The Effect of Sulfur Segregation on the Adherence of the Thermally-Grown Oxide on NiAl—I: Sulfur Segregation on the Metallic Surface of NiAl(001) Single-Crystals and at NiAl(001)/Al2O3 Interfaces

The aim of this study was to improve the understanding of the deleterious effect of sulfur impurities on the adherence of the thermally-grown oxide on the boundary layer in thermal-barrier-coating systems. In Part I, the sulfur segregation on the free surface of NiAl(001) and at different interfaces between metal and transient alumina scales has been characterized by AES, XPS and LEED. The sulfur diffusion coefficient in the alloy has been determined (D = 0.15 exp(–218,000/RT) cm²/s). It is by three orders of magnitude larger than the nickel and aluminum self-diffusion coefficients. It has also been observed that the sulfur de-segregates upon Al enrichment of the metallic surface. The saturation of the metallic surface with an amorphous alumina layer formed at room temperature blocks the segregation of S. However, in the initial stages of oxidation where the transient -alumina grows by cationic transport and inject vacancies at the interface, S segregates at the interface between the alumina thin films and the metallic substrate.     

Experimental Investigation of the Impact of Cathode Grade on Sludge Formation at the Cathode Block-Aluminum Interface of Hall–Héroult Cells

Metallurgical and Materials Transactions B - The presence of resistive sludge on the cathode surface in Hall–Héroult cells can increase the aluminum production costs and reduces cell...     

Cathodic Wear by Delamination of the Al4C3 Layer During Aluminium Electrolysis

Metallurgical and Materials Transactions B - In aluminium reduction cells, an electrochemical reaction occurs between the molten electrolyte film below the aluminium pad and the carbon cathode...     

The Effect of Sulfur Segregation on the Adherence of the Thermally-Grown Oxide on NiAl—II: The Oxidation Behavior at 900°C of Standard,Desulfurized or Sulfur-Doped NiAl(001) Single-Crystals

In Part II of this study, the characterization by TGA, SEM and AFM of the oxidation behavior at 900°C of NiAl(001) samples with various sulfur concentrations is reported. The formation of interfacial cavities is observed for all samples. A constant ratio of the oxide thickness to cavity depth is found showing that the formation of cavities at the metal–oxide interface is not due to sulfur but only to vacancy injection during the cationic growth of transient -alumina. It is also observed that the presence of sulfur in the alloy decreases the oxidation rate of the nickel aluminide and, consequently, lowers the formation of interfacial cavities. This effect is interpreted as an indirect evidence of the control of the transient-alumina growth by the aluminium diffusion in the alloy, also advanced as an explanation for the interfacial nucleation of alpha alumina. These results are combined with those presented in Part I to propose a model that explains how sulfur, present in small quantities in the alloy, has a deleterious effect on the oxide adherence. The indirect role of the cavities formed during the growth of the transient alumina is to create transitory conditions for the rapid segregation of sulfur at the interface. The segregated sulfur remains as a vestige of the initial stages of growth after the transformation of the scale into mature alumina and weakens its adherence.