Bimetallic and Alloy Welds in HP

Hydrogen and Nitrogen Service

Three failures of bimetallic welded joints in ammonia plants occurred in 1999 and in 2000 at one
inlet and in two shells of Ammonia Converter Effluent Exchangers (123Cs). Some of the
metallurgical failure investigation completed for one of the welded joints is reviewed. These failures
indicated prudent action was required in order to provide safe repairs for return to service. An
'Advisory' was issued to other operators in order to avoid failures of similar welded joints in other
plants.

Jim B. Sievert
Kellogg Brown & Root, Inc., Houston, TX 77001

Introduction ducted by Metallurgical Consultants, Inc. in Houston,

TX. What the investigation found was a small zone of

I
n June of 2000, a weldment failure caused a
process side leak in an ammonia converter efflu-
ent boiler feed water exchanger (item 123-C1) at
Palembang, Indonesia (Pusri IB). The failure will be
discussed within this article. A similar weldment failure
had occurred earlier at the P.T. Petrokemia Gresik
Indonesia at an inlet nozzle in 1999, and a subsequent
similar fusion line separation was found in the Gresik
heat exchanger shell in 2000. The Pusri failure consist-
ed of a circumferential fracture along one side of a girth
weld that joined the heavy wall (145 mm, 5.7-in. thick)
shell forging of the vessel to the tubesheet forging.
Verbal and digital photograph information from the
plant site indicated that the fracture occurred on the
shell side of the weld. This separation encompassed
one-half of the circumference of the vessel shell.
KBR identified sampling for metallurgical investiga-
tion of the Pusri failure, which was subsequently con-
high hardness adjacent to the nickel butterpass in the
low-chrome ferritic shell forging on one side of the cir-
cumference of the heat exchanger. This very small,
localized hard zone rendered the area susceptible to
cracking and subsequent separation due to hydrogen
embrittlement and crack separation. Generally, these
types of failures are associated with temperatures lower
than plant operating temperatures. The report further
indicated that the thermal history of the forgings in the
exchanger apparently resulted in a different micro-
structure for the cracked side vs. the uncracked side.
Background
The exchanger which was investigated and discussed
in this article for the Pusri failure was fabricated by
Belleli in Italy in 1991. Note that a similar unit for P. T.

AMMONIA TECHNICAL MANUAL 77 2002

Petrokimia Gresik, had also been fabricated in Italy by
Industrie Meccanihe Bagnalo. The height of the Pusri
exchanger is approximately 7,733 mm (25.4 ft), with
an outside diameter of 1,601 mm (5.25 ft) and a shell
thickness of 145 mm (5.7 in.). The shellside inlet and
outlet nozzles have an internal diameter of approxi-
mately 408-420 mm (16-16.5 in.), and a 690-700 mm
(27-27.5 in.) outside diameter. A general cross-section
arrangement of the exchanger noting the crack location
is shown in Figure 1.

Metallurgy and Process

The shell and tubesheet both met the composition

requirements for l-l/4Cr-l/2Mo steel forgings,
(ASME SA 336 Fil). The clad composition on the
inside surface was confirmed to be a stainless steel,
AWS SFA-5.4 E 347 or SFA-5.9 ER 347. It was report-
ed that the closing weld was made with Inconel 82,
AWS SFA-5.14 ERNiCr-3, after buttering each side
with Inconel 600 followed by thermal stress relief.
The process gas inlet stream temperature of the vessel
was 458°C (856°F) and the outlet temperature was
357°C (675°F). Process design for the upstream con-
verter effluent was for about 177 bar (2,567 psi) total
pressure while the exchanger inlet operating conditions
included high hydrogen and nitrogen partial pressures Figure 1. Ammonia converter effluent/boiler
due to the hydrogen content, about 53 vol. %, and the feedwater exchanger general arrangement.
ammonia content, about 17.6 vol. %. The hydrogen
laboratory (Metallurgical Consultants, Inc.) for analy-
partial pressure was reported to be 92.66 kg/cm2 (1,318
sis. Figure 2 shows the general zone of this failure
psi). Due to the boiler feedwater supply of 266.5°C
along with the five sample locations, which had been
(511.7°F) to the channel which exits at 328°C (622°F),
provided for investigation.
the normal operating temperature near the weldment
which failed operates at approximately 427°C (800°F).
Fabrication Detail and Crack Separation
Sampling and Repairs
Area

Figure 3 shows a cross-sectional detail from the fab-

Kellogg Brown & Root, Inc. provided an equipment
rication drawings of the shell-closing seam with the
engineer followed by a welding engineer on-site in
failed weldment.
order to assist in repairs. The repairs were completed
Figure 4 provides a cross-sectional photograph from
by a contracted crew from Engineers and Fabricators
the item following section removal, rough polishing,
Company from Houston, TX. Samples were requested
and etching. The photograph shows the interior stain-
and taken from the failure by EFCO, then boxed and
less steel weld overlay (at the left), the butterpass to the
shipped to KBR in Houston. These samples were sub-
tubesheet forging (top), and the butterpass to the shell
sequently provided to an independent metallurgical

AMMONIA TECHNICAL MANUAL 78 2002

 123-C Ammonia Converter Effluent/BF W Heat Exe hanaer

Zone of assimila r weld separation from

shell plate

#1and#2

180 degrees of Sample 4

circumference was is the top and bottom
separated at bottom of weld mating zone in an
dis similar weld area 180 degrees from
the center! ine of the
major separation/crack
area

Sample 1 and 2
is the top (I ow chrome'
forging with butterpass and
inconel weld) and the
bottom half of a mating
zone (any remnant inconel
butterpass weld with the
low chrome shellplate) in
the crack area
stainless on the internal
Sample 3
is the bottom half of
another zone in the
separation/crack area
(low chrome with
diameter)
Sample 5- is across an
unfailed dissimilar weld in
the s hells ide 20-inch
diameter inlet nozzle
(inconel to low chrome
with internal diameter ss
clad or weld overlay)
(about 12-inch long x 3-
inch wide x thickness)

Figure 2. General fracture zone and sample removal locations.

AMMONIA TECHNICAL MANUAL 79 2002

forging (bottom). The through-thickness (145 mm or Summary Findings and Conclusions
about 5.7-in.) separation can be seen at the bottom.
During repairs to the Pusri unit, five samples were
removed by EFCO and subsequently sent from KBR to
Fracture Face Metallurgical Consultants, Inc. (MC) for examination.
The purpose of the examination was to determine the
As shown in Figure 4, the shell forging alloy butter- cause of the failure.
pass weld had separated along the ferritic to nickel The vessel fractured along the fusion line of the nick-
alloy weld fusion zone. This is further evidenced when el-alloy weld, on only the shell side of the weld. In
the cross-section is opened and viewed over the sepa- addition to the fracture along the weld fusion line, there
ration thickness facing the previously mating fracture were intergranular cracks extending into the base metal
surfaces. Figure 5 represents a section of the circum-
ference from the 145 mm (5.7-in.) thickness at the
interface fusion line separating the ferritic shell
from the butterpass nickel weld. The top of the pho-
tograph shows the outside diameter of the exchang-
er shell, and the bottom of the photograph shows the
inside diameter of the exchanger shell at the stain-
less weld overlay thickness. The numerous weld-
ment butter passes for the shell thickness are por-
trayed in the left and right sample sections of each
face, which had previously been mated together. The SA33CF11+W.O.
fracture appeared to follow the contour of the many
individual passes of the weld in the heavy-wall
exchanger.

Similar Fracture from a Nozzle Failure

For reference only, Figures 6 and 7 show an exam-

ple of a similar-looking failure which had occurred SA33fF11+347 w,
earlier in the inlet nozzle of the same service Figure 3. Cross-section of closing seam from fabrication
exchanger at another processing unit. drawing.
The weldment, however, joined an
austenitic to a low chrome clad nozzle.
This appeared with the face of the frac-
ture in an approximately 50.8 mm (2-
in.) thick section of the 50.8 mm (20-
in.) diameter on the left and the cross
section of the nickel weldment (with
essentially no remaining ferritic avail-
able for investigation).

Figure 4. Photo at cross-section of closing seam weldment, separation at

shell forging interface.

AMMONIA TECHNICAL MANUAL 80 2002

of the shell. No cracks or fractures were observed on
the tubesheet side of the weld.
Sample 2 had a crack that extended along most of
one side of the weld, but had not completely separated;
no cracks were apparent along the other side. Figure 4
shows the weld profile in the same orientation as in the
design. After etching, this shows the area with a crack
along the bottom fusion zone with the shell forging.
Specimens of the cracked and intact sides of the weld
near the inside surface (Sample 2) were prepared for

Figure 5. Photograph mating weldment separation faces.

Figure 7. Cross section of the

weldment for a prior inlet noz-
Figure 6. Internal diameter cladding with the remainder of zle failure in another unit.
the face showing separation.

AMMONIA TECHNICAL MANUAL 81 2002

metallographic examination. Photomacrographs of the
two sides are shown in Figure 4 (cross-section) and
Figure 5 (facings). At this radial location of the
exchanger, the crack extended along the fusion line and
arrested in the stainless steel cladding. As presented
later within the hardness survey, smaller cracks were
also found adjacent to the butterpass extending into the
low-alloy steel. There were no cracks along the fusion
line on the weld opposite the major fracture at 180
degrees around the girth weld or in the tubesheet side
of the weldment.
Metallurgical acid etching of the cross-sections of the
girth weld in both shellside and tubeside metallograph-
ic specimens showed a light-etching zone near the
fusion lines and darker-etching passes towards the cen-
terline of the weld, which indicated that the two sides
had been buttered before the closing weld was made.
Although the two sides of the weld were both report-
ed to be SA 336 Fil, there was a difference in the
respective microstructures. In the figures to follow,
microstructures show the grain size on the nonfailed
tubesheet side of the weld to be uniformly fine: a num-
ber 8 according to ASTM E 112. The microstructure of
the cracked side had a mixed grain size. Some of the
grains were very large, 4 according to ASTM E 112,
and other grains were finer, 8 according to E 112. There
is no grain-size requirement for SA 336 Fil forgings.
Photomicrographs at 100X magnification (after
etching) showed a basic difference in the microstruc-
ture from the tubeside (top) and shellside (bottom)
forgings near the weldments (Figures 8 and 9).
Figure 8. A336F11 tubesheet (intact side)
near dissimilar weldment.
AMMONIA TECHNICAL MANUAL
The features of consequence in Figures 8 and 9 are
distinct differences in thermal history which result in
varying grain size for the different forgings.
Metallographic examination of the weld near the
inside surface showed narrow light-etching microstruc-
tures next to the fusion line on each side of the weld,
with darker-etching weld passes joining them. The dif-
ferences in weld microstructure indicated that the shell
and tubesheet had been "buttered" with an alloy, as
reported.
Examination of the inside stainless clad surface
showed a dark-etching layer with cracks. As the layer
was too hard for saw cutting, and it was brittle, the
layer appeared to be nitriding from service (Figures 10
and 11).
Hardness
Vickers tests showed that the hardness of the weld
and low-alloy steel next to the weld fusion line were
significantly harder on the fractured shell side than on
the intact tubesheet side of the weld. The differences in
hardness between the two sides of the weld indicated
that at the fracture, the shell side had not been suffi-
ciently stress-relieved, but that the tubesheet side had
been stress-relieved.
Similar hardness tests on specimens from both sides
of the girth weld at an uncracked location of the vessel
opposite the failure showed a hardness range corre-
sponding to that of the tubesheet weld. The lower hard-
Figure 9. A336F11 shellside (cracked side) near
dissimilar weldment.
82 2002
ness on both sides of the girth weld on the opposite side
of the vessel indicated satisfactory stress relief of the
shell and tubesheet at this radial location.
Elemental Analysis
Elemental analyses across the fractured side and
intact side of the weld showed generally similar distri-
bution of chemical composition, but there were wider
compositional gradients on the cracked side compared
with the intact side of the weld. For example, there was
carbon detected in the weld near the fractured fusion
line, but virtually none in the weld next to the tubesheet
fusion line. The compositional gradients are attributed
to greater dilution on the shell side from buttering. The
chemical compositions of the weld and of the low-alloy
steel forgings on both sides of the weld satisfied the
requirements for the reported alloys of construction.
Figure 10. Cracking detail.
Photomicrograph of small intergranular cracks,
indicated by dark arrows, and fracture along the
weld fusion line with weld-metal remnanats, white
arrows.
AMMONIA TECHNICAL MANUAL
Analysis by Energy-Dispersive X-Ray
Spectroscopy
Scans across the fusion lines of the cracked and intact
sides of the weld were performed by energy-dispersive
X-ray Spectroscopy (EDS) at the approximate locations
of the hardness surveys and mapped, as shown in
Figure 12. Each scan was centered on the crack or
fusion line, and consisted of 128 points at an approxi-
mate interval of 0.0007-in. (0.02 mm) between points.
Scans included the base metal and weld metal on each
side of the fusion lines. The results were plotted with
points on the abscissa and the approximate weight per-
cent for each point, as determined by an iterative semi-
quantitative standardless procedure, on the ordinate. A
similar scan was performed near the inside surface of
the weld cladding on the cracked side of the girth weld.
Some of the results of the EDS analyses were shown
paired, from the shell to the tubesheet. An abrupt
change in chemical composition indicates the crack or
the fusion line, as is apparent from the zero readings.
One of the plots provided the approximate percent-
age of nickel (Figure 12). As anticipated, the nickel
content of the girth weld was high and that of the low-
alloy steel on each side of the weld was low. Near the
fusion line of the cracked side of the weld, the nickel
content within the weld increased over a distance of
approximately 0.015 in. (0.38 mm) to the maximum
detected. On the intact side, the nickel content of the
weld increased to the maximum detected within 0.004
in. (0.1 mm) from the fusion line. There was also a
slightly higher average nickel content on the cracked
side than on the intact side. The difference in the rate of
Figure 11. Nitriding Layer.
Photomicrograph of dark nitrided layer, arrows, in the weld
overlay on the inside surface.
83 2002
change of nickel content for the two sides of the weld
probably indicated different dilution during buttering.
Three points of high nickel content were apparent on
the low-alloy steel side of the crack, which probably
represented a narrow weld fragment attached to the
shell.
The plotted results for chromium were also provided
(Figure 13), with high chromium content found in the
weld and lower chromium content in the low-alloy
steel. The chromium content on the cracked side of the
weld was slightly higher than on the intact side. As was
the case for the nickel content, on the cracked side of
the weld, there was a gradual increase of chromium
content from the fusion line to the maximum observed.
From the intact weld fusion line the chromium content
increased to the maximum within 0.004-in. (0.1 mm).
Although there were significant local variations in
molybdenum content in both the weld and low-alloy
steel, this element showed generally equal distribution
when averaged for the weld metal and low-alloy steel,
as shown in Figure 14.
The manganese content of the weld was higher than
that of the low-alloy steels (Figure 15).
The silicon content showed wide variations within
the weld and within the low-alloy steel, but the average
content appeared similar for both.
Predictably, the iron content varied little within the
weld and within the steel, as shown in Figure 16. The
niobium content of the weld locations was found high-
er than that of the low-alloy steels because this element
comprises part of the composition for the welding con-
sumable.
Aluminum was distributed throughout the weld and
low-alloy steels at normal concentrations.
The element of greatest interest in these surveys was
carbon, which showed a relatively high concentration
on the side of the weld with higher hardnesses and the
crack (Figure 17). Carbon was detected in the weld
metal up to 0.050 in. (1.25 mm) away from the edge of
the crack. Carbon was detected at only one point in the

Hicftgl • CrackMl Shall W*M MfeUI - Intact rufanliMi Vftt*

TulMdwn

Figure 12. Line scans of nickel composition at 256 points, from left to right, across the shell, the
cracked shell weld fusion line, the two sides of the weld, the intract tubesheet weld fusion Une and the
tubesheet.
- O»e*ed ShW w«*d

"f TubWIWK
«Ml

^yuv*

Figure 13. Line scans of chromium composition at 256 points, from left to right, across the shell, the
cracked shell weld fusion line, the two sides of the weld, the intact tubesheet weld fusion Une and the
tubesheet.

AMMONIA TECHNICAL MANUAL 84 2002

 Oactad Shut W«M • hm«t Tttwftut W*W
WrtJ TulmtWif

WM»

Figure 14. Line scans of molybdenum composition at 256 points, from left to right, across the shell, the cracked
shell weld fusion line, the two sides of the weld, the intact tubesheet weld fusion line and the tubesheet.
Mang«*** - Cricted S**H W«lij

Figure 15. Line scans of manganese composition at 256 points, from left to right, across the shell, the
cracked shell weld fusion line, the two sides of the weld, the intact tubesheet weld fusion line and the
tubesheet.
Iron - Ciackinl Sti«n Wold Iron • Iniftet Tubesho«! WeM

\\ f
m-
30
SO
^SfojiM^V^M**»"»
SO
9 — (0 — «Î «* 0 •- O

Figure 16. Line scans of iron composition at 256 points, from left to right, across the shell, the cracked
shell weld fusion line, the two sides of the weld, the intact tubesheet weld fusion line and the tubesheet.

weld metal on the intact side.
There were differences between the semi-quantita-
tive EDS (Energy Dispersive) analyses and the quanti-
tative OES (Optical Emission) and AA (Auger) analy-
ses of the two steels and of the weld metal in particu-
lar. The EDS gives semi-quantitative results only. It is
also important to remember that the line scans were
performed along the sides of the weld to determine the
possibility of diffusion or dilution, whereas the analy-
sis of the weld metal was performed at the middle of
the weld to determine its composition.
The line scan across the weld cladding at the inside
surface showed a chromium-nickel stainless steel with
significant niobium, confirming the use of a consum-
able such as ER 347 for cladding. Figure 18 shows the
niobium line scan of the weld cladding, with the inside

AMMONIA TECHNICAL MANUAL 85 2002

 Orten - CwcMd Sta» VMä
SMI
j
slfill i!.'. i\tw '
'2SSsS53ï,SS8s
Figure 17. Line scans of carbon composition at 256 points, from left to right, the cracked shell
fusion line, the two sides of the weld, the intact tubesheet weld fusion line and the tubesheet.
surface.
High nitrogen content was detected in a surface gra-
dient of the cladding. Figure 19 shows the nitrogen dis-
tribution in the cladding. The first 19 points, starting at
the inside surface (at 0.02 mm per point), show on
average much higher nitrogen content than the remain-
der of the line scan. These 19 points correspond to the
dark-etching layer observed during metallographic
observation. The nitrogen line scan confirmed that a
dark-etching layer was a nitrided layer.
Nitriding
Chemistry scans for nitrogen showed higher contents
to a depth of 0.42 mm (0.017-in.). However, an actual
nitride brittle layer of only 0.18 mm (0.007-in.) was
found. Since a cover of austenitic material at the inner
surface of the weld repair was not included, that small
section will be subject to surface hardening by nitriding
due to diffusion by nitrogen. This surface hardening
may lead to embrittlement and would occur over some
length of time, for which accurate estimates of rates or
depths would be unlikely. The MCI report showed the
depth of nitriding within the first 19 to 21 points of the
cladding (at 0.02 mm or 0.0007 in. per reading). These
nitrogen percentage values are only indicative of point
measurements following the current service history of
about 9 years, and do not reflect bulk nitrogen chem-
istry. These readings begin at the internal cladding and
extend into the ferritic, and, as noted above, do not pro-
vide an indication of hardness and/or of cracking.
Nitriding observed along the weld overlay on the
AMMONIA TECHNICAL MANUAL
Caibon •
r- f t* « « n U
inside surface of both sides of the girth weld was nor-
mal for this service and was not a factor in the failure.
The inside surface of the clad metal on both sides of
the girth weld showed a very hard, brittle layer with a
depth of 0.007 in. (0.18 mm). Nitriding during service
caused the hard, brittle layer, but the intruded layer was
not found significant to the failure.
In addition to the 7 mils (0.007 in.) depth following
nearly nine years of service, a somewhat confirming
indicator of nitriding rate by a prior formulation can be
applied to produce the graph shown in Figure 20. The
lower curve shows the rate of depth progression for a
relatively thick member; whereas, a higher rate is
denoted for relatively thin-walled members or where
cracking has begun.
The formula (from van Greiken) for this provides a
nitrogen diffusion rate of (Nt depth in \im for t years)
for stainless steels according to process conditions of
temperature (T, kelvin), partial pressure of NH3 (bars),
nickel content (wt. %) and time (t, years). Log(Nt) =
7.69 - 2900/T + 0.67Log(Pnh3) -2.37Log(Ni) +
C*Log(t), where C is 0.5 for thicker or 1.0 or thin (or
surface cracking) members.
The sample results for the above suggest a slightly
greater depth (2 mils/year for 9 years or 18 mils) for
thick stainless steel than actually found, as stated
above. Note also that the ammonia content would have
been about 17%. However, the bare steel exposure left
during the repair is the concern.
In the case of bare steel, the formula is only valid for
stainless, although other experience has shown bare
steels, such as 2 l/4Cr, had a 90 mil (0.090 in.) nitride
depth after nine years exposure at 482°C (900°F) hi
86 2002
 Niobium at ID

Points
Figure 18. Niobium line scan of the cladding on the cracked side of the girth weld,
with the inside surface at the left, confirming the use of E347 for cladding.

Nitrogen at ID

Figure 19. Nitrogen line scan of the cladding on the cracked side of the girth weld,
showing decreasing nitrogen gradient from the inside surface at left.

AMMONIA TECHNICAL MANUAL 87 2002

16% ammonia, while a 5 Cr Nitriding Rate of 8%Ni at 825F/1500psi (total)
received 48 mils in 11% ammonia vs NH3 Content
in a similar exposure time. Of
course, neither of these (penetra- E
«•
,10.00

tion depths) reflects crack occur- n

rence.
1.00
o
Hardness Tests ô

Vickers hardness tests were per-

formed in surveys across the
cracked and intact fusion lines,
Ii
0.10 4
1 2 4 5 6 7 B 9 10 11 12 13 14 15 16 17 18 19 20

%NH3
and across the fusion line of the •Thick •Thin or Cracking
stainless overlay on each side of
the weld, using a 5-kgf load. Figure 20. Rate of depth progression for thick- vs. thin-walled members.
The hardness test results for
Sample 2 are tabulated below and mapped in Table 1. much higher than its counterparts on and near the intact
Except as noted, the interval between test indentations fusion line. The hardness in the weld next to the
was 1 mm (0.040 in.). For ease of reference, the cracked fusion line was also somewhat higher than its
Vickers readings have been converted to Rockwell B or counterparts on the intact side of the weld. No tests
C according to ASTM E 140. were performed in the nitrided layer.
The hardness near the cracked fusion line was high, Cross-sectional views of each side of the weldment

Table 1. Hardness Test Results for Sample 2

Cracked Fusion Line Side Intact Fusion Line Side
Test HV5 Test HV5
No. Location (Rockwell) No. Location (Rockwell)

1 Shell 204 (94B) 16 Tubesheet 181 (89B)

2 Shell 201 (93B) 17 Tubesheet 179 (89)
3 Shell 202 (93B) 18 Tubesheet 196 (92B)
4 0.30 mm from Crack 373 (38C) 19 Weld Fusion Line 243 (21C)
5 0.15 mm from Crack 449 (45C) 20 Weld Fusion Line 229 (98B)
6 0. 15 mm from Crack 368 (38C) 21 Weld Fusion Line 225 (97B)
7 Weld 217 (96B) 22 Weld Fusion Line 226 (98B)
8 Weld 215 (96B) 23 Weld Fusion Line 232 (99B)
9 Weld 216 (96B) 24 Weld 191 (91B)
10 Steel 221 (97B) 25 Weld 195 (92B)
11 Steel 245 (21C) 26 Weld 200 (93B)
12 Cladding Fus. Line 247 (22C) 27 Steel 193 (92B)
13 Cladding 270 (26C) 28 Steel 193 (92B)
14 Cladding 275 (26C) 29 Cladding Fus. Line 233 (99B)
15 Cladding 261 (24C) 30 Cladding 251 (22C)
31 Cladding 246 (22C)
32 Cladding 240 (20C)

AMMONIA TECHNICAL MANUAL 88 2002

to the upper tubesheet (on the right) and the shellside
(on the left), with corresponding hardness readings
below, indicate the basic problem.
Figure 21 shows Photomacrographs (5 1/2X) for
shellside (left) and for tubeside (right) with correspon-
ding Vickers hardness traverses below.
Additional Hardness Testing
As a result of the finding that hardness in the frac-
tured sample 2 varied from the forging on one side of
the weld to the forging on the other side, additional
Vickers tests were performed across the fusion lines
near the inside surface of the nonfailed portion of the
girth seam sample 4. The test interval between indenta-
tions was again 1 mm. Individual test indentations were
also made subsequently along the fusion lines. Since
the shell and tubesheet sides of Sample 4 were not
identified or apparent, we referred to the two sides as A
and B. The readings at all locations indicated similar
hardness, generally below 248 HV 5, which indicated
that both sides of each weld had been stress-relieved.
See Table 2. No hardness testing of the girth weld in the
nozzle sample 5 was performed, because metallograph-
ic examination of this sample had shown that it con-
sisted of austenitic weld metal joining an austenitic
tube.
Discussion
The work performed by Metallurgical Consultants,
Inc., confirmed fracture and cracks along the shell side
of the girth weld in Exchanger 123-C1. The cracks gen-
erally followed the fusion line, and some extended in
an intergranular manner into the shell, at the hardest
locations on the shell side. The microstructure of the
low-alloy steel forging near the girth-weld fusion line
on the shell side showed much higher hardness than the
corresponding tubesheet side, and the bulk carbon con-
tent of the girth-weld metal at the cracked side was
higher than the noncracked side. The microstructure
with high hardness was susceptible to cracking, which
is attributed to hydrogen.
The characteristics of the fracture and cracks and
high hardness of the cracked side indicated that the fail-
ure was caused by hydrogen at low or intermediate
temperatures. It appeared that the apparent absence of
stress-relief predisposed the weld fusion line on the
shell side to failure. There was no evidence of high-
temperature hydrogen attack (HTHA).
The relationship of hydrogen cracking to the con-
struction and operating conditions of the exchanger
was presented by MCI as follows: "Diffusion of atom-
ic hydrogen through steel promoted by high hydrogen
partial pressures may crack microstructures that are
unusually hard or highly stressed at low or intermedi-
ate temperatures. In this case, a narrow zone along the

Table 2. Hardness Test Results for Sample 4

Sample 4. Side A Sample 4. Side B
Test HV5 Test HV5
No. Location (Rockwell) No. Location (Rockwell)

1 Base metal 188 (9 IB) 12 Base metal 207 (94B)

2 Base metal 186 (90B) 13 Base metal 206 (94B)
3 Base metal 187 (90B) 14 Base metal 229 (98B)
4 Fusion line 249 (22C) 15 Fusion line 252 (23C)
5 Weld 195 (92B) 16 Weld 198 (93B)
6 Weld 200 (93B) 17 Weld 195 (92B)
7 Weld 194 (92B) 18 Weld 198 (93B)
8 Fusion line 230 (98B) 19 Fusion line 226 (98B)
9 Fusion line 240 (20C) 20 Fusion line 235 (99B)
10 Fusion line 219 (96B) 21 Fusion line 222 (97B)
11 Fusion line 227 (97B) 22 Fusion line 222 (97B)

AMMONIA TECHNICAL MANUAL 89 2002

 l

Figure 21. Photomacrographs for shellside (at left) and for tubeside (at right), with corresponding Vickers
hardness traverses.

AMMONIA TECHNICAL MANUAL 90 2002

fusion line on the shell side of the exchanger weld was
sufficiently hard to be susceptible to hydrogen crack-
ing. As the operating temperature of the exchanger was
above the normal temperature range for hydrogen
cracking, it appeared that the cracks initiated and grew
during cool-down periods when hydrogen is less
mobile." Similar failures have been documented by
other investigators for these conditions.
Cracks occur preferentially along the weld fusion
line of dissimilar welds not only because of hard
microstructures, but also as a result of the difference in
the solubility of hydrogen in austenitic weld metal
compared to that in ferritic microstructure. Hydrogen
solubility is many tunes higher in austenite than in the
neighboring low-alloy steel. The resulting concentra-
tion of hydrogen along this interface between austenitic
and ferritic microstructures can cause cracks in suscep-
tible microstructures upon cool-down. Generally, many
cycles of exposure to high hydrogen partial pressures
and cool-down are required to cause cracking of dis-
similar welds to the extent that they leak.
The differences in hardness between the shell side
and tubesheet side of the weld are attributed to differ-
ences in thermal history from construction. Although
buttering and stress-relief were reportedly specified for
both sides, it appeared that the shell side of the weld
had been prepared for the final closing weld by butter-
ing, but had been only partially stress-relieved. The
partial stress-relief was indicated by the hardness read-
ings, generally below 248 HV 5 from the shell side
opposite the fracture. In contrast, the hardness and
appearance of the tubesheet side indicated buttering
and stress-relief at both the fractured side and side
opposite the fracture.
Normally, a difference in carbon content between the
two sides of such a weld with different thermal histo-
ries would indicate carbon diffusion from the low-alloy
side into the low-carbon austenitic weld metal.
However, in this case, the higher carbon content was
observed on the hard, cracked side, which apparently
was not stress-relieved. It is possible that there was
greater dilution by the low-alloy steel of the buttering
metal on the cracked side than on the intact side, which
resulted in the higher carbon content. There did not
appear to be any influence of the higher carbon content
in the weld on susceptibility to cracking, since the car-
AMMONIA TECHNICAL MANUAL
bon content of the low-alloy steel on each side was
similar.
The more gradual change in weld-nickel content on
the cracked side than on the intact side also indicated
more dilution, but the significance was not clear. It is
our opinion that the MCI conclusion, stated as wider
compositional gradients on the cracked side, related to
carbon and not nickel. Nickel results showed reason-
ably uniform results while that the variation was dis-
tinctively different only for the carbon. The carbon on
the weld side specifically shows more point readings
involving carbon on the cracked side vs. the uncracked
side. This relates to carbon dilution of the weldment
more than the results for dilution by nickel.
While there have been many published sources
which relate the suitability in applying dissimilar weld-
ments and broadening the range in which these welds
should be suitable, it is also useful to acknowledge that
some sources do recognize problems associated with
these. For example, in a proposal for industry study of
dissimilar weldments, The Materials Property Council
stated the following: "When nickel alloy weld metal is
used to join a low alloy steel boiler tube to an austenitic
stainless steel boiler tube, failure of the joint occurs by
the formation of a planar accumulation of chromium
carbide particles along the low alloy steel/nickel alloy
fusion line. These carbides develop slowly and subse-
quently develop creep cavities surrounding each one.
These cavities grow in size until the cavities link. The
research previously accomplished by MPC has shown
that this weld type shows little or no metallographical-
ly detectable damage at 85% life consumed or later in
component life. Note: The presence of undetectable
damage this late in the expected life of the weld results
hi NDE damage detection at significantly greater than
90% life consumed. This situation results in nickel
based welds being nearly impossible to inspect and
manage using conventional ultrasonic inspection meth-
ods. The development of damage, its detection with
current methods and tube failure, occurs over a short
time interval. This interval can be less than 3 years for
tubes with a life expectancy of 30 years."
For this reason, it is suggested that detection of
cracking may require timely, rather than delayed,
repairs.
The investigation, completed with metallurgical
91 2002
work provided by Metallurgical Consultants, Inc., ana-
lyzed available samples and reached the conclusion
that there was apparently insufficient heat treatment to
reduce and/or avoid small local zones of high hardness.
Based on the information provided to us, neither KBR
nor MCI could conclude that, as one prior theory for a
similar separation stated, there was a "nickel migration
that led to formation of austenite that was subsequent-
ly strained to convert to martensite." In either event, the
resultant limitation was that hard zones did develop
within a narrow fusion line for this case, and, in com-
bination with hydrogen, this caused cracking and sub-
sequent separation.
Furthermore, the low chrome base material was not
found to be damaged by "HTHA" (High Temperature
Hydrogen Attack) as described or defined within the
criteria of API 941 "Recommended Practice," other-
wise known as "Nelson Curves". This form of attack
results in decarburization of the steel with subsequent
development of fissures. The MCI investigation
showed that decarburization was not detected and was
not involved hi the mechanism that resulted in failure.
However, it is advised that using a chrome steel oper-
ating hi a hydrogen environment at a level above the
current API Recommended Practice does require mon-
itoring in order to assure long-term safe operation.
Again, decarburization was not detected during this
failure investigation.
Repairs
The repairs undertaken on the Pusri exchanger did
not repeat the nickel butterpass weldment. The repair
was done by applying a low chrome weldment, which
was subsequently postweld heat-treated. Note that
about six months following these repairs, some shallow
(4 mm maximum depth) outside diameter cracking was
again observed in the fusion zone of the shell to weld-
ment repair. The plant performed grinding and reweld-
ing and re-PWHT was recommended. Due to the boil-
er feedwater supply to the channel, the normal operat-
ing temperature near the weldment which failed is
approximately 427°C (800°F). This is therefore
believed lower than reports such as by Welding
Research Council studies regarding repair cracking in
coarse grain heat affected zones for low chromes oper-
AMMONIA TECHNICAL MANUAL
ating in excess of 441°C (825 °F). These overall repairs
left a small area on the inside diameter exposed to a
nitriding environment, which will harden over time. It
was considered much more manageable than the poten-
tial abrupt separation involving a dissimilar weldment.
For the repaired exchanger, in KBR's opinion, moni-
toring for either microfissures due to decarburization
or for cracking due to high hardness and fissuring
from nitrogen diffusion are essentially equivalent.
Monitoring techniques generally involve ultrasonic
flaw detection and looking for the development of
cracking. Since surface hardening by nitriding (or by
other mechanisms) does not ensure development of
through thickness cracking, it is believed that the prop-
er approach would be to monitor these areas. An exam-
ple is monitoring dissimilar metal weld seams (or at
repairs near prior dissimilar weldments which left a
small zone bare, rather than back-clad with stainless)
for signs of crack initiation. If cracks are observed, they
should be repaired. It should be noted, however, that
some companies offer evaluations wherein cracks
could be evaluated using fitness for service type of
analysis.
H. D. Marsch did an interesting study hi 1982 regard-
ing nitriding for bare low alloy steels (without stainless
protection), and found severe effects in excess of about
410°C (770°F) in tests up to about 5.6 years. While he
noted disbonding of nickel weldments in these envi-
ronments, the testing also showed that nitriding rates
accelerated by a factor of 3 to 5 under higher stress sit-
uations.
Preventative Actions Taken
There have been prior studies on the suitability of
dissimilar weldments. In particular, these have been in
the application of clad or weld overlayed piping for
refinery applications. One recent study noted that
"inspection of the most critical welds using automated
ultrasonic methods during fabrication and shutdowns
are considered necessary to ensure freedom from in-
service cracking". This reference suggests that the
microstructural width of the "Local Hard Zone" is a
determinant in the suitability for similar services. This
shows a narrow zone using nickel base weldments and
wider zones with kon based austenitic butter welds.
92 2002
However, it would be suggested that it will be difficult
to control microstructure patterns within normal fabri-
cation techniques, especially for heavy wall thickness-
es.
While details of heat exchanger fabrication drawings
have not been historically available, Kellogg Brown &
Root, Inc. made a decision to develop and send out an
"Advisory" to operating plants which may have had
similar designs so that appropriate inspections could be
undertaken. Although KBR received responses from a
few operators, the specific shellside dissimilar weld-
ment was apparently only involved in two designs pro-
vided for the two facilities in Indonesia by different
fabricators in Italy. In response to the survey, one oper-
ator advised KBR that they have similar weldments in
synthesis loop services which are undergoing routine
inspection programs. They noted that they may be fol-
lowing similar studies by TNO, The Netherlands, in a
report entitled "Integrity of Austenitic/Ferritic dissimi-
lar welded joints in hydrogen services" (Apr. 27,1998).
KBR is also aware of some separations involving
reformer (fired heater) tube tops, which also employ a
dissimilar weldment transition.
KBR has not been advised of any further shellside
dissimilar weldments or problems with shells or inlet
transitions for these exchangers. Recent and current
Kellogg Brown & Root, Inc. designs have not and do
not apply the specific heavy wall thickness closing
seam detail as were applied in the exchangers investi-
gated. Where similar transitions cannot be avoided,
particular attention needs to be paid to thermal history
of the materials, welding parameters, and final heat
treatment.
Acknowledgement
A substantial portion of this report, including all of
the metallurgical laboratory work, was taken from an
investigation completed for the failure and reported by
Mr. Mark Buehler of Metallurgical Consultants, Inc. in
Houston, TX.
Literature Cited
APIRP941 Recommended Practice 941, Steels for
Hydrogen Service at Elevated Temperatures and
AMMONIA TECHNICAL MANUAL
Pressures in Petroleum Refineries and
Petrochemical Plants, 5th ed., Supplement 1 (April,
1998).
AWS Welding Handbook, "Materials and Applications-
Part 2," Vol. 4, AWS, pp. 353-362 (1998).
Buehler, W. M., "Examination of Failed Weld from
123-C1 Ammonia Converter Effluent Steam
Exchanger," Pusri-lB, Palembang, Indonesia,
Metallurgical Consultants, Inc., MCI Report 20
(Nov. 2000).
Craig, B. D., and R. B. Setterlund, "Catastrophic SSC
Failure of a Dissimilar Metal Weld in High-Pressure
Hydrogen Vessel," Corrosion/91, Cincinnati, OH
(Mar. 1991).
Grotz, B. J., and G. R. Prescott, "Disbonding between
5Cr-l/2Mo and Inconel and Nitriding of
5Cr-l/2Mo," Ammonia Plant Safety & Related
Facilities, Vol. 33, AIChE, New York (1993).
Hotman, E., and Ismudjoko, "Failure of
Inlet Nozzle 123-C1 Ammonia Effleunt Steam
Generator," Ammonia Plant Safety & Related
Facilities, Vol. 41, AIChE, New York (2001).
http://www.forengineers.org/mpc/dis_metal_welds/dis
_metal_welds.htm (May 2000).
Lang, M. C, E. Yelverton, D. Hansen, and J. Sievert,
"Inspection of C-l/2Mo Components for Hydrogen
Damage," Ammonia Plant Safety & Related
Facilities, Vol. 32, AIChE, New York (1992).
Lewis, K. R., R. W. J. Koers, H. C. van Wortel, and
A. H. M. Krom, "Assessment of Operating Limits
for Critical Dissimilar Metal Welds in a
Hydrocracker," NACE International Paper 01532,
CORROSION/2001.
Lochhead, J. C., and Ken Rodgers, The Practical
Welding Engineer, AWS, p. 95 (2000).
Lundin, C., P. Liu, C. Y. P Qiao, G. Zhou, K. K. Khan,
and M. Prager, "An experimental Study of Causes
and Repair of Cracking of 1 l/4Cr-l/2Mo Steel
Equipment," WRC Bulletin, 411 (May 1996).
Marsch, H. D., "Nitriding of Steels," Plant Operations,
1(3), (July 1982).
Penuela, L. E., J. G. Chirinos, and J. D. Dobis,
"Analysis of Dissimilar Welds Exposed to High
Temperature H2/H2S Conditions in a
Hydrodesulfurizing (HDS) Unit," NACE
International, Paper 383, CORROSION/1999.
93 2002
Prescott, G. R., and Brian Shannon, "Process
Equipment Problems Caused by Interaction with
Hydrogen," Ammonia Plant Safety
& Related Facilities, Vol. 41, AIChE, New York
(2001).
QUESTIONS AND ANSWERS
Pan Orphanides, Orphanco: Heat input during butter-
ing shall be considered: according to the Schaeffler dia-
gram, high dilution of base metal forms martensitic
structures having high hardness values and is not easy
to eliminate by PWHT. Has this aspect been considered
in the analysis?
Jim B. Sievert, Kellogg Brown & Root: Thank you for
your comment/question regarding whether we consid-
ered the possibility of predicting a result of martensite
formation in relation to the Schaeffler diagram due to
high heat input welding. The short answer is "not
directly". However, the undertaking of EDS Chemical
analysis plotting across the separation zone was specif-
ically an attempt to discover this type of result as was
examining microstructures for narrow or wide hard
bands in the interface zone. The metallurgical laborato-
ry determined no specific Schaeffler diagram correla-
tion. Hard zones were determined at the failure, and
nonhard zones in unfailed zones. We could not conclu-
sively suggest that, following nine years of service, the
original welding heat-input was excessive which might
have lead to dilution effects that resulted in martensite.
Nor could we also conclusively suggest that the forging
was properly heat treated originally, or that the original
weld heat treatment was satisfactory. Rather, it was
suggested that the high hardness remained owing to
poor prior thermal history. The point of the presentation
was to advise of a potential inherent inability to control
AMMONIA TECHNICAL MANUAL
van Greiken, C. A., "Factors Controlling the Nitriding
of Stainless Steels in Ammonia Synthesis Loops,"
Ammonia Plant Safety & Related Facilities, Vol. 29,
AIChE, New York (1989).
and/or sufficiently detect susceptible microstructures in
production welds that would later be applied in envi-
ronments that might lead to abrupt and catastrophic
failure. It is believed that bi-metallic weldments in high
temperature/pressure hydrogen environments may
eventually be more susceptible to embrittlement and/or
disbonding. However, there are many instances of dis-
similar weldments in HP/HT hydrogen environments in
refinery processes connecting piping to reactor pressure
vessels, which apparently have not experienced similar
effects. We believe, where dissimilar welds are found in
synthesis gas environments, they should be routinely
examined or monitored by appropriate means, such as
UT. In addition, while the article specifically deals with
a thick-walled dissimilar weldment for the shell of the
heat exchanger, we presented information related to
other similar cracking for three different forging
sources and fabrications by two different vendors. The
separations found only involved one-half of one zone of
the nickel butterpass welds on shell-side forgings and
on a nozzle forging. We believed it would be rather
coincidental to suggest that different fabricators
achieved excessively high heat inputs in nearly identi-
cal locations at different fabrication shops for some-
what similar designs. Had that been the case, it would
have seemed likely that the nearly identical weld zones
on the tubesheet forging may also have been affected,
but these were not.
94 2002