude of the atomsU in the fluence region where a decrease of the superconducting transition temperatureT _c was observed. The functional dependence ofT _c onS andU was found to depend on the ion species used for irradiation. After irradiation with 10¹⁶ N²⁺ / cm² the A15 phase transformed into an A2 phase. Furnace annealing caused a retransformation into the A15 phase with improved superconducting properties.     

Mechanisms of Hf dopant incorporation during the early stage of chemical vapor deposition aluminide coating growth under continuous doping conditions

A laboratory-scale chemical vapor deposition (CVD) reactor was used to perform “continuous” Hf doping experiments while the surface of a single-crystal Ni alloy was being aluminized to form an aluminide (β-NiAl) coating matrix for 45 minutes at 1150 °C. The continuous doping procedure, in which HfCl₄ and AlCl₃ were simultaneously introduced with H₂, required a high HfCl₄/AlCl₃ ratio (>∼0.6) to cause the precipitation of Hf-rich particles (∼0.1 μm) at grain boundaries of the coating layer, with the overall Hf concentration of ∼0.05 to 0.25 wt pct measured in the coating layer by glow-discharge mass spectroscopy (GDMS). Below this ratio, Hf did not incorporate as a dopant into the growing coating layer from the gas phase, as the coating matrix appeared to be “saturated” with other refractory elements partitioned from the alloy substrate. In comparison, the Hf concentration in the aluminide coating layer formed on pure Ni was in the range of ∼0.1 wt pct, which was close to the solubility of Hf estimated for bulk NiAl. Interestingly, the segregation of Hf and the formation of a thin γ′-Ni₃Al layer (∼0.5 μm) at the coating surface were consistently observed for both the alloy and pure-Ni substrates. The formation of the thin γ′-Ni₃Al layer was attributed to an increase in the elastic strain of the β-NiAl phase, associated with the segregation of Hf as well as other refractory alloying elements at the coating surface. This phenomenon also implied that the coating layer was actually growing at the interface between the γ′-Ni₃Al layer and the β-NiAl coating matrix, not at the gas/coating interface, during the early stage of the coating growth.     

Correlation of damage, dry band arcing energy, and temperature in inclined plane testing of silicone rubber for outdoor insulation

Silicone rubber samples, filled with 30% alumina trihydrate, subjected to the ASTM inclined plane test, show good correlation between the measured harmonic power components of dry band arcing and the surface temperature recorded with a thermovision camera. The simultaneous study of the low frequency fast Fourier transform and variations in temperature shows that when the temperature rises above 100/spl deg/C there is a well defined increase in the low frequency harmonic components of the measured power; however, this trend is not verified by the fundamental component. The eroded mass of the samples is measured independently by a laser approach and a model to rank the tested samples using the inclined plane test is developed. The model is validated by applying it to both the recorded harmonic power components and temperature, resulting in the correct ranking of damage on the samples tested in the inclined plane test.