Ordering induced by chemical, thermal and mechanical constraints at solid interfaces

We know that classical thermodynamics even out of equilibrium always leads to stable situation which means degradation and consequently d sorder. Many experimental evidences in different fields show that gradation and order (symmetry breaking) during time and space evolution may appear when maintaining the system far from equilibrium. Order through fluctuations, stochastic processes which occur around critical points and dissipative structures are the fundamental background of the Prigogine-Glansdorff and Nicolis theory. The thermodynamics of macroscopic fluctuations to stochastic approach as well as the kinetic deterministic laws allow a better understanding of the peculiar fascinating behavior of organized matter. The reason for the occurence of this situation is directly related to intrinsic non linearities of the different mechanisms responsible for the evolution of the system. Moreover, when dealing with interfaces separating two immiscible phases (liquid - gas, liquid -liquid, liquid - solid, solid - solid), the situation is rather more complicated. Indeed coupling terms playing the major role in the conditions of instability arise from the peculiar singular static and dynamic properties of the surface and of its vicinity. In other words, the non linearities are not only intrinsic to classical steps involving feedbacks, but they may be imbedded with the non-autonomous character of the surface properties. In order to illustrate our goal we discuss three examples of ordering in far from equilibrium conditions: i) formation of chemical structures during the oxidation of metals and alloys; ii) formation of mechanical structures during the oxidation of metals iii) formation of patterns at a solid-liquid moving interface due to supercooling condition in a melt of alloy. © 1984, Walter de Gruyter. All rights reserved.

Surface enrichment in gold/silver alloys: effects of temperature studied by atom probe tomography

Bimetallic alloys are increasingly used in heterogeneous catalysis. This interest is explained by the emergence of new features that are absent in the parent single metals. Synergistic effects between the two combined elements create a more efficient catalyst. One of the most challenging aspect of multicomponent materials in catalysis is the ability to fine-tune the catalytic properties of an alloy by controlling the nature and composition of the surface [1]. For example, the gold/silver alloy combines a high activity and a large selectivity for a broad range of oxidation reaction.It is well established that the surface composition of alloys may deviate from that of the bulk phase. Surface enrichment has also important consequences in some applications of heterogeneous catalysis. In some cases, the thermal and chemical treatments can lead to opposite trends regarding the nature of the metal prone to surface enrichment. Using atom probe tomography we aim to link the physicochemical conditions the composition of the very first atomic layers of bimetallic catalysts and eventually to fine-tune the catalytic features of the latter.

Catalytic CO2 hydrogenation: study at the molecular scale using field emission techniques

An accurate characterization of the rhodium specimen was obtained via FIM experiments. Reaction behaviors between H2 and CO2 were observed in FEM mode at 700 K. At this temperature, CO desorption occurs, preventing CO+H2 reaction. Surface is mainly recovered by oxygen; reaction with hydrogen occurs. Finally, we can identify the reaction as the Reverse Water Gas Shift.