▪ Abstract  Metal-hydrogen (M-H) systems are interesting from both a theoretical and a practical point of view. M-H systems are utilized for energy-storage systems, in sensor applications, and in catalysis. These systems are often exploited as models for studying basic material properties, especially when the size of these systems is small and nonbulk-like contributions become dominant. Surfaces, nanocrystals, vacancy- and dislocation-rich materials, thin films, multilayers, and clusters as systems of major interest are addressed in this review. We show that the hydrogen solubility of M-H systems is strongly affected by the morphology and microstructure of and the stress between regions of different hydrogen concentration. For small-sized systems, surface- or interface-related sites become important and change the overall solubility as well as the phase boundaries of M-H systems. In thin films deposited on stiff substrates, compressive stresses evolve during hydrogen loading because the films are effectively clamped to substrates. These stresses are in the GPa range and strongly depend on microstructure. Nanoparticles even change their crystallographic structure, which results in completely new phases.

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Grain refinement through severe plastic deformation enables synthesis of ultrahigh-strength nanostructured materials. Two challenges exist in that context: First, deformation-driven grain refinement is limited by dynamic dislocation recovery and crystal coarsening due to capillary driving forces; second, grain boundary sliding and hence softening occur when the grain size approaches several nanometers. Here, both challenges have been overcome by severe drawing of a pearlitic steel wire (pearlite: lamellar structure of alternating iron and iron carbide layers). First, at large strains the carbide phase dissolves via mechanical alloying, rendering the initially two-phase pearlite structure into a carbon-supersaturated iron phase. This carbon-rich iron phase evolves into a columnar nanoscaled subgrain structure which topologically prevents grain boundary sliding. Second, Gibbs segregation of the supersaturated carbon to the iron subgrain boundaries reduces their interface energy, hence reducing the driving force for dynamic recovery and crystal coarsening. Thus, a stable cross-sectional subgrain size <10  nm is achieved. These two effects lead to a stable columnar nanosized grain structure that impedes dislocation motion and enables an extreme tensile strength of 7 GPa, making this alloy the strongest ductile bulk material known.