One composition of Pr–Ce mixed oxide and a range of compositions of Pr–Zr mixed oxide were prepared by coprecipitation methods and characterized by x-ray powder diffraction, thermogravimetric analysis, and x-ray photoelectron spectroscopy. Based on phases formed, the PrOy—ZrO2 system in an oxygen-containing atmosphere at moderate temperatures (up to 800–1000 °C) is analogous to that of CeO2–ZrO2. Addition of either Ce or Zr to pure Pr oxide affects both the total amount of oxygen that can be reversibly exchanged between oxide and gas phase and the kinetics of the redox processes. Ce dramatically increases the amount (per Pr atom) and lowers the temperature of exchange, Zr slightly decreases the amount and also lowers the temperature of exchange, and both modifiers speed up the rate. These observations are rationalized in terms of bulk and surface structural features of the mixed oxides.
We describe a quantitative method for using the quartz crystal microbalance (QCM) to characterize the high frequency viscoelastic response of glassy polymer coatings with thicknesses in the 5-10 μm regime. By measuring the frequency and dissipation at the fundamental resonant frequency (5 MHz) and at the third harmonic (15 MHz), we obtain three independent quantities. For coatings with a predominantly elastic response, characterized by relatively low phase angles, these quantities are the mass per unit area of the coating, the density-shear modulus product, and the phase angle itself. The approach was demonstrated with a model polyurethane coating, where the evolution of these properties as a function of cure time was investigated. For fully cured films, data obtained from the QCM are in good agreement with results obtained from traditional dynamic mechanical analysis.
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