T

FAILURE ANALYSIS his article concerns the failure of

a pipe reactor separator vessel in

SCC Failure of
an ammonium nitrate (NH4NO3)
plant. Fabricated from Type
304L stainless steel (SS) (UNS S30403),
the vessel experienced severe internal
corrosion after two years of operation.

a Super Duplex
The bottom half of the vessel was re-
placed using super duplex SS (UNS
S32750, Table 1). Within two months of
operation, leaks were observed from

Separator
welds in the boot section, requiring re-
pairs and eventual replacement of the
bottom section with Type 310S SS (UNS
S31008). The results of the failure inves-
tigation are discussed along with corro-

Vessel in an
sion issues that were identified in the as-
sociated pipe reactor.

Background

Ammonium Process Description

The pipe reactor is a 2-m length of
100-mm outside diameter pipe, in which
60% nitric acid (HNO3) is mixed with

Nitrate Plant
liquid anhydrous ammonia (NH 3 ) to
produce NH4NO3. The design through-
put is 33.3 t/h, giving a flow rate of ~1.4
m/s. The exothermic reaction generates
steam, leading to maximum temperatures
V. LINTON, University of Adelaide, South Australia of ~190 °C and a pressure of ~400 KPa.
N. LAYCOCK(1) AND D. KEEN, MPT Solutions, Lower Hutt, New Zealand The pipe reactor feeds into the separator
P. BOON, Queensland Nitrates, Queensland, Australia vessel, where process fluid is drawn off
from the bottom of the vessel while steam
and unreacted NH3 are extracted from
the top (Figure 1). The process fluid in the
Tis article presents findings of a failure investigation separator boot section is nominally a pH
1 solution at 170 to 190 °C and 400 KPa,
on a separator vessel in an ammonium nitrate with composition (wt%) 82% NH4NO3,
16% H2O, 0.8% NH3, and 0.8% HNO3.
(NH4NO3) plant. Te super duplex stainless steel vessel
Pipe Reactor Corrosion
The pipe reactor had been fabricated
leaked due to stress corrosion cracking initiated in the from UNS S30403 and was replaced ap-
proximately every three months because
heat-affected zones of welds exposed to the
NH4NO3 solution at ~180 °C. (1)
Author is currently with Shell Todd Oil
Services, New Plymouth, New Zealand.

64 MATERIALS PERFORMANCE September 2008

 M AT E R I A L S S E L E C T I O N & D E S I G N

TABLE 1
Nominal composition of all commercial alloys referred to in
this article (major alloy elements only; balance Fe)
Alloy Name (UNS No.) Cr Ni Mo
of rapid erosion-corrosion damage. On- Type 304L (S30403) 18-20 8-10 —
line wall thickness measurements indi- Type 316L (S31603) 16-18 10-14 2-3
cated typical maximum general corrosion Type 2507 (S32750) 25 7 4
rates of ~20 mm/y (Figure 2). Measure-
Type 310S (S31008) 24-26 19-22 —
ments of a trial super duplex SS (UNS
S32750) pipe reactor indicated a maxi-
mum corrosion rate of ~10 mm/y (Fig-
ure 2). Examination of the trial piece FIGURE 1
showed significant preferential attack of
the circumferential weld heat-affected
zone (HAZ), however, which was prob-
ably not captured by the online ultra-
sonic measurements.

Separator Failure History

The separator vessel had been fabri-
cated from UNS S30403, but there were
unacceptably high corrosion rates in the
boot section and in the impingement zone
where the process fluid enters from the
pipe reactor. Given the good perfor-
mance of the trial super duplex SS pipe
reactor (based on the online thickness
tests), the bottom half of the separator was
replaced using UNS S32750. The inlet
flange between the pipe reactor and the
separator was replaced with a forged
UNS S32750 flange. After seven weeks
of operation, product started leaking from
cracks associated with baffle plates in the
boot of the vessel and the circumferential
weld joining the boot and torespherical
head. Over the next few weeks, further
leaks were detected at the latter circum-
ferential weld, at the pad flange, and at
the inlet flange to the nozzle weld (Figure
1). The leaks were patched on the outside
of the vessel, and eventually the entire
bottom section of the vessel was replaced
using UNS S31008. Schematic drawing of the reactor separator vessel, showing locations of cracking.

Investigation Method
Super duplex SS samples were ob-
tained from the inlet flange to nozzle re-
gion, the pad flange, boot sections includ-
ing a baffle plate, and patched areas of
the boot to transition piece weld and boot
to torespherical head weld (Figure 1).
Metallographic cross sections were pre- Investigation Results
pared from the samples and examined
using an optical microscope. Beraha’s Inlet Flange
etchant was used to reveal the presence Transverse cracking was found in the
of a sigma phase (Fe-Cr-Mo intermetallic) weld (Figure 3). The cracks were signifi-
in the microstructure. cantly branched and predominantly in-
September 2008 MATERIALS PERFORMANCE 65
M AT E R I A L S S E L E C T I O N & D E S I G N SCC Failure of a Super Duplex Separator Vessel
in an Ammonium Nitrate Plant

FIGURE 2

running predominantly along the ferrite-

austenite boundaries with a small number
of transgranular “jumps” across the aus-
tenite phase (Figure 4[b]). The pad flange
had a typical duplex microstructure and
no third phases were observed.

Boot
Wall thickness measurements on the
boot samples showed typical wall loss of
0.3 to 0.4 mm, with localized loss of up
to ~1 mm. A 14-mm-long through-wall
transverse crack ran out from the tores-
Online wall thickness measurement results for the pipe reactor, showing results for
several different replacements of pieces 2 (dashed lines) and 3 (solid lines), which pherical head to the boot weld. This crack
are consecutive sections of the reactor, joined together by a circumferential weld. was significantly branched and had initi-
ated from the HAZ on the inside of the
vessel. The baffle plates were welded to
FIGURE 3
the boot shell, and these regions were
cracked extensively both in the shell and
baffle. Two large cracks (10 and 25 mm
long) ran along the HAZ of the circum-
ferential weld joining the boot to the
transition piece (Figure 5).

Discussion
At the separator inlet, the pipe reactor
contains a gas phase of steam and unre-
acted NH3, and a liquid phase that is the
same as that in the boot of the separator
vessel. This liquid causes rapid erosion-
corrosion in the pipe reactor, and is
characterized by its flow rate (1.4 m/s),
acidity (~pH 1), temperature (180 °C),
and its oxidizing power (due to free
HNO3). The general (uniform) corrosion
rate of Type 316 SS (UNS S31600) is
slightly higher than that of Type 304 SS
(UNS S30400) in concentrated HNO3
Through-wall cracks in the inlet flange sample, microscopic view, etched to show solutions due to the detrimental effect of
austenite as the lighter phase. The cracks are predominantly intergranular, but molybdenum on transpassive corrosion
some transgranular “jumps” through the austenite phase are present. resistance.1-4 Nevertheless, for the pipe
reactor, online measurements show the
tergranular, although some transgranular Pad Flange general corrosion rate of UNS S32750 to
“jumps” through the austenite phase The pad flange contained cracking in be less than that of UNS S30403 (Figure
were present. The flange had a typical the HAZ adjacent to the weld, with some 2), suggesting that the potentially detri-
forged duplex structure, but up to 2% of of the cracking running through the thick- mental effect of molybdenum alloying is
a third phase, probably sigma phase, was ness of the plate (Figure 4[a]). The cracks more than counter-balanced by the rela-
observed in the cracked regions. were branched and mainly intergranular, tively increased chromium content in
66 MATERIALS PERFORMANCE September 2008
 M AT E R I A L S S E L E C T I O N & D E S I G N

FIGURE 4

UNS S32750. The preferential attack of

the circumferential weld HAZ in the
UNS S32750 pipe reactor is most likely
due to the detrimental effect of third
phases, such as sigma. For the boot of the
separator vessel, wall thickness measure-
ments suggest typical UNS S32750 cor-
rosion rates of 1 to 1.3 mm/y, with local-
ized attack at up to 4 mm/y. This
compares with ~2 mm/y in the original The pad flange: (a) macroscopic view, as received; (b) microscopic cross section,
UNS S30403 boot. etched.

Weld Quality and Sigma Phase

FIGURE 5
Super duplex SS can form third phases
as a result of welding or heat treatment.
These are usually present at <5 vol%, but
can have a significant influence on the
material’s corrosion resistance. For ex-
ample, <0.2% sigma phase does not af-
fect the critical pitting temperature (CPT)
of UNS S32750, but 1.3% causes a reduc-
tion of ~15 °C and 7 to 9% can reduce it
more than 40 °C.5 In this case, third
phases were not detected in any of the
failed weld regions, except in the inlet
flange where 1 to 2% was detected in
the HAZ.

Stress Corrosion Cracking

The cracks have the classic branched
appearance of SCC, with a maximum
through-wall propagation rate of ~1 mm
per week. Through-wall crack propaga-
tion generally occurred in the HAZ, at
least partly because this location has sig-
nificant weld residual stress, which drives
crack propagation. In these areas, the
cracks either take the tortuous path along Macroscopic view of a cross section through the circumferential weld joining the
the ferrite-austenite boundary around the boot to the transition piece. This section had a patch on the outside of the vessel.
austenite islands or “jump” transgranu-
larly across the austenite phase (Figure 4).
Some cracks also extend into the parent Much of the literature on SCC of duplex SS does not suffer SCC in 3%
material, propagating mostly along fer- duplex SS is focused on chloride-induced sodium chloride (NaCl) at up to 150 °C.7
rite-austenite boundaries. This is consis- SCC in near-neutral solutions, often set- The process fluid in this case has an ex-
tent with the absence, away from the ting “safe” temperature limits. UNS tremely low chloride content (a few ppm),
welds, of any significant residual stresses S32750 is reportedly effectively immune however, with an excess of nitrate, mak-
that could promote crack propagation to chloride-induced SCC at temperatures ing a chloride-based corrosion mecha-
through the vessel wall. up to 300 °C.6 Similarly, UNS S31803 nism very unlikely. Temperature is a
September 2008 MATERIALS PERFORMANCE 67
M AT E R I A L S S E L E C T I O N & D E S I G N
significant factor in the SCC of SS, how-
ever, so this failure constitutes an observa-
tion of rapid SCC in UNS S32750 at
~180 °C. Moreover, this SCC has oc-
curred in material without any detrimen-
tal third phase (within the detection limits
of optical microscopy).
Overall, given the predominantly in-
tergranular crack propagation mode and
the fairly active but nonuniform corro-
sion of the exposed SS surfaces, we sug-
gest that this failure is an example of
Type A SCC, according to the definitions
proposed by Newman.8 This is SCC of a
metal with a susceptible metallurgy, in a
state of imperfect passivity near an ac-
tive-passive transition. We also note
some strong similarities between this
failure and that of UNS S32750 in vinyl
chloride monomer strippers9-10 and this
has been discussed in greater detail else-
where.11
Conclusions
The super duplex SS separator vessel
failed by SCC initiated in the HAZ of
welds exposed to the hot process fluid.
This is nominally a pH 1 solution of 82
wt% NH4NO3 at 180 °C, with <1 wt%
free HNO3.
The shell and flange-nozzle welds ap-
pear to have been welded appropriately.
There were observable levels of sigma
phase in the HAZ of the inlet nozzle and
the baffle-to-shell welds were of poor
quality, but extensive cracking was ob-
served in areas without these problems.
The cracks propagated predominantly
along the ferrite-austenite phase bound-
aries, but also showed occasional “jumps”
through the austenite phase.
According to the definitions proposed
by Newman, this failure can be classified
as an example of Type A SCC; that is,
SCC of a metal with a susceptible metal-
lurgy, in a state of imperfect passivity near
an active-passive transition.
68 MATERIALS PERFORMANCE September 2008
SCC Failure of a Super Duplex Separator Vessel
in an Ammonium Nitrate Plant
Acknowledgments VALERIE LINTON is a professor at the University of
Adelaide, School of Mechanical Engineering,
The authors thank Queensland Adelaide, 5061 South Australia. She holds a chair in
Nitrates for permission to publish this welded structures at the university. Prior to that,
article, particularly Mark Patman for his she was a consultant for MPT Solutions (now Quest
generous assistance with the work. Lay- Reliability), New Zealand and a senior engineer at
British Gas, U.K.
cock and Keen’s work was funded by the
New Zealand Foundation for Research NICK LAYCOCK is a senior materials & corrosion
Science and Technology, contract engineer at Shell Todd Oil Services (STOS), 167
CO8X0409. Devon St. W., New Plymouth, New Zealand. He is
responsible for corrosion management and
inspection across the Kapuni, Maui, and Pohokura
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Using the MT-1 Procedure,” in Avesta and Ph.D. from the Corrosion & Protection Centre at
UMIST, received the L.L. Shreir Award in 1994, and
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