M. Schütze

Abstract The paper critically reviews the state of the art on the oxidation of TiAl. At the beginning differences compared to the oxidation of conventional Fe, Ni and Co alloys are discussed. The Knowledge of the TiAlO phase diagram as a basis for an understanding of the processes occurring during oxidation is very incomplete. Three different scale structures can be distinguished as functions of time or scale thickness. In the sub‐surface zone two phases with high oxygen solubilities can be identified after a certain time. These phases do not follow from the existing phase diagram. Nitrogen can have two different effects depending on the time it is added to the oxidation environment. The micro‐structure also affects the oxidation behaviour significantly, so this effect can lead to a misinterpretation of the influence of other parameters such as alloying elements. The influence of alloying elements is not yet understood. Mechanical loading leads to scale cracking, however, the system has a significant scale repair capacity, though about twothirds of the scale grows by inwards transport.

Phenomenological and electrochemical fundamentals of corrosion fundamentals of high temperature corrosion passivity of metals and alloys microbial corrosion environment sensitive fracture corrosive wear and erosion advanced investigation techniques cathodic and anodic protection environmentally friendly inhibitors the effect of coatings and surface modification.

Basic Requirements for the Protective Action of Oxide Scales. Development of Oxide Scales in High Temperature Technology. Mechanical Stresses in Oxide Scales and Their Causes. Deformation Behaviour and Deformation Mechanisms in Oxides. Damage to the Oxide Scale Resulting from Mechanical Stresses. Healing of Oxide Scale Damage. Depletion by Oxidation and Crack Healing of Alloying Elements Which Form Protective Scales. Oxide Scale Damage Diagrams. Concluding Remarks. References. Index.

Abstract Recent experimental investigations have widened the understanding of metal dusting significantly. Microscopic observations have been used to dissect dusting mechanisms. Iron dusts by growing a cementite surface scale, which catalyses graphite nucleation and growth. The resulting volume expansion leads to cementite disintegration. Cementite formation on iron can be suppressed by alloying with germanium. Nonetheless, dusting occurs via the direct growth of graphite into the metal, producing nanoparticles of ferrite. This process is faster, because carbon diffusion is more rapid in α‐Fe than in Fe 3 C. Austenitic materials cannot form cementite, and dust via formation of graphite at external surfaces and interior grain boundaries. The coke deposit consists of carbon nanotubes with austenite particles at their tips, or graphite particles encapsulating austenite. TEM studies demonstrate the inward growth of graphite within the metal interior. It is therefore concluded that the dusting mechanism of austenitic materials like high alloy Cr–Ni steels and Ni base materials is one of graphite nucleation and growth within the near surface metal. In all alloys examined, both ferritic and austenitic, the principal mass transfer process is inward diffusion of carbon. Alloying iron with nickel leads to a transformation from one mechanism with carbide formation to the other without. Copper alloying in nickel and high nickel content stainless steels strongly suppresses graphite nucleation, as does also an intermetallic Ni–Sn phase, thereby reducing greatly the overall dusting rate. A surface layer of intermetallic Ni–Sn Fe‐base materials facilitates the formation of a Fe 3 SnC surface scale which also prevents coking and metal dusting. Current understanding of the roles of temperature, gas composition and surface oxides on dusting rates are summarised. Finally, protection against metal dusting by coatings is discussed in terms of their effects on catalysis of carbon deposition, and on protective oxide formation.