Corrosion by Sulphur Chapter j 8 409

complex, consisting in the case of Fe-Nb alloys of Fe1dS, FeNb2S4, NbS2 and
particles of intermetallic Fe2Nb. Intercalation of iron into the layered NbS2
structure and the coexistence of iron-rich sulphides in the inner layer are
thought to explain the disappointing performance of these alloys. Ternary Fe-
Nb-Al alloys developed similar scales, with aluminium concentrated in the
inner layer. The phase constitution of these layers was not established, and a
lack of knowledge of the sulphide properties hampers discussion. It is clear,
however, that the presence of aluminium affects both iron and sulphur trans-
port, as both layers grew much more slowly.
The inner layer developed on Ni-Nb alloys consists of NiNb3S6 plus NbS2.
Nickel diffuses through this layer, but nickel sulphide growth is slowed
considerably. Thus although the alloys are unable to form a continuous, pro-
tective NbS2 layer as a result of ternary compound formation, the diffusional
blocking effect of the NbS2 particles and the presumably low value of DNi in
the mixed sulphide lead to a degree of protection. Similar benefits have been
obtained for Co-Nb alloys [93,94].
Some limited information is available for titanium sulphide scaling as a
result of an interesting application. Because TiO2 and Al2O3 are of comparable
stability, the intermetallic TiAl provides marginal resistance to rapid TiO2
growth. However, titanium sulphides are more stable than Al2O3. Selective
sulphidation of titanium has been used by Narita et al. [95e97] to form
aluminium-enriched alloy surface regions on g-TiAl in order to improve its
subsequent oxidation resistance. Reaction at 900 C in H2/H2S gas corre-
sponding to pS2 ¼ 1:3  105 atm leads to growth of multilayer scales enriched
in titanium. The inner layers consist mainly of TiS and Ti3S4. However, these
layers also contain some aluminium, which diffuses outwards to form a mixed
layer of Al2S3 and titanium sulphide in roughly equimolar proportions. Sul-
phidation rates were low.
It is recognised from the foregoing that very high alloying levels of Mo, Al,
Nb and/or Mn are required to achieve any benefit in protecting iron and nickel-
base materials against high sulphur potentials. No practical alloys have been
found. However, coatings based on refractory metals and aluminium may
prove to be of use in high sulphur potential environments [98,99]. It should
also be observed that the very high sulphur potentials (0.01e1 atm) used in
much of the research on refractory metal alloys are seldom encountered in
practice. Of more relevance to petroleum and coal conversion processes are
H2/H2S atmospheres, which are now considered.

8.4 SULPHIDATION IN H2/H2S

Low sulphur potentials result from the equilibrium
1
H2 S ¼ H2 þ S2 [8.4]
2
for which the standard free energy charge is given in Table 2.1. Mixtures of H2
and H2S have often been used in laboratory reactors to control pS2 values.