International Journal of Pressure Vessels and Piping 81 (2004) 499–506

www.elsevier.com/locate/ijpvp

In service embrittlement of cast 20Cr32Ni1Nb components used

in steam reformer applications
D.M. Knowlesa, C.W. Thomasa,*, D.J. Keenb, Q.Z. Chenc
a
Materials Performance Technologies, P.O. Box 31310, Lower Hutt, New Zealand
b
Plant Reliability Solutions, P.O. Box 263, Carina, Qld 4152, Australia
c
University of Hong Kong, Pokfulam Road, Hong Kong, China

Abstract
Severe embrittlement has been experienced in a number of cast manifold components. This has manifested itself as cracking at tee to
manifold connections. Attempts to weld repair proved futile leading to concern about the integrity of the entire system. This experience
contrasts with similar components that have successfully remained in service for many years. The paper describes the investigations into
these failures and laboratory investigations into the properties of cast 20Cr32Ni1Nb alloys. Results indicate that variations in alloy chemistry
within the stated allowable range are sufficient to cause embrittlement.
q 2004 Elsevier Ltd. All rights reserved.
Keywords: Embrittlement; Creep–fatigue

1. Introduction of a reformer and an outlet manifold system. Traditionally

Steam reformer furnaces are at the front end of a number of
industrially important processes. These furnaces take a
supply feed of methane and steam and ‘reform’ them to
hydrogen and carbon monoxide which subsequently become
the basic building blocks in industries such as ammonia,
methanol, DR iron production and petroleum refining. A
typical reformer furnace consists of an array of vertical tubes
in a firebox. The smallest furnaces may have only ten such
tubes but the largest, with up to 700 tubes, are very significant
and capital intensive items of plant. These tubes contain a
catalyst and the feed gas flows internally from the top to the
bottom. Effectively, each tube behaves as a separate reactor.
At the bottom of the furnace, the various tubes are all
connected to a system of manifolds that collects the gas into a
single stream for distribution to further processing units. The
operating temperatures required in these furnaces are high.
Skin temperature of the reformer tubes is approximately 850 –
950 8C and gas outlet temperatures are around 760 –850 8C.
These temperatures and the need to operate reliably for
scheduled campaigns of possibly five years put huge demands
on the materials of construction used in these furnaces.
The present paper addresses problems encountered in the
outlet manifold system. Fig. 1 shows a schematic illustration
* Corresponding author. Tel.: þ 64-4-569-0027; fax: þ64-4-569-0431.
E-mail address: c.thomas@matperf.com (C.W. Thomas).
0308-0161/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijpvp.2003.12.025
manifold components have been manufactured from
wrought alloy 800H or 800HT. As systems have increased
in size, there has been a shift to the more economic and
nominally better performing cast 20Cr32Ni1Nb alloy which
has become an industry standard. This alloy is offered by a
number of manufacturers using various trade names but in
reality, there is little variation between them.
2. The alloy
The material is covered by ASTM Standard A351-94
where it is described as alloy CT15C. Reference to this
standard, however, is rarely made and the material is more
commonly identified by its various trade names such as
CR32W or KHR32C. This standard describes composition
and manufacturing requirements but makes no reference to
elevated temperature mechanical properties.
The material is essentially, a cast version of alloy 800.
Alloy 800 contains 20% chromium and 32% nickel with an
upper limit of 0.1% carbon. It is a solid solution alloy but
also contains small amounts of aluminium and titanium
which lead to the formation of carbides and sometimes,
a small amount of gamma prime g0 phase. The ‘H’ and ‘HT’
grades involve manipulation of grain size and minor
variations in the carbon, aluminium and titanium content.
500 D.M. Knowles et al. / International Journal of Pressure Vessels and Piping 81 (2004) 499–506

Fig. 1. Schematic illustration of a reformer furnace [1].

Table 1
Chemical compositions of CT15C and alloy 800H

%C %Cr %Ni %Si %Mn %Nb %Ti %Al

CT15C 0.05–0.15 19–21 31–34 0.5 –1.5 0.15– 1.5 0.5–1.5

800H 0.1 max 19–23 30–35 1.0 max 1.5 max 0.15–0.6 0.15–0.6
Sample 0.11 19.74 31.37 1.03 0.90 0.98

The adoption of a cast variant saw the use of similar levels
of the prime alloying elements, chromium and nickel.
Titanium and aluminium were not used in the cast variant.
However, in parallel with the development of spun cast
reformer tube alloys involving alloying with small amounts
of niobium, the manifold alloy similarly was alloyed with
approximately 1% of niobium to improve creep properties.
Table 1 lists chemical composition requirements of
ASTM A351 alloy CT15C and compares them with the
wrought alloy 800H. The similarities are clearly shown.
There are no standardised creep or stress rupture
properties for the cast 20Cr32Ni1Nb alloy. Instead,
designers are required to make use of data supplied by
manufacturers. Alloy 800 on the other hand, has been in use
for many years and stress rupture data is available from
a number of sources. Fig. 2 shows a comparison of
published stress rupture data for the cast material (based
on a manufacturer’s data) and the wrought alloy 800H [2]
(based on API 530 data). According to these data, the
expected life of the cast material is an order of magnitude
higher than that of the wrought material at typical design
stress levels around 10 MPa.
3. The problem
The problem that was encountered with this material was
severe in-service embrittlement. After only relatively short
periods in service, routine inspection at scheduled plant
outages led to the discovery of cracking at the weldments

Fig. 2. Comparison of stress rupture data for cast alloy CT15C and wrought alloy 800H.
 D.M. Knowles et al. / International Journal of Pressure Vessels and Piping 81 (2004) 499–506 501

Fig. 3. Schematic illustration of typical manifold and bull-T arrangements.

connecting the main manifold arms to the bull-T. The bull-T What was not expected, however, was the extreme
typically connects the arms of the manifold to the main brittleness of the parent bull-T material. Attempts to grind
transfer line. Typical schematic manifold/bull-T arrange- out and re-weld the damage simply led to the generation of
ments are shown in Fig. 3. Fig. 4 shows a bull-T in position more cracks as can be seen in Fig. 6.
below the furnace. This problem was encountered at two It is not uncommon for in-situ solution anneal heat
independent plants. treatments to be conducted on these materials to improve
In service, the manifold undergoes significant thermal weldability. The temperature required, however, is in excess
expansion. The tube to manifold pigtail connections, of 1100 8C and a recent recommendation was that this
despite being deliberately flexible to account for thermal should be increased to 1200 8C. Such heat treatments can be
expansion loads are numerous and, in acting together, are readily done for small areas in the immediate vicinity of the
capable of exerting significant system loads on the weldment. This did not, however, provide confidence that
manifold. These thermal loads lead to significant bending the remaining parts of the manifold system were sufficiently
applied to the manifold arm to bull-T weldment and it is ductile to ensure their integrity when returned to service.
not uncommon for cracking to be found at this location.
The most common failure mode in these manifold
systems is in fact, creep – fatigue at the welds and this
was found to have occurred at two independent plants.
Fig. 5 shows the sort of cracking that was observed.
Based on the stress rupture data shown in Fig. 2, an
effective life of 5 years and a service temperature of
760 8C, an approximate mean stress of 45 –50 MPa is
implied. This is significantly higher than pressure based
hoop stresses which are typically below 10 MPa and upon
which design is based and indicates the relatively high
level of thermal stress.

Fig. 4. Typical bull-T. Fig. 5. Creep fatigue crack.

502 D.M. Knowles et al. / International Journal of Pressure Vessels and Piping 81 (2004) 499–506

Fig. 6. Cracking after and during attempted weld repair. Fig. 7. Charpy impact data.

This, led to the decision in both cases investigated, that the service temperature. The intention was to determine if
temporary repairs should be made until such time that the apparent loss of ductility was a low temperature
replacement components could be installed. One of the bull- phenomenon or if toughness was also compromised at
Ts was made available for metallurgical investigation. It had service temperatures. Tensile testing similarly was under-
been in service for approximately 5 years at service taken at room temperature and at 800 8C to simulate service
temperatures of approximately 760 8C. The analysis of conditions.
this material is included in Table 1. The solution annealing heat treatment involved holding
at 1100 8C for 3 h followed by air cooling. The small
laboratory specimens were removed from the furnace and
4. Mechanical testing cooled relatively rapidly in air.
The Charpy impact test results are listed in Table 2 and
The issue of concern was apparent extremely low illustrated in Fig. 7. The tensile test results are contained in
ductility that led to an inability to weld the bull-T without Table 3.
cracking. Consequently, the mechanical testing undertaken The Charpy data exhibited some scatter. However, while
to date has concentrated on toughness using Charpy impact there was a modest increase in toughness with increasing
testing on standard 10 £ 10 mm samples. In addition, a temperature, the toughness as revealed by impact testing
series of tensile tests have also been undertaken. The testing remained low even at temperatures close to the operating
has been conducted on the material removed from service temperature. The tensile data also revealed extreme
(as received) and after a solution annealing heat treatment. brittleness at room temperature for the as-received ex-
For the as-received material, a series of Charpy impact tests service material with no measurable elongation on the test
were undertaken at a series of temperatures approaching piece itself. The stress –strain curve for this sample showed
a plastic strain of less than 0.4%. Only one test was
Table 2
undertaken for this condition because the material was so
Charpy Impact Results
brittle, the duplicate specimen failed during machining.
Condition Temperature (8C) Impact energy J The as-received material however, had significant ductility
at service temperatures. In fact, the elongation and reduction
Annealed 23 32
Annealed 23 38 Table 3
Annealed 23 26 Tensile test results
Ex service 23 6
Ex service 23 9 Condition Temperature UTS 0.2%Proof % Elong % ROA
Ex service 23 7 (8C) (MPa) (MPa)
Ex service 105 14
Ex service 200 11 Sol annealed 20 340 158 15 13
Ex service 295 13 Sol annealed 20 16 15
Ex service 320 20 Sol annealed 800 180 91 39 45
Ex service 390 10 Sol annealed 800 171 80 39 54
Ex service 590 12 Ex service 20 200 177 0 0
Ex service 710 25 Ex service 800 171 80 51 55
Ex service 760 10 Ex service 800 174 82 34 33
 D.M. Knowles et al. / International Journal of Pressure Vessels and Piping 81 (2004) 499–506 503

Fig. 8. As-cast 20Cr32Ni1Nb.

Fig. 9. 20Cr32Ni1Nb alloy after 1 day at service temperatures.

of area results were as high or higher for the as-
received material than the solution annealed test pieces at
800 8C.
5. Metallography
The microstructure of 20Cr32Ni1Nb consists of an
interdendritic network of primary carbides in an austenitic
matrix. The microstructure is illustrated in Fig. 8. Despite
the interdendritic eutectic carbides and the relatively low
carbon content of this material, the austenite matrix is
typically supersaturated with carbon and some fine intra-
dendritic carbides can be seen in the matrix.
The density of intra-dendritic carbides typically
increases dramatically when the material first enters service.
Fig. 9 shows a similar sample to that shown in Fig. 8 except
that it has been held at 800 8C (approximate service
temperature) for 24 h.
The number and density of intra-dendritic secondary
carbides is extremely high. It is these carbides and the
complexity of the interdendritic eutectic carbides that have
been attributed with generating the good creep properties of
similar alloys [3].
In the ex-service material, the relatively long term aging at
approximately 800 8C had led to the agglomeration and
dissolution of many of the intra-dendritic carbides. A
significant number however, remain as can be seen in Fig. 10.

Fig. 10. 20Cr32Ni1Nb alloy ex-service.

504 D.M. Knowles et al. / International Journal of Pressure Vessels and Piping 81 (2004) 499–506
Fig. 11. 20Cr32Ni1Nb alloy ex-service and solution annealed.
The in-service exposure has not led to wholesale changes in the
microstructure. It is considered significant, however, that the
network of primary carbides appears continuous in many areas
and has adopted a two phase appearance.
After solution annealing (3 h at 1100 8C), the microstruc-
ture has again not changed in any major way. The density of
intra-granular secondary carbides remained similar to the ex-
service material except a precipitate free zone has developed
adjacent to the primary carbides. In addition, the dual phase
nature of the eutectic carbides was removed and the strings of
interdendritic precipitate that were present in the ex-service
material tended to break up into discreet particles (Fig. 11).
As part of an on-going program to understand the
microstructure of this alloy, the ex-service material has
been examined using a scanning electron microscope.
The dual phase nature of the primary carbides was
evident as illustrated in Fig. 12 which shows an example
of primary eutectic precipitation viewed using the back
scatter detector to highlight atomic weight differences.
Analysis of these precipitates using an energy dispersive
X-ray analysis system in conjunction with the SEM
showed the two phases within the precipitates to be
strongly segregated (Fig. 13). One was chromium rich
while the other was essentially free of chromium and
contained niobium and silicon. This silicon/niobium rich
phase was not found in the as-cast or solution annealed
materials.
6. Discussion
The Charpy impact testing confirmed the brittle nature
of the ex-service material. There was a modest improve-
ment in toughness with increasing temperature but the
impact energy of the ex-service material was always
below that of the solution annealed material. The low
ambient temperature tensile tests also showed the ex-
service material to be extremely brittle with no measur-
able elongation being recorded on the test pieces. It was
of interest however, that in tensile tests at 800 8C, tensile
ductility of ex-service material was high. The solution
annealing heat treatment re-established a significant level
of toughness. These mechanical test results are consistent
with the observation that the original bull-T was
extremely difficult to weld. However, the relatively high
tensile ductility at operating temperatures suggest that
integrity at operating temperature is not an issue. Thermal
loads at start up or shut down however may lead to
cracking while the bull-T is relatively cold.
The metallographic examination revealed no immedi-
ately obvious reason for the embrittlement. More in depth
examination however, revealed the presence of a silicon and
niobium rich phase in the interdendritic precipitates. These
materials are part of an on-going investigation to charac-
terise the microstructure and establish the influence of these
phases on material properties. Similar phases in
20Cr32Ni1Nb have however been identified by other
workers[4,5] who have identified the silicon rich phase as
‘G-phase’ reported to be Ni16Nb6Si7. In similar but higher
carbon alloys such as HP50Nb reformer tube materials [6],
the silicon rich phase was identified as a silicide having an
h-carbide (M6C) structure.. In all these cases, extreme
brittleness at ambient temperatures have resulted.
It is concluded therefore that the problem of brittleness in
the outlet manifold components examined was caused by
Fig. 12. SEM backscattered electron image of primary eutectic interden-
dritic precipitates in ex-service material.
 D.M. Knowles et al. / International Journal of Pressure Vessels and Piping 81 (2004) 499–506
Fig. 13. Element map showing distribution of silicon, chromium and niobium in interdendritic precipitates in ex-service material.
the formation of intermetallic niobium rich silicide phases.
The observation that improvement in weldability can be
obtained by solution annealing is consistent with the
observation that these silicide phases were not present in
the solution annealed samples.
Based on the observations made, the formation of these
deleterious phases can be considered a normal consequence
of in-service aging. This is clearly an undesirable situation.
It has been suggested [4] that the formation of the silicides
can be controlled if not prevented, by ensuring that the
niobium level is maintained below that necessary to
stoichiometrically accommodate all the carbon as NbC,
i.e. the wt% ratio of niobium to carbon should be held below
7.7. The observation of silicides in HP50Nb materials where
the carbon content is higher at 0.4– 0.5% would suggest that
this is not sufficient to prevent the formation of silicides.
It would appear that niobium is a prerequisite for the
formation of silicides. It is therefore questioned why
niobium needs to be used in this application at all. Alloying
of cast alternatives to alloy 800 with niobium appears to
have been adopted by manufacturers because of experience
with tube alloys and an apparent improvement in creep
properties that this produces. Experience with HP50 alloys
[7] has shown that in aged materials, the stress rupture
strength of tube materials are not significantly better than in
the niobium free versions, i.e. any strength advantage
gained by alloying with niobium is soon lost once the tubes
have entered service, probably because of the formation of
intermetallic silicides. In addition, in manifold components,
wall thickness is not important and strength can therefore be
obtained by design rather than material strength.
505
However, more work is clearly required before the use of
niobium alloyed materials should be condemned in this
application. For example, a benefit that has been observed in
the performance of aged niobium alloyed materials is their
relatively good creep ductility [7]. This property is
important in maximising resistance to creep fatigue, which
after all, was the problem that initiated this investigation in
the first place. The good high temperature ductility of the
20Cr32Ni1Nb material is suggested by the high tensile
ductility of the ex-service material which was superior to the
solution annealed material.
7. Conclusions
20Cr32Ni1Nb cast material has become an industry
standard for reformer furnace outlet manifold components
In-service aging of this material, however, leads to serious
embrittlement that yields the material unweldable. This
problem can be at least mitigated by solution annealing at
temperatures in excess of 1100 8C, but this is not practical
for complete outlet manifold systems which remain
embrittled. Furthermore, solution annealed materials are
likely to re-embrittle on further exposure.
The cause of the embrittlement is the formation of
niobium rich silicide intermetallics which have also been
observed in closely related HP50Nb reformer tube alloys.
The presence of niobium appears to be a prerequisite for the
formation of these intermetallics. It is therefore suggested
that niobium free grades are developed to avoid the problem
of in service embrittlement.
506 D.M. Knowles et al. / International Journal of Pressure Vessels and Piping 81 (2004) 499–506

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