The sulfidation of three Cu-Cr alloys with nominal Cr contents of 25,
50, and 75 wt.% and of the two pure metals has been studied at 400-600
degrees C in H-2-H2S mixtures under sulfur pressures of 10(-12) atm a
t 400 and 500 degrees C and 10(-10) arm at 500 and 600 degrees C, slig
htly above the Cu-Cu2S equilibrium All the alloys were two-phase, cont
aining a mixture of the solid solution of chromium in copper with near
ly pure chromium. The corrosion rates of the three materials under the
same conditions were similar and intermediate between those of the tw
o pule metals and increased with temperature and sulfur pressure. The
scales had a complex composition, often containing an external Cu2S la
yer, which became discontinuous or even disappeared, in some cases, fo
llowed by an intermediate layer of the double Cu-Cr sulfide CuCrS2 and
an innermost complex layer, which generally consisted of a mixture of
the double Cu-Cr sulfide CuCr2S4 with the chromium sulfide CrS and al
so commonly contained unsulfidized chromium metal particles. No chromi
um depletion was developed in the alloys beneath the corrosion-affecte
d region. Moreover; no internal sulfidation of chromium was observed i
n the alloy richest in copper and no exclusive external sulfidation of
chromium in those richest in chromium, in spite of the large differen
ce in the thermodynamic stabilities of the sulfides of the two pure me
tals. These peculiar scale features are interpreted by taking into acc
ount the special two-phase nature of these alloys.