The EDS and XPS results indicate that there is unoxidized metallic

Ni0 incorporated in oxides from the free surface to the crevice

surface.
At the early stage of oxidation, the hydrochemistry conditions in
both the crevice and bulk solutions are identical. Fe and Ni
selectively dissolve from the matrix into high-temperature water
and the residual metallic elements are oxidized to predominant Cr-
rich oxides.
Cr released into the solution as HCrO4- under the condition of high
DO concentration.
(Ni, Fe)Fe2O4 oxide particles in the outer layer and the porous NiO
in the inner layer form on the free surface.
Cr released into the solution as HCrO4- under the condition of high
DO concentration.
(Ni, Fe)Fe2O4 oxide particles in the outer layer and the porous NiO
in the inner layer form on the free surface.
The DO concentration in the crevice solution gradually reduces and
the Fe2+ and Ni2+ are enriched at the crevice mouth.
NiFe2O4 spinels gradually develop at the crevice mouth through the
precipitation of the Fe2+ and Ni2+.
Ni2+ ions react with DO to form NiO particles.
Hydrolysis of Cr3+ produce large amount of Cr(OH)3 and result in
a decrease of pH value of solution.
NiO and Ni(OH)2 form due to large amount of Ni2+.
The low potential and the massive Ni2þ lead to the formation
of NiCr2O4 at the site within the crevice near the crevice
mouth.
At the deeper sites within the crevice, both the pH value of
solution and DO concentration are very low, resulting in the
formation of FeCr2O4 spinel.
At the same time, more and more Cr2O3 form in the inner layer
of oxide film.
Alloys with high Cr content such as Alloy 600 and 304 SS,
exhibited good anti-corrosion performance through forming a
Cr-rich protective layer.
The Cr content of Alloy 690 is higher than that of Alloy 600 and
304 SS, thus it exhibits good corrosion resistance within the
crevice.
However, very thick oxide films form at the crevice mouth due
to precipitation of Ni2+ and Fe2+ which migrate from the crevice.
The oxidation products formed on the crevice surface could
promote the initiation of crack of fretting corrosion fatigue
within the crevice.
During long term service of PWRs, fretting wear and fretting
corrosion fatigue can occur at the joint point between the SG
tubes (Alloy 690) and support plates.
Based on the present work, the oxide films formed at the
crevice mouth may become increasingly thick with increasing
operation time of PWRs.