The relationship between charge density and polyelectrolyte brush profile using simultaneous neutron reflectivity and in situ attenuated total internal reflection FTIR

We report on a novel experimental study of a pH-responsive polyelectrolyte brush at the silicon/D2O interface. A poly[2-(diethylamino)ethyl methacrylate] brush was grown on a large silicon crystal which acted as both a substrate for a neutron reflectivity solid/liquid experiment but also as an FTIR-ATR spectroscopy crystal. This arrangement has allowed for both neutron reflectivities and FTIR spectroscopic information to be measured in parallel. The chosen polybase brush shows strong IR bands which can be assigned to the N-D+ stretch, D2O, and a carbonyl group. From such FTIR data, we are able to closely monitor the degree of protonation along the polymer chain as well as revealing information concerning the D2O concentration at the interface. The neutron reflectivity data allows us to determine the physical brush profile normal to the solid/liquid interface along with the corresponding degree of hydration. This combined approach makes it possible to quantify the charge on a polymer brush alongside the morphology adopted by the polymer chains. © 2013 American Chemical Society.

Isothermal fatigue of an aluminide-coated single-crystal superalloy:Part I

The isothermal fatigue behavior of a high-activity aluminide-coated single-crystal superalloy was studied in air at test temperatures of 600 °C, 800 °C, and 1000 °C. Tests were performed using cylindrical specimens under strain control at ∼0.25 Hz; total strain ranges from 0.5 to 1.6 pet were investigated. At 600 °C, crack initiation occurred at brittle coating cracks, which led to a significant reduction in fatigue life compared to the uncoated alloy. Fatigue cracks grew from the brittle coating cracks initially in a stage II manner with a subsequent transition to crystallographic stage I fatigue. At 800 °C and 1000 °C, the coating failed quickly by a fatigue process due to the drastic reduction in strength above 750 °C, the ductile-brittle transition temperature. These cracks were arrested or slowed by oxidation at the coating-substrate interface and only led to a detriment in life relative to the uncoated material for total strain ranges of 1.2 pet and above 800 °C. The presence of the coating was beneficial at 800 °C for total strain rangesless than 1.2 pet. No effect of the coating was observed at 1000 °C. Crack growth in the substrate at 800 °C was similar to 600 °C; at 1000 °C, greater plasticity and oxidationrwere observed and cracks grew exclusively in a stage II manner.

Isothermal fatigue of an aluminide-coated single-crystal superalloy:Part II. Effects of brittle precracking

The effect of brittle coating precracking on the fatigue behavior of a high-activity aluminide-coated single-crystal nickel-base superalloy has been studied using hollow cylindrical specimens at test temperatures of 600 °C, 800 °C, and 1000 °C. Three types of precrack were studied: narrow precracks formed at room temperature, wide precracks formed at room temperature, and narrow precracks formed at elevated temperature. The effect of precracking on fatigue life at 600 °C was found to depend strongly on the type of precrack. No failure was observed for specimens with narrow room-temperature precracks because of crack arrest via an oxidation-induced crack closure mechanism, while the behavior of wide precracks and precracks formed at elevated temperature mirrored the non-precracked behavior. Crack retardation also occurred for narrow room-temperature precracks tested at 800 °C - in this case, fatigue cracks leading to failure initiated in a layer of recrystallized grains on the inside surface of the specimen. A significant reduction in fatigue life at 800 °C relative to non-precracked specimens was observed for wide precracks and elevated temperature precracks. The presence of precracks bypassed the initiation and growth of coating fatigue cracks necessary for failure in non-precracked material. No effect of precracking was observed at 1000 °C.