Resisting metal dusting corrosion
Metal dusting corrosion can limit operating conditions, but recent
developments in alloys are helping to combat the phenomenon
RAMESH VENKAT
Tubacex
M
etal dusting occurs in
environments contain-
ing carbon monoxide
and hydrogen in the tempera-
ture range 350-800°C. Several
industrial applications are sub-
ject to metal dusting corro-
sion such as plants producing
hydrogen by steam reforming
processes in industries includ-
ing oil refining and ammo-
nia and methanol production.
Other examples could be coal
gasification plants, synthetic
gas production and direct iron
reduction plants.
The extent of corrosion in
terms of general loss of mate-
rial and/or pitting corrosion
is severe, and pre-mature fail-
ure of tubes and pipes can lead
to loss of revenue and jeopard-
ise the safety of equipment and
plant. Lots of research activ-
ity has taken place and sev-
eral studies are still in progress
to mitigate metal dusting cor-
rosion. Some of the ways and
means developed by indus-
try to increase the life of tubes
and pipes from metal dusting
include use of gas phase inhib-
itors and diffusion coatings.
This article is not going to dis-
cuss the pros and cons of these
www.digitalrefining.com/article/1002256
Figure 1 Surface resulting from severe
metal dusting
alternatives and we believe
each solution could be effec-
tive in given circumstances.
The article will discuss nickel
alloys and their performance
and effectiveness in combating
metal dusting corrosion.
Mechanism
Metal dusting involves the dis-
integration of bulk metals and
alloys to metal particles, oxides
and graphite at high temper-
atures in environments that
are supersaturated with car-
bon. It is generally believed
that the phenomenon is most
widespread in the tempera-
ture range 400-800 °C. Such
corrosion has been observed in
processes in chemical and pet-
rochemical industries where
hydrocarbons or other strongly
carburising atmospheres are
encountered. It is a catastrophic
form of corrosion that occurs
when materials are exposed to
environments with high carbon
activity. It breaks up bulk metal
to metal powder (see Figure 1).
The suspected mechanism is
firstly the deposition of carbon
on the surface of the metal. The
carbon is, for instance, derived
from carbon monoxide in a gas
with a carbon activity much
higher than 1. This carbon
forms iron carbides in the case
of an iron alloy or diffuses into
the metal in the case of a nickel
alloy and, in both cases, after
super saturation the matrix
decomposes to carbon and fine
metal particles (and carbides).
In a general understanding of
the chemistry, at lower tem-
peratures the rate of reaction
is too low to be significant,
and at much higher tempera-
tures carbon activity and dep-
osition decrease. A critical item
of equipment that encoun-
ters metal dusting corrosion
is a boiler where the operat-
ing temperature zone is in the
range 400-800°C.
PTQ Q4 2018 1
 Nominal composition of commercial alloys
shows that normalised maxi-
mum mass loss for VDM Alloy
699XA was close to 0.001 after
Alloy Ni, % Cr, % Fe, % Mn, % Si, % Al, % Ti, % C, % Others
Nominal % 4000 hours of exposure. Also,
600 72 16 8 0.3 0.3 0.3 0.3 0.08 no pitting showed in a total
exposure time of 5692 hours;
601 60.5 23 13 0.2 0.2 1.4 0.4 0.05
602CA 62 25 9 2 0.18 Y, Zr
690 59 29 9 0.2 0.1 0.3 0.3 0.02 the time to first pit was signifi-
693
VDM Alloy
62 29 4 3 0.02 Nb, Zr
cantly higher than 602CA, 601
699XA Balance 30 Max. 2.5 2 0.02 Nb, Zr and 690.

Table 1 Weldability, workability and

Nickel alloys
The use of high nickel, high
chromium alloys is preferred
as they have much better corro-
sion resistance to metal dusting
than normal austenitic steels.
While alloying has enabled an
increase in resistance to metal
dusting corrosion, it also leads
to other non-desirable proper-
ties such as difficult workability
and weldability.
Importance of alloys in metal
dusting corrosion resistance
VDM Alloy 699XA, an alloy
developed by VDM and
Tubacex in partnership, can
produce seamless tubes and
pipes. Three key require-
ments for steels in this appli-
cation besides resistance to
metal dusting corrosion are
creep strength, weldability and
workability.
Corrosion resistance
A high percentage of chro-
mium is important in any stain-
less steel and in nickel alloys
for metal dusting corrosion
resistance as it provides a sta-
ble passive layer of chromium
oxide. As can be seen in Table
1, the latest alloys developed
to fight metal dusting, such
as VDM Alloy 699XA, have a
maximum chromium content of
30%, which makes it one of the
better alloys to be used in this
application.
However, any localised rup-
ture of the chromium oxide
layer can lead to significant
intake of carbon from the pro-
cess atmosphere into the alloy.
Here, the addition of alu-
minium leads to the forma-
tion of a protective aluminium
oxide scale or sub-scale. From
Table 1 we can see that VDM
Alloy 699XA has an alumin-
ium content as high as 2%. A
much higher aluminium con-
tent, such as 3%, would reduce
workability.
Increasing chromium to
about 30% together with a low
iron content is necessary for
high metal dusting corrosion
resistance in nickel alloys.
This combination of alloy-
ing elements makes VDM Alloy
699XA one of the best alloys for
resistance to metal dusting cor-
rosion in combination with its
good workabilty. Laboratory
results of metal loss through
metal dusting in a highly car-
bonising gas (37% CO, 9% H2O,
7% CO2, 46% H2, ac=163, p(02)=
2.5*10-27 bar at 600°C, 20 bar)
creep
VDM Alloy 699XA has good
weldability under argon.
Welding recommendations and
requirements need to be fol-
lowed. Workability at room
temperature is comparable to
601. Also creep resistance is
similar to or better than 601.
Conclusion
Refiners would like to run
their plant under peak operat-
ing conditions to take advan-
tage of cost and efficiency but
corrosion of steel alloys under
such harsh conditions has been
a deterrent factor. While a lot
of effort is being put into the
research and development
of alloys for metal dusting,
recently developed alloys have
so far shown promising results.
Ramesh Venkat is Heat Exchanger
Product Manager with Tubacex’s Group
Global Technical Marketing department.
Email: vramesh@tubacex.com
LINKS
More articles from the following
categories:
Corrosion and Fouling Control

2 PTQ Q4 2018 www.digitalrefining.com/article/1002256