Properties and Microstructures of

Outlet Manifold Components

A metallurgical evaluation was performed on centrifugal cast 20Cr, 32NÎ, INb outlet manifold
components. The components were examined after 21 and 192 months aging in a hydrogen
reformer. The tensile properties, Charpy impact, stress rupture strengths, and microstructures were
evaluated on the aged material and after solution annealing treatments at 1,900°F (1,038°C),
2,000°F (1,093°C), 2,100°F (1,140°C), and2,200°F (1,204°C). The results of this investigation are
presented and the influence on serviceability and weldability are discussed.

John J. Hoffman
Air Products and Chemicals, Allentown, PA 18195

G. £. Gapinski
MetalTek International, Waukesha, WI 53188

Introduction cracks developed hi one inlet leg of the tee. The cracks
were ground out, the tee was given an in-situ solution

A
n extensive metallurgical analysis was per-
formed on segments of a hydrogen reformer
outlet manifold system. The outlet manifold
contained synthesis gas at 1,600°F (870°C) and had
been in service up to 16 years (192 months). The com-
ponents examined consisted of two manifold segments,
labeled as Manifold-end and Manifold-center, and a
tee. The chemical compositions are listed in Table 1.
Wisconsin Centrifugal manufactured the manifold
using centrifugal cast alloy 20-32Nb pipe, tee, and out-
let cone components. The overall length of the mani-
fold was 37 ft (11.3 m). The inlet legs were 5.468 in. ID
x 1.125 in. thick (138.9 mm x 28.58 mm) centrifugal
cast pipe with alloy 800H wrought fittings. The center
outlet tee was 14.3 in. OD x 8 in. ID (363.2 mm x
204.8 mm) with a centrifugal cast reducer (Figure 1).
The manifold was installed in 1983. In 1996, fatigue
anneal of 2,100°F (1,150°C) for 3 h and repair welded.
The repaired manifold operated without incident until
it was replaced as part of a major furnace rebuild in
February 2000. The manifold system was installed for
17 years. Considering typical plant downtime, it was
estimated that the manifold was operated at tempera-
ture approximately 16 years (192 months).
A metallurgical evaluation was performed on the cast
material removed with up to 192 months aging to
observe the extent of secondary precipitates and to
quantify the effect of the precipitates on the mechani-
cal properties and weldability. The results obtained
were compared to cast 20Cr32NilNb material previ-
ously analyzed after only 21 months aging (Hoffman,
2000).

AMMONIA TECHNICAL MANUAL 10 2002

 Table 1. Chemical Compositions of Cast Components, wt %

Element As-Cast Tee Manifold-End Manifold-Center

Cr 19.0-21.0 21 21 21
Ni 31.0-34.0 32 32 32
Nb 0.90-1.35 1.30 1.08 0.93
C 0.06-0.12 0.09 0.08 0.08
Si 0.50-1.00 0.8 0.9 0.6
Mn 0.50-1.50 1.0 0.9 0.9
Fe Bal. Bal. Bal. Bal.
Ti - 0.13 0.01 -

Nb/C 14.4 13.5 11.6

Experimental Procedure in an electric furnace. The samples were removed from

Metallographie cross sections were prepared from
the aged tee and manifold pipe sections. AU métallo-
graphie specimens were polished to a 0.05-micron fin-
ish. The microstructures were characterized using opti-
cal microscopy and scanning electron microscopy
(SEM). Elemental chemical analysis of the bulk matrix
and precipitated phases were performed using energy
dispersive X-ray spectroscopy (EDS). Phase identifica-
tion was performed using electron backscattered dif-
fraction (EBSD) in the SEM. The phases were identi-
fied by the Kikuchi patterns obtained from the EBSD
analysis. Additional phase identification was performed
by selective etching and/or extractive metallography.
Conventional x-ray diffraction (XRD) was performed
on the extracted residues.
The effect of the precipitated phases on the mechan-
ical properties of the aged cast material was determined
via conventional room temperature tensile testing.
Charpy impact and accelerated stress rupture tests were
also performed on the aged material. Weldability test-
ing was also performed on the aged material by
depositing stringer beads of Inconel 617 using the
tungsten inert gas method. Followup metallography
was performed to investigate the propensity of crack-
ing in the weld heat-affected zones.
Samples of the aged components were solution
annealed for 3 h at 1,900°F (1,038°C), 2,000°F
(1,093°C), 2,100°F (1,140°C), and 2,200°F (1,204°C)
the furnace at the end of the treatment and air cooled to
ambient temperature. Additional samples were solution
annealed at 2,100°F (1,140°C), furnace cooled to
below 1,000°F (538°C), removed from the furnace and
cooled to room temperature. Thermocouples were
attached to the samples to monitor the heat treatment
temperature and the cooling rate of the coupons.
Cooling rates of 250°F (139°C) / min. were observed
for the air cooled samples. The furnace cooled samples
had a cooling rate of 4.3°F (2.4°C) / min. from 2,100°F
(1,140°C) to 1,000°F (538°C) followed by a 250°F
(139°C) / min. cooling rate to room temperature.
Metallographie analyses were performed on samples
representing the manifold tee, manifold-end, and man-
ifold-center. Mechanical property evaluations were per-
formed on tee and manifold-end samples. Room tem-
perature tensile tests, Charpy impact tests, and acceler-
ated stress rupture tests were performed on samples in
the aged and solution annealed conditions. Sample
locations are shown in Figure 1.
Results
The as-cast microstructure of the 20Cr32NilNb
material typically consists of an austenite matrix with
primary niobium carbide (NbC) and chromium carbide
(typically M7C3 or M23Cg). Optical microscopy per-
formed on polished cross sections of the manifold and

AMMONIA TECHNICAL MANUAL 11 2002

 Figure 1. Reformer outlet manifold system.

tee after aging revealed abundant intra- and interden- metallic silicides in the aged tee finding all of the pre-
dritic second phase precipitates in the microstructures. cipitates analyzed to have a face-centered cubic (fee)
The precipitated phases were observed through the crystal structure with a lattice parameter of 11.2Â. The
entire thickness of the aged components. However, a crystal structure and lattice parameter measured were
greater concentration of intradendritic precipitates was consistent with published data on two intermetallic sili-
observed adjacent to the ID surface of the tee (Figure cide phases, G-phase (NiigNb7Si6) and rj'-phase
2). (Nb3Ni2Si). The chromium carbide phases (dark phase
SEM examination (using backscattered electron in Figure 3) could not be identified by EBSD. Selective
imaging) of the aged tee cross section in the as-pol- etching techniques were employed for identification of
ished condition clearly revealed the multiple interden- the chromium carbide phase. The response to electro-
dritic precipitates (Figure 3). Elemental chemical
analysis using EDS indicated the dark pre-
cipitates (see Figure 3) were chromium
carbides, while the white precipitates were
niobium carbides. The EDS analysis also
indicated that the medium gray phase
located at the periphery of the niobium
carbides was highly enriched in nickel
(Ni), niobium (Nb), and silicon (Si). Thus,
the interdendritic precipitates appeared to
be an intermetallic silicide phase(s). The
intradendritic precipitates were very
small, inhibiting reliable chemical analy-
sis. However, EDS analysis suggested the
intradendritic precipitates were chromium
and niobium carbides. The tee also con-
tained 0.13 wt. % titanium that enabled
the formation of titanium carbonitrides
(TiCN). The EDS analysis found a no-
table Nb content in the carbonitride parti-
Figure 2. Micrograph showing abundant secondary precipitates
cles indicating Nb substituted for Ti form-
at the ID of the aged tee.
ing (TiNb)(CN) particles. (Oxalic, acid, 500X original magnification).
EBSD was performed on the inter-

AMMONIA TECHNICAL MANUAL 12 2002

 Figure 3. SEM micrograph showing typical interdendritic
precipitates in the aged tee.

Figure 4. SEM micrograph of typical interdendritic precipitates

in the aged manifold-end section.

AMMONIA TECHNICAL MANUAL 13 2002

etching in a chromic acid (CrO3) solution indicated the phases.
carbide phase was the M23C6 type. XRD analysis of Microstructural analyses were also performed on the
extracted residues found an abundance of NbC with a solution annealed samples. Scanning electron
second phase having a lattice parameter of 11.27Â. The microscopy of the tee and manifold-end sections
lattice parameter indicated the second phase in the annealed at 1,900°F found the interdendritic chromium
extracted residue was the intermetallic suicides. carbides partially dissolved into solid solution.
However, M23C6 was not identified via XRD analysis However, a small concentration of the interdendritic
suicide precipitates remained at the periphery of the
of extracted residues.
NbC's. SEM examination of the samples annealed at
Similar microstructural evaluations were performed
2,000°F, 2,100°F, and 2,200°F found all of the inter-
on the manifold-end section. The microstructure of the
dendritic chromium carbide and intermetallic silicides
manifold-end section appeared to have fewer intraden-
phases effectively returned to solid solution. The NbC
dritic second phase precipitates as compared to the tee.
precipitates generally became smaller in diameter and
EDS and EBSD analysis of the interdendritic precipi-
acquired an unusual morphology as the annealing tem-
tates found chromium carbides, a large amount of inter-
perature increased. Ti(CN) precipitates were observed
metallic suicide phases, and a notable decrease in NbC
hi the tee section, which contained 0.13 wt. % Ti, after
concentration. The intermetallic suicide phase
all of the annealing temperatures.
appeared to essentially replace the niobium carbide
The minimum room temperature tensile properties
phase along the dendrite boundaries (Figure 4). The
for this alloy in the as-cast condition are an ultimate
manifold-center section microstructure was representa-
tensile strength (UTS) of 65 Ksi (448 MPa), yield
tive of as-cast material. The microstructure contained
strength of 27 Ksi (186 MPa), and 25% elongation.
the typical eutectic niobium carbides with minimal
Room temperature tensile tests were performed on
intradendritic precipitates and no intermetallic suicide

Table 2. Tensile Properties of Components in the Aged and Annealed Conditions*

Component Condition**,' UTS, Ksi (MPa) Yield, Ksi (MPa) Elong. (%)
As-Cast (min.) 65 (448) 27 (186) 25

Tee Aged 42.7 (294) 25.5 (176) 7.3

SA at 1,900F/AC 69.5 (479) 31.7(219) 25.8
SA at 2,OOOF/AC 60.9 (420) 25.8 (178) 28.0
SAat2,100F/AC 72.9 (503) 29.5 (203) 36.8
SAat2,100F/FC 70.3 (485) 28.3 (195) 27.0
SA at 2.200F/AC 69.1 (476) 25.5 (176) 35.8

Manifold-End Aged 48.3 (333) 29.2 (201) 7.0

SA at 1,900F/AC 74.2(512) 30.7 (212) 37.6
SA at 2,OOOF/AC 74.9(516) 37.3 (257) 41.0
SA at 2,100F/AC 75.3 (519) 32.0 (221) 44.6
SA at 2,100F/FC 75.0(517) 28.2 (194) 39.6
SA at 2,200F/AC 75.3(519) 32.8 (226) 41.1
Notes:
* All tensile test performed at room temperature.
** SA = solution annealed; AC = air cooled; FC = furnace cooled.
' Solution annealed samples were held at temperature for 3 h.

AMMONIA TECHNICAL MANUAL 14 2002

samples machined from the tee and manifold-end sec- (61.4 MPa). Test conditions using a minimum life of
tions in the aged condition showed significant degrada- 150 h were calculated from the Larsen-Miller stress
tion in elongation and UTS as compared to the speci- rupture curve published for this alloy. The manifold tee
fied minimum as-cast values. The most severe decreas- samples exhibited the lowest rupture life for each test
es in mechanical properties occurred in the tee, which condition. The best rupture life was obtained with the
had a 34% decrease in UTS and a 71% decrease in 2,200°F (1,204°C) anneal treatment. Test samples in
elongation. The yield strengths of the components gen- this condition were the only manifold tee samples to
erally remained near the minimum as-cast value (see exceed the 150 h minimum life. Manifold-end samples
Table 2). exceeded the desked minimum life after annealing at
Tensile test results indicate property recoveries 2,100°F (1,140°C) and 2,200°F (1,204°C). The aged
approaching minimum as-cast values with the 1,900°F samples and the 1,900°F (1,038°C) and 2,000°F
(1,038°C) annealing treatment. Continued tensile prop- (1,093°C) solution annealed samples exhibited similar
erty improvements were evident as the annealing tem- rupture properties. Stress rupture tests were not con-
peratures increased. The best properties were observed ducted for the 2,100°F (1,140°C) furnace cool condi-
with annealing temperatures of 2,100°F (1,140°C). The tion. Accelerated stress rupture test values are shown in
highest ductility was observed after the 2,200°F Table 4.
(1,204°C) solution anneal. Tensile properties for the Weldability testing was performed on the aged spec-
furnace cooled samples were lower than the correspon- imens using a conventional bead-on-plate method.
ding air cooled samples. Inconel 617 filler metal was deposited on the surface of
Charpy V-notch impact testing is not required for this three aged components using the gas tungsten arc
application, but was included in this study
to measure material toughness. Compar- Table 3. Charpy V-Notch Impact Properties in the Aged and
ison of impact test results reveals signifi- Annealed Condition*
cant variation between the aged and solu-
tion annealed material. The lowest impact
Component Condition**,' Impact Strength,
values, 7.6 and 6.0 ft-lb, were recorded for
ft-lb (J)
the aged material and the highest for the
material solution annealed at 2,200°F
Tee Aged 7.6 (10.3)
(1,204°C). The manifold-end material
SA at 1,900F/AC 25.0 (33.9)
exhibited both the lowest and highest
SA at 2,OOOF/AC 28.0 (38.0)
impact values. Solution annealing had a
SAat2,100F/AC 29.0 (39.3)
pronounced influence on impact strength.
SAat2,100F/FC 25.0 (33.9)
Impact values for the tee increased to 26 ft-
SA at 2,200F/AC 33.3 (45.2)
lb to 33 ft-lb as annealing temperatures
increased. Greater increases in impact
Manifold-End Aged 6.0(8.1)
strength were evident with the annealed
SAatl,900F/AC 28.5 (38.6)
manifold end samples where impact values
SA at 2,OOOF/AC 47.5 (64.0)
increased to 29 ft-lb to 60 ft-lb. Cooling
SAat2,100F/AC 50.0 (67.8)
rate significantly influenced impact
SAat2,100F/FC 45.0 (61.0)
strength similar to the influence on tensile
SA at 2.200F/AC 60.0(81.4)
properties. Impact values dropped 10-15%
Notes:
when samples were slow cooled following
* All impact tests were performed using standard size
solution anneal treatment (see Table 3).
specimens at room temperature.
Stress rupture properties were evaluated
** SA = solution annealed; AC = air cooled; PC = furnace
using accelerated stress rupture tests con-
cooled.
ducted at 1,500°F (815°C) and 8.9 Ksi
' Solution annealed samples were held at temperature for 3 h.

AMMONIA TECHNICAL MANUAL 15 2002

 Table 4. Stress Rupture Data in the Aged and Annealed Conditions4

Component Conditiont,tt Life, h Elongation, %

L-M (min.)** As-Cast 150 (min.)

Tee Aged 29.2 45.0

SAatl,900F/AC 37.8 46.0
SA at 2,OOOF/AC 91.8 47.2
SAat2,100F/AC 140.6 42.4
SAat2,200F/AC 192.3 40.5

Manifold-End Aged 114.8 54.5

SA at 1,900F/AC 86.8 55.4
SA at 2,OOOF/AC 99.8 52.0
SAat2,100F/AC 308.4 57.8
SAat2,200F/AC 446.2 59.2
Notes:
* AU tests were performed at 1,500°F and 8.9 Ksi.
** Larsen-Miller 95% confidence curve minimum for 20Cr, 32Ni, INb
alloy.
T SA = solution annealed; AC = air cooled.
'T Samples were solution annealed for 3 h at temperature.

method. Metallographie cross sections were prepared
from the samples and the weld heat-affected zones
examined via optical microscopy. No evidence of
cracking was observed in the weld heat-affected zones.
Since the samples did not experience any cracking in
the aged condition, weldability testing was not per-
formed on the annealed specimens.
Discussion
Carbon, in levels of <0.20%, is typically added to
cast heat resistant Cr-Ni-Fe alloys for fluidity and solid
solution and carbide strengthening purposes. Niobium
additions of approximately 1.0% will increase rupture
strength of these alloys by solid solution strengthening
and formation of primary carbides. Thus, a portion of
the Nb addition will go into solid solution and a portion
will form MC carbides. When cast Cr-Ni-Fe and Cr-Ni-
Fe-Nb alloys are exposed to temperatures above
1,000°F (540°C) for prolonged periods, secondary car-
bides will precipitate in interdendritic regions and
especially hi areas adjacent to eutectic carbides. In Cr-
Ni-Fe alloys, these carbides will be chromium rich car-
bides, while carbide precipitates hi Cr-Ni-Fe-Nb alloys
may include Nb rich and Cr rich carbides.
The metallographic analysis revealed three distinct
interdendritic precipitates hi the aged microstructures.
Chemical analysis indicated that two of the interden-
dritic phases were the anticipated M23Cg type chromi-
um carbides and MC type niobium carbides. The third
phase was enriched in nickel, niobium, and silicon sug-
gesting an intermetallic silicide phase. EBSD analysis
found the intermetallic silicide precipitates to have an
fee crystal structure with a lattice parameter of 11.2Â.
The crystal structure and measured lattice parameter
corresponded to two intermetallic silicide phases, G-
phase (Ni16Nb6Si7) and T| '-phase (Nb3Ni2Si). The
Kikuchi patterns obtained from the intermetallic sili-
cides did not contain sufficient information to differen-
tiate between G-phase and v\'-phase. Previous electron
probe x-ray microanalysis on 20Cr32NilNb material
with 21 months aging found the majority of the inter-
metallic silicide precipitates to be G-phase (Hoffman,

AMMONIA TECHNICAL MANUAL 16 2002

2000).
The precipitated phases were primarily located along
the dendrite boundaries associated with the NbC parti-
cles. The location of the intermetallic precipitates is not
surprising. Nb and Si are rejected to the liquid phase
during solidification (DuPont et al., 1998). The rejec-
tion of these solute elements rninimizes the concentra-
tion of Nb and Si in the dendrite core. However, the
outermost periphery of the dendrites and the dendrite
boundaries were enriched hi Nb and Si since these
areas are associated with the last remaining liquid to
solidify. Thus, high temperature aging appears to read-
ily precipitate intermetallic phases within the solute
rich areas of the microstructure. A published time-tem-
perature-precipitation diagram for a 20Cr25Ni0.6Nb
alloy suggests that grain boundary G-phase and M^Cg
precipitates can form in less than one hour aging at
1,427°F (775°C) (Ecob et al., 1987).
G-phase precipitation has been reported in Nb-modi-
fied heat resistant castings (Ecob et al., 1987;
Barbabela et al., 1991). In the previous study, the G-
phase precipitates tended to be associated with NbC's,
but there was no evidence of NbC particles transform-
ing to G-phase. The material in the current study had
significantly increased aging times as compared to the
previous study. The longer aging time resulted in a
large concentration of the intermetallic suicide phase
with decreased concentration of the NbC phase. This
was especially apparent in the manifold-end segment
where only small islands of NbC were observed
engulfed in large suicide precipitates. This finding sug-
gests the NbC becomes unstable upon prolonged high
temperature exposure and eventually transforms into
an intermetallic silicide phase.
Tensile test results indicate that tensile and impact
properties of the tee and pipe components are similar.
This similarity becomes significant when we consider
the difference in operating history between the two
samples. The tee received a 2,100°F (1,140°C) in-situ
solution anneal treatment after 156 months of service,
then operated an additional 36 months before replace-
ment. The manifold-end operated for 192 months with-
out benefit or interruption of in-situ solution anneal.
The extent of secondary precipitation in the
microstructure of these two parts was essentially the
same, suggesting the aging process is rapid at the early
AMMONIA TECHNICAL MANUAL
phase of continued exposure. This observation is con-
sistent with short term (that is, < 5,000 h) aged ductili-
ty properties previously reported for this alloy (Collins,
1980).
The property similarity did not extend into the aged
stress rupture test results where rupture life of the man-
ifold-end sample was 3X higher than the tee. This dif-
ference hi rupture life suggests the possibility of addi-
tional factors, other than aging response, having an
influence on mechanical properties. Grain boundary
phase distribution is responsible for the decrease'in
UTS, elongation, and impact strength. Concentrations
of complex MC carbide + intermetallic silicides +
M23Cg carbide particles decorate the grain boundaries
of both aged components. The concentration and distri-
bution of these complex particles is similar in both
components and, therefore, does not account for the
difference in rupture life.
Solution anneal heat treatments of aged material
influenced mechanical properties and microstructure
differently. This is understandable considering that
solutionizing is a time-temperature dependent reaction.
For example, solution annealing at 1,900°F (1,038°C)
partially eliminated M/^Cg carbide and significantly
increased tensile ductility and impact strength. It did
not have a visible effect on non-ft/^Cg grain boundary
microconstituents. This trend continued with the
2,000°F (1,093°C) anneal where almost all M23C6 car-
bides were eliminated with little observable effect on
phases other than the M23Cg carbide. Tensile ductility
and impact strength improved slightly with the higher
annealing temperature. Stress rupture properties were
similar with the aged and 1,900°F (1,038°C) conditions
and slightly improved after 2,000°F (1,093°C) anneal.
Marked changes in microstructure, tensile, impact
and stress rupture properties were evident after anneal-
ing at 2,100°F (1,140°C). Precipitated carbides were
solutionized, grain boundary phases were partially
spheroidized, elongation and impact strength
increased, and rupture strength increased dramatically.
A second set of samples was furnace cooled to below
1,000°F (538°C) and then air cooled to room tempera-
ture, rather than being removed from the furnace at the
completion of the heat treatment and ah- cooled to room
temperature. These samples had a much slower cooling
17 2002
 Figure 5. Micrograph obtained on tee after solution annealing at
2,100°F (1,140°C) followed by air cooling.
(Mixed acids, 500X original magnification.)

Figure 6. Micrograph obtained on tee after solution annealing

at 2,100°F (1,140°C) followed by furnace cooling.
(Mixed acids, 500X original magnification.)

AMMONIA TECHNICAL MANUAL 18 2002

rate and the microstructure contained very fine M23C6
precipitates that obviously precipitated during the slow
cool in the carbide precipitation range of 1,650°F
(900°C) - 1,200°F (650°C), (see Figures 5 and 6).
Somewhat lower elongation and impact values were
observed for the furnace cooled material.
The improvements in microstructure, toughness, and
rupture strength continued with the 2,200°F (1,204°C)
annealing treatment. The microstructure indicated
complete spheroidization of the grain boundary phases.
The stress rupture strength significantly increased with
the 2,200°F (1,204°C) solution anneal treatment. This
treatment exhibited the best overall combination of
structure and properties, suggesting that salvage
annealing treatments be raised to take advantage of the
increase in properties.
Differences in mechanical properties are evident
between the two manifold components. These differ-
ences are most evident in solution annealed material. It
is thought that these differences are related to the sec-
tion size differences of the two components rather than
their modest differences in chemical composition. The
manifold-end is a centrifugal cast pipe with a finished
cross section of 1.12 in. (28.4 mm). The tee is also cen-
trifugal cast, but has a solid bottom, a finished cross
section of 3.10 in. (78.7 mm), and a larger gram size.
The tee also has a wider dendrite arm spacing and sig-
nificantly coarser carbide structure.
In-situ solution anneal of aged 20Cr32NilNb mani-
fold components is standard industry practice in prepa-
ration for weld repair. Results obtained in this study
indicate that the solution annealing temperature and the
cooling rate at the conclusion of the anneal treatment
are critical. Low solution annealing treatments will not
solution the semi-continuous grain boundary networks.
Solutioning temperatures of 2,200°F (1,204°C), which
provide the best properties, may be difficult to attain
using conventional equipment. The cooling rate to
room temperature at the completion of the annealing
treatment is also critical. The cooling rate between
1,650°F (900°C) and 1,200°F (650°C) should be suffi-
cient to prevent precipitation of carbides. Water quench
would be optimum, but test results suggest that con-
ventional air cooling rates are sufficient to prevent pre-
cipitation of M23Cg carbide precipitation.
Aging of the 20Cr32NilNb alloy resulted in the pre-
AMMONIA TECHNICAL MANUAL
cipitation of interdendritic intermetallic silicides.
Compared to NbC, the intermetallic silicide particles
are soft, deformable, and do not strongly inhibit dislo-
cation movement leading to weaker material.
Additionally, the intermetallic silicides contained large
concentrations of Ni and Nb. The Nb would normally
be in the form of niobium carbide with excess Nb
remaining in solid solution. Ni would also normally
remain in solid solution. Thus, the formation of the
intermetallic silicide phase results in a net decrease in
the NbC concentration resulting in decreased strength.
The intermetallic silicides phase also removes Ni and
excess Nb from the matrix resulting in a decrease in
solid solution strengthening.
The performance of the 20Cr32NilNb alloy could
likely be optimized by modification of the nominal
chemistry to inhibit precipitation of the intermetallic
silicides. The precipitation of the intermetallic phases
is initiated by the segregation of Si in the microstruc-
ture. The manufacturer's specification allowed up to
1.5 wt. % Si in this alloy. The aged tee and manifold-
end section contained 0.8 wt. % Si and 0.9 wt. % Si,
respectively. The Si addition is beneficial to the
foundry since Si increases the fluidity of the molten
metal. Si additions also inhibit carburization attack of
alloys while in service by the formation of a protective
SiO2 layer. However, the moderate operating tempera-
tures of hydrogen reformers are too low to form a pro-
tective surface layer of SiO2 while in service. Thus, the
Si addition probably does not improve the performance
of the 20Cr32NilNb alloy and should be minimized.
Lowering the Si content would decrease the tenden-
cy to form intermetallic silicides and subsequent
decreases in tensile properties. Therefore, the silicon
content should be kept as low as possible. This appears
to be verified by the manifold-center section. The man-
ifold-center section contained only 0.6 wt. % Si and
had no intermetallic silicides phases present in the aged
microstructure. The manganese (Mn) content of the
alloy could be increased to help restore some of the flu-
idity of the molten metal. The UTS and elongation of
aged 20Cr32NilNb has been shown to increase with
decreasing Si and increasing Mn concentrations
(Shibasaki et al., 1987).
The intermetallic silicides also contained large con-
centrations of Nb. Nb is added to the alloy to form sta-
19 2002
blé NbC's that improve creep resistance. The aged tee
contained 0.09 wt. % C and 1.30 wt. % Nb producing
a Nb/C ratio of 14.4. The Nb/C ratios of the manifold-
end and manifold-center sections were 13.5 and 11.6,
respectively. In the formation of NbC, one Nb atom is
required for every C atom. With a C content of 0.09 wt.
% in the tee, only 0.70 wt. % Nb is required to ensure
there is one atom of Nb for every C atom. A Nb con-
centration of 0.70 wt. % would yield a stoichiometric
Nb/C ratio of 7.7. The Nb/C ratios of all of the aged
components examined were well above 7.7 (hyperstoi-
chiometric) indicating the components had excess Nb
in solid solution. However, the manifold-center seg-
ment, which had the lowest Nb/C ratio and the lowest
Si content, had no intermetallic suicides precipitates in
the aged microstructure. This suggests that the Nb/C
ratio for this alloy should be targeted at 7.7. The metal-
lographic analysis found that the aged material precip-
itated M/^Cg carbides consuming some of the carbon
available to form NbC's. Thus, the Nb/C ratio could be
reduced below the 7.7 target value to limit the amount
of excess Nb in solid solution upon initial solidifica-
tion.
Previous analysis of the material aged for 21 months
showed a strong propensity for weld heat-affected zone
cracking using the bead-on-plate weldability test. The
material in the current study was aged considerably
longer and had niobium to carbon ratios as high as
14.4. However, no HAZ cracks were generated in the
aged samples via bead-on-plate testing. This indicates
that the bead-on-plate method does not provide suffi-
cient sensitivity to determine weldability in the aged
condition. More sensitive techniques, such as
Varestraint testing, are required to access aged weld-
ability.
Conclusions
The following conclusions were reached based on
the results of the metallurgical evaluation of aged
20Cr32NilNb centrifugal castings:
(1) High temperature aging of the 20Cr32NilNb
alloy results in the precipitation of intermetallic sui-
cides and chromium carbides, as well as carbide coa-
lescence.
AMMONIA TECHNICAL MANUAL
(2) Carbide coalescence in conjunction with inter-
metallic silicide and chromium carbide precipitation
significantly degrades the mechanical properties of the
alloy. Most of the mechanical property degradation
occurs within the first three years of service with neg-
ligible property degradation upon continued aging
beyond three years.
(3) Solutionizing of M23Cg carbides and intermetal-
lic silicide phases was accomplished by solution
annealing at 2,000°F (1,093°C).
(4) Complete solutionizing of secondary precipitates
and spheroidization of the primary carbide network
required a minimum solution annealing temperature of
2,100°F (1,140°C).
(5) Additional stress rupture life and impact strength
improvements were achieved by solution annealing at
2,200°F (1,204°C).
(6) A minimum cooling rate of 250°F (139°C) / min.
upon completion of solution annealing is sufficient to
prevent carbide precipitation and subsequent mechani-
cal property degradation.
(7) The alloy chemistry should be modified to inhib-
it precipitation of the intermetallic silicide phases.
Specifically, the silicon content should be held as low
as possible while maintaining a stoichiometric Nb/C
ratio of 7.7.
Acknowledgments
The authors would like to express sincere thanks to
Dr. John Radavich for his assistance with selective
etching and extractive metallography. Thanks to the
MetalTek International Metallurgical lab and Heat
Treat Department for sectioning, mechanical testing,
and heat treating. Thanks to Michael Wert and Jim
Stets, both of APCI, for their assistance in métallo-
graphie sample preparation and phase identification,
respectively.
Literature Cited
Barbabela, G. D., L. Henrique de Almeida, T. Luiz de
Silveira, and I. Le May, Matls. Characterization,
26(1), 1 (1991).
20 2002
Collins, P. A., "Effect of Elevated Temperature
Exposure on the Mechanical Properties of a Cast
Niobium-Containing Alloy," NACE International
Paper No. 170, Corrosion/1980.
DuPont, J. R, C. V. Robino, A. R. Marder, and M. R.
Notis, Metallurgical and Materials Trans. A, 29A,
2797 (Nov. 1998).
Ecob, R. C., R. C. Lobb, and V. L. Kohler, J. Material
Sei., 22(8), 2867 (Aug. 1987).
Hoffman, J. J., "High Temperature Aging
Characteristics of 20Cr32NilNb Castings," NACE
QUESTIONS AND ANSWERS
Rob Gommans, Gommons Metallurgical Services: I
doubt the presence of G-phase. My investigation show
M6C carbide 3Ni, ISi, IFe/Gr, 1N6.
John J. Hoffman, Air Products: Our analysis indicat-
ed the Ni-Nb-Si rich phases was face centered cubic
with a lattice parameter of 11.2 angstroms, consistent
with G-phase. In addition, no significant carbon was
detected in this phase. Hence, the conclusion in the
phase was G-phase. G-phase has been reported in the
literature hi several aged casting with similar composi-
tions to that investigated in this article. In all cases, G-
AMMONIA TECHNICAL MANUAL
International Paper No. 512, Corrosion/2000,
Houston, TX, NACE International (2000).
Shibasaki, T., K. Takemura, T. Kawai, and T. Mohri,
"Experience with 20Cr-32Ni-Nb Cast Material for
Steam Reformer Furnaces," Ammonia Plant Safety
& Related Facilities, Vol. 27, AIChE, New York
(1987).
Shinozaki, K., H. Kuroki, et. al, Yosetsu Gakkai
Ronbunshu (Collection of papers of the Japanese
Welding Society), 16(2), 223 (1998).
phase formation led to mechanical property degrada-
tion as similar to that demonstration in the article.
There is some literature stating M23C6 can transform
to M6C upon aging. However, M6C has never been
reported in this alloy.
Charles Thomas, Materials Performance
Technologies: In addition to the room temperature ten-
sile ductility you reported in your talk, do you have
information relating to high temperature stress rupture
ductility?
Hoffman: The stress rupture ductility data is available
and simply was not reported in the article.
21 2002