Nitridation of Ni-based alloys: thermodynamics, kinetics, and deformation phenomena accompanying internal precipitation

When a moderately stable phase is precipitated out during an internal reaction, the behaviour of the penetrating atoms within the diffusion zone can be interpreted based on thermodynamic considerations. Evidence for “up-hill” diffusion of the penetrating species through the matrix towards the precipitation front during the internal nitridation of Ni-Cr alloys at 1125°C and 6000 bar of N2-pressure was predicted. Such behaviour of nitrogen is opposite to the boundary conditions in Wagner's description of internal reactions. A volume change associated with the precipitation reaction resulted in a stress gradient between the alloys surface and the internal nitridation front. Stress relief occurred mainly by transport of nickel to the gas/metal interface. Pipe diffusion-controlled creep is the dominant stress accommodation mechanism during nitriding of dilute Ni-Cr alloys at 700°C under a flowing NH3 + H2 gas mixture.