Corrosion Basics

Understanding the basic principles and causes of corrosion

High-Temperature Corrosion by Sulfidation
he major constituent in Nevertheless, the basic mechanism of

T
TAbLE 1
flue-gas corrosion that sulfidation is closely akin to air oxidation
and, to a considerable degree, the same Differences between metal
differentiates it from
alloying elements are useful in providing and sulfide eutectic melting
common high-temper- resistance to attack. The behavior of points
ature atmospheric cor- chromium follows the same pattern in Melting Point (°C)
rosion is the sulfur content. In sulfidation as in oxidation. It is particu- Metal-Sulfide
general, oxidation by sulfur, or larly interesting to note that, when suffi- Element Metal Eutectic
cient chromium is present, the relative Co 1,495 877
sulfidation, is a considerably
amount of nickel or iron is of secondary
more destructive form of high- Cr 1,850 1,350
importance, despite the fact that pure
temperature corrosion than oxi- nickel is much more susceptible to sulfur Cu 1,083 1,070
dation by oxygen. Sulftde scales attack than pure iron. Because chromium Fe 1,539 985
tend to crack and spall more is much more attracted to sulfur than Mn 1,260 —
either nickel or iron, the scale formed is Ni 1,455 645
readily than oxides, which can
essentially a chromium sulfide, when suf-
remain continuous and provide ficient chromium is present in the alloy,
some degree of corrosion pro- whatever the balance of the composition.
tection. In some cases, depend- Eventually, of course, when the chromi- on the performance of a number of
ing on the form in which sulfur um is depleted, the remaining base metal iron/nickel/chromium alloys with and
will be attacked rapidly. without aluminum. In every case, the
is present in the atmosphere,
The form in which sulfur is present presence of aluminum provided an addi-
continuous sulfide scales can- will affect the rate of attack. When oxy-
tional degree of resistance. Similar
not form, so attack will proceed improvement could be expected when
gen is also present, as would be the case
cementation techniques are used to
linearly; that is, the scale will af- with sulfur dioxide (SO2) or sulfur triox-
develop siliconized, chromized, or alumi-
ford no protection. The melting ide (SO3), a mixed oxide/sulfide scale fre-
quently forms and offers a greater degree nized coatings on ferrous alloys.
points of metallic sulftdes usu-
of protection than the sulfide scale pro- This article is adapted by MP
ally are lower than those of the duced by hydrogen sulfide (H2S) or Editorial Advisory Board Member
corresponding oxides. organics (which in most cases decompose Norm Moriber from Corrosion
Table 1 compares the melting points to give H2S) and, of course, sulfur vapor. Basics—An Introduction, Second
among a few metal sulfide/metal eutec- As with oxygen attack, aluminum may be
Edition, Pierre R. Roberge, ed.
tics with the base metal melting points. a useful addition to improve sulfida- (Houston, TX: NACE International,
Note that most sulfide eutectics are mol- tion resistance. Table 2 gives some data
2006), pp. 245-246.
ten at temperatures well below the melt-
ing points of the base metals. Oxide
eutectics usually melt at temperatures TAbLE 2
much closer to the melting points of the Influence of aluminum on sulfidation resistance of alloys(A)
metals on which they form. Thus, the (corrosion rate in mm/y)
sulfide-eutectic melting temperature fre- Aluminum Addition
quently will constitute a limit to the upper Material 0% 3% 4%
service temperature of the metal or alloy, 18 Cr-8 Ni 1.13 0.43 0.08
whereas only rarely does this occur with
20 Cr-32 Ni 0.41 0.18 —
an oxide. The presence of a molten phase
16 Cr-78 Ni 2.51 0.31 —
generally will cause a vast increase in the
(A)
corrosion rate of any metal. Test conditions: 530 °C, 3.1 MPa (480 psi) H2S in H2. Vol% from 1.4 to 1.7.

96 MATERIALS PERFORMANCE August 2009