Phase separation and surface segregation in ceria-zirconia solid solutions

Using a combination of density functional theory calculations and statistical mechanics, we show that a wide range of intermediate compositions of ceria – zirconia solid solutions are thermodynamically metastable with respect to phase separation into Ce-rich and Zr-rich oxides. We estimate that the maximum equilibrium concentration of Zr in CeO2 at 1373 K is ~2%, and therefore equilibrated samples with higher Zr content are expected to exhibit heterogeneity at the atomic scale. We also demonstrate that in the vicinity of the (111) surface, cation redistribution at high temperatures will occur with significant Ce enrichment of the surface, which we attribute to the more covalent character of Zr-O bonds compared to Ce-O bonds. Although the kinetic barriers for cation diffusion normally prevent the decomposition/segregation of ceria-zirconia solid solutions in typical catalytic applications, the separation behaviour described here can be expected to occur in modern three-way catalytic converters, where very high temperatures are reached.

Evaluation of high-resolution surface wind products at global and regional scales

High resolution surface wind fields covering the global ocean, estimated from remotely sensed wind data and ECMWF wind analyses, have been available since 2005 with a spatial resolution of 0.25 degrees in longitude and latitude, and a temporal resolution of 6h. Their quality is investigated through various comparisons with surface wind vectors from 190 buoys moored in various oceanic basins, from research vessels and from QuikSCAT scatterometer data taken during 2005-2006. The NCEP/NCAR and NCDC blended wind products are also considered. The comparisons performed during January-December 2005 show that speeds and directions compare well to in-situ observations, including from moored buoys and ships, as well as to the remotely sensed data. The root-mean-squared differences of the wind speed and direction for the new blended wind data are lower than 2m/s and 30 degrees, respectively. These values are similar to those estimated in the comparisons of hourly buoy measurements and QuickSCAT near real time retrievals. At global scale, it is found that the new products compare well with the wind speed and wind vector components observed by QuikSCAT. No significant dependencies on the QuikSCAT wind speed or on the oceanic region considered are evident.Evaluation of high-resolution surface wind products at global and regional scales

Processes controlling surface, bottom and lateral melt of Arctic sea ice in a state of the art sea ice model

We present a modelling study of processes controlling the summer melt of the Arctic sea ice cover. We perform a sensitivity study and focus our interest on the thermodynamics at the ice–atmosphere and ice–ocean interfaces. We use the Los Alamos community sea ice model CICE, and additionally implement and test three new parametrization schemes: (i) a prognostic mixed layer; (ii) a three equation boundary condition for the salt and heat flux at the ice–ocean interface; and (iii) a new lateral melt parametrization. Recent additions to the CICE model are also tested, including explicit melt ponds, a form drag parametrization and a halodynamic brine drainage scheme. The various sea ice parametrizations tested in this sensitivity study introduce a wide spread in the simulated sea ice characteristics. For each simulation, the total melt is decomposed into its surface, bottom and lateral melt components to assess the processes driving melt and how this varies regionally and temporally. Because this study quantifies the relative importance of several processes in driving the summer melt of sea ice, this work can serve as a guide for future research priorities.