Superalloys 718, 625, 706 and Derivatives 2005 Edited by E.A.

Loria
TMS (The Minerals, Metals & Materials Society), 2005

A New Alloy Designed for Superheater Tubing in Coal-Fired Ultra Supercritical Boilers
B. A. Baker

Special Metals Corporation

3200 Riverside Drive
Huntington, WV 25705

Keywords: Nickel-base, superalloy, coal ash corrosion, ultra supercritical

ABSTRACT
Future increases in the demand for clean and efficient electrical power production will be
unrelenting. Meeting the coming challenges will require power generating systems capable of
operating with increased boiler pressures and temperatures. In turn, meeting the demands of the
application will also require materials which can withstand these extreme conditions. This paper
describes a new nickel-base tubing alloy, INCONEL® alloy 740, developed for the purpose of
meeting this challenge. This material possesses a unique combination of elevated temperature
strength properties and resistance to coal ash corrosion required by the application. The material
was developed to fulfill the minimum stress rupture requirement of 100,000 hour rupture life at a
stress of 100 MPa and at a temperature of 750°C. In addition, metal loss of less than 2mm in
200,000 hours was defined as the target corrosion resistance for this material. The mechanical
properties of this new material will be described, in addition to its coal ash and steam corrosion
resistance and weldability. Thermal stability will also be discussed, focusing upon
microstructural features of long-term exposed samples. Early methodology utilized to arrive at
the current chemical composition will also be presented.
INTRODUCTION
When ultra supercritical steam conditions employing greater than 300 bar steam and 600°C
steam temperature are adopted, it has been demonstrated that the efficiency of pulverized coal-
fired boilers can be increased to over 50% LHV (lower heating value). At this steam
temperature, the superheater/reheater midwall temperature may be at 660°C or higher. At these
metal temperatures, the conventionally used 9-12% Cr steels must be replaced by austenitic
stainless grades. Projects like the European AD700 project and the German MARCKO DE2
project are planning for steam pressures up to 375 bar and steam temperatures to 700°C. This
will lead to superheater/reheater mid-wall temperatures at over 740°C. Under these conditions,
austenitic stainless steels cannot meet the stringent requirements of 100,000 hour rupture life at
750°C and 100 MPa and corrosion resistance defined as metal loss not exceeding 2mm after
200,000 hours.
ALLOY DEVELOPMENT METHODOLOGY
With no alloy in existence that could meet both the mechanical and corrosion demands of the
described applications, an alloy development program was initiated. It was determined that the
existing superalloy NIMONIC® alloy 263 possessed the required rupture strength but lacked the
needed corrosion properties. This alloy was used as the basis for the development, utilizing
additions of Cr and Nb for enhancement of corrosion resistance while maintaining the required
volume percentage of gamma prime for precipitation hardening.

® INCONEL and NIMONIC are trademarks of the Special Metals Corporation group of
companies.

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A rapid method of assessing rupture strength properties was utilized, involving testing samples
and fixed stress of 100 MPa over a broad temperature range. Figure 1 shows a plot of collected
data. The solid line represents the strength capability of NIMONIC alloy 263. Materials falling
below that line were rejected from the program. Data shown for developmental alloys 1 and 2
fall above the alloy 263 data while data for alloy 3 lie well below.

1.0E+05

1.0E+04

1
Rupture Life, Hours

1.0E+03
3 2

1.0E+02

1.0E+01

1.0E+00
750 800 850 900 950
Temperature, °C

Figure 1. Plot showing rupture life in hours versus temperature in

degrees Celcius. The solid line is the isocline for NIMONIC alloy 263.
The data points shown represent experimental materials evaluated in the
alloy development program.

Figure 2 shows the results of predictions made using Thermo-Calc of the atomic percentage of
gamma prime as a function of Al and Ti content. The chart was constructed by mapping
interpolated data. A minimum percentage of 15% was deemed acceptable.

Assessment of preliminary data acquired to evaluate mechanical and corrosion properties of

developmental heats of INCONEL alloy 740 resulted in the nominal composition shown in Table
1 being established. Nominal composition for other alloys mentioned in this study are included
as well.

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 Table 1. Nominal Composition of the Alloys of This Study.

Alloy C Ni Cr Mo Co Al Ti Nb Mn Fe Si
740 0.03 Bal. 24.5 0.5 20 0.9 1.8 2 0.3 1 0.5
617 0.085 Bal. 22 9.7 11.5 1.1 0.3 --- 0.1 1.5 0.1
263 0.05 Bal. 20 5.8 19.5 0.5 2.1 --- 0.35 0.5 0.1
671 0.03 Bal. 46.5 --- --- 0.3 0.4 --- --- --- ---
693 0.02 Bal. 29 --- --- 3.1 0.4 0.6 0.2 4 0.1
690 0.03 Bal. 29 --- --- 0.25 0.3 --- 0.2 10 0.05

MECHANICAL PROPERTIES OF INCONEL ALLOY 740

Stress rupture properties of INCONEL alloy 740 as determined by the AD700 consortium are
shown in Figure 3. Table 2 shows tensile properties for hot-rolled 16mm diameter bar of
INCONEL alloy 740.

Table 3 shows room-temperature tensile data and Rockwell hardness values for 6.4mm thick hot-
rolled and solution annealed plate after receiving aging treatments at either 760°C or 800°C with
aging timed varied between 4 hours and 16 hours. Strength levels were slightly higher for
samples aged at 760°C versus 800°C; longer aging times resulted in slight strength increases at
both temperatures. Elongation and reduction of area did exhibit a slight downward trend as
aging time increased at each temperature; ductility values were in a similar range at both
temperatures. Table 4 shows the effect of the same aging temperatures and times upon impact
properties. Samples were half-size; a favorable impact strength of 75 J/cm2 was retained after
aging for 16 hours at both 760°C and 800°C.
1.7

20 25
1.6

1.5
15
1.4

20 25
1.3
Aluminum, Weight %

1.2
15
1.1
20

1.0

0.9 10
15

0.8
20

0.7

10
0.6 15
5
0.5
0.5 1.0 1.5 2.0 2.5

Titanium, Weight %

Figure 2. Predictions made using Thermo-Calc of the atomic percentage

of gamma prime as a function of Al and Ti at 750°C content for Ni-
24Cr-20Co-1Fe-0.5Mo-0.03C.

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 1000

700ºC
Stress MPa

750ºC 725ºC

775ºC

800ºC

100
10 100 1000 10000 100000
Rupture Life - hours

Figure 3. Stress rupture properties of INCONEL alloy 740 as determined by the

AD700 consortium.

Table 2. Tensile Property Data for INCONEL alloy 740 Hot-Rolled Bar

Test 0.2% Yield Tensile Strength Elongation Reduction of Material

Temperature Strength
°F °C ksi MPa ksi MPa % Area, % Condition
74 23 45.5 313.7 115.5 796.4 57.5 67.5 Annealeda
74 23 104.5 720.5 169.5 1168.7 51.34 49.4 Annealed and Agedb
1000 538 89.4 616.4 142.1 979.8 31.3 39 Annealed and Agedb
1100 593 88.1 607.4 143.9 992.2 31.4 32.8 Annealed and Agedb
1200 649 90.1 621.2 148.4 1023.2 38.4 39.8 Annealed and Agedb
1300 704 94 648.1 132.5 913.6 37.9 43.7 Annealed and Agedb
1400 760 88.2 608.1 111.1 766 32.5 43.9 Annealed and Agedb
1472 800 80.7 556.4 94.5 651.6 34.8 46.2 Annealed and Agedb
1500 816 74.6 514.4 88.2 608.1 37.7 47.8 Annealed and Agedb
1600 871 44.1 304.1 53 365.4 55.2 67.8 Annealed and Agedb
1700 927 21.5 148.2 29 200 63.5 79.4 Annealed and Agedb
1800 982 8.7 60 15.2 104.8 112.5 93.1 Annealed and Agedb
a
2100°F/30 minutes/water quench.
b
2100°F/30 minutes/water quench + 1472°F/16 hours/air cool.

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 Table 3. Room Temperature Tensile and Hardness Data for 6.4mm Thick Hot-
Rolled and Solution-Annealed INCONEL alloy 740 Plate

Rockwell C Hardness 0.2% YS, ksi UTS, ksi Elong., % R of A, % Aging Treatment
33.6 118.7 175.3 36.4 47.6 760°C/4hr/ac
34.4 120.9 178.2 37.4 43.0 760°C/8hr/ac
35.5 123.2 180.1 33.4 43.0 760°C16hr/ac
35.6 114.8 173.4 37.0 45.8 800°C4hr/ac
33.8 116.6 175.7 35.2 44.8 800°C/8hr/ac
33.8 114.2 176.3 33.6 42.8 800°C/16hr/ac

Table 4. Room Temperature Charpy Impact Data for 6.4mm Thick Hot-Rolled
and Solution-Annealed INCONEL alloy 740 Plate

Impact Energy, Ft-Lb Impact Energy, J/cm2 Aging Treatment

29.5 100.0 760°C/4hr/ac
25.1 85.0 760°C/8hr/ac
22.1 75.0 760°C/16hr/ac
28.0 95.0 800°C/4hr/ac
24.3 82.5 800°C/8hr/ac
22.1 75.0 800°C/16hr/ac
Note: Sample cross section = 0.4 cm2 at notch; average of triplicate tests.

MICROSTRUCTURAL CHARACTERIZATION AND STABILITY OF INCONEL

ALLOY 740

Detailed studies of the microstructural stability of INCONEL alloy 740 have been carried out by
Dr. Xie and his colleagues at the University of Beijing, and also by Evans, et al., at Oak Ridge
National Laboratory [1,2].

Xie, et al., examined the microstructure of solution annealed INCONEL alloy 740 hot-rolled and
solution annealed bar after aging at 704°C (1300°F) and 725°C (1337°F) for 500, 1,000, 1,500
and 2,000 hours [1]. The SEM images are shown in Figures 4 The precipitate morphologies are
fairly similar among the various exposure conditions. Very fine Ȗ’ precipitates (16.6 wt. % after
2,000 hours) were distributed throughout the grains, which contribute the main strengthening
effect. Larger (Nb,Ti)C particles (0.15% after 2,000 hours) were also observed throughout the
grains, while the grain boundary precipitate after long term aging at 704°C (1300°F) was Cr23C6
(0.15% after 2,000 hours). After aging at 725°C (1337°F) for 4,000 hours, a small amount of
needle-like (η) and blocky precipitates (G-phase) had also formed in the grain boundaries.
Figure 5 shows the coarsening rate of the Ȗ’ precipitates at 704°C (1300°F), 725°C (1337°F) and
760°C (1400°F) for times to 4,000 hours. Gamma prime increases with time and temperature in
the temperature range studied. At the initial stage of aging, the Ȗ’ particles were small and
spherical and eventually became cuboidal with time and temperature, confirming the work of
Evans, et al [2], who examined a sample which had been solution-annealed and aged, followed
by creep testing at 816°C (1500°F) and 138 Mpa (20 ksi). The relationship between the radius of
Ȗ’ and time is linear and follows the kinetics of diffusion controlled particle growth [1].

Both investigations confirmed the presence of the following precipitates: γ’, η, G-phase, M23C6
carbides and MC carbides. The composition for these respective precipitates is shown in Table 5
as reported by the Evans study, found in a creep sample tested at 816°C (1500°F) and 138 MPa

605
 Figure 4. SEM images after aging for 500h (a), 1000h (b), 2000h (c) and 4000h
(d) at 704°C (left) and 725°C (right).

(20 ksi) for 2500 hours. While the η phase in this sample was not determined to have had an
embrittling effect upon the alloy, it was noted that the laths extending across grains did appear to
have grown at the expense of γ’ precipitates. In addition, at this high exposure temperature, the
gamma prime had coarsened from ~60 nm to 240 nm in diameter and lost coherency with the
matrix. However, the precipitates were still presumed to have enhanced matrix strength via
dislocation pinning.

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 Figure 5. Coarsening of Ȗ’ Precipitates in
INCONEL alloy 740 (1).

Table 5. Measured Composition (atom %) of the Phases Present After Creep Testing of
INCONEL alloy 740 at 815°C (1500°F)/138 MPa (20 ksi) for 2,500 hours (2)

Phase Ni Cr Co Fe Ti Al Nb Mo Si
γ 44.6 32.7 21.2 0.5 0.3 0.1 0.2 0.1 0.3
γ’ 73.3 1.6 6.2 0.3 10.0 6.1 2.4 0 0
η 71.0 1.3 8.9 0.1 10.4 2.3 6.0 0 0
M23C6 3.5 93.5 1.6 0 0.1 0 0 1.2 0
MC 1.2 0.9 0.6 0 32.0 0.1 64.5 0.2 0.5
G 47.3 2.1 10.1 0.1 2.8 0.1 15.3 0 21.9

CORROSION RESISTANCE OF INCONEL ALLOY 740

Corrosion testing was carried out in the interest of simulating coal ash corrosion conditions. The
ash mixtures utilized consisted of 5% Na2SO4-5% K2SO4-90% (Fe2O3-Al2O3-SiO2 in 1:1:1 ratio
by weight). The ash mixture was prepared by grinding with mortar and pestle. The synthetic flue
gas was mixed using electronic flow meters from component gases (including a pre-mixed
cylinder of N2-1.8% SO2) and consisted of N2 - 15% CO2 - 3.5% O2 - 0.25% SO2. Test samples
consisted of 7.6 mm diameter X 19 mm long cylindrical pins machined to a 32 microinch finish.
Prior to testing, the synthetic coating was applied to the samples surfaces by first diluting with
acetone and then using a bristle brush. The approximate mass gain resulting from application of
the coating was 40 mg/cm2. Samples were allowed to dry completely before testing. The coated
samples were placed in a cordierite ceramic boat and exposed in a sealed horizontal, electrically
heated muffle furnace having a 100 mm OD mullite tube. Samples were placed into the heated
section of the furnace after sufficient purging and introduction of the test gas, using a sealed
pushrod mechanism. Samples were cycled at approximately 500 h, 1000 h, 2000 h and 4000 h.
Exfoliated surface products were removed and the coating was re-applied after each of the given
time intervals.

Metal loss and average depth of attack were assessed from sample cross sections. Average
values for metal loss and depth of attack were determined from a total of six measurements made
around the circumference of each pin. In the case of the depth of attack measurement, the
maximum depth of intrusion was determined for each of the six fields examined at
approximately 60 degree intervals around the circumference of the pin.

Figure 6 shows depth of attack measurements for alloys tested at 700°C with the simulated flue
gas and applied salt as described above. Alloys 617, A1 and A2 (alloy 740 variants with 6%
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Mo) suffered significant thickness loss, exhibiting linear kinetics. These results could indicate
that molybdenum at 6-9% is undesirable for coal ash corrosion resistance. Perhaps incorporation
of molybdenum into the trisulfate ash forming at the material surface leads to an increased
corrosion rate by affecting the solubility of protective chromium oxides, as observed in Mo-
containing alloys which undergo high temperature Type I hot corrosion at about 825-950°C
[3,4].

260
240 617
Depth of Attack, Microns 220 A-2
200 A-1
180 740-3
160 740-4
140 671
120
690
100
740-1
80
740-2
60
40 693
20
0
0 2000 4000 6000
Expsoure Time, Hours

Figure 6. Depth of attack after exposure at 700°C in N2 - 15% CO2

- 3.5% O2 - 0.25% SO2 with samples having a salt consisting of
5% Na2SO4-5% K2SO4-90% (Fe2O3-Al2O3-SiO2 in 1:1:1 ratio by
weight) applied to the surface (re-coated at the intervals shown).

Figure 7 shows results from three different data sources after testing under fairly similar
conditions. These data represent a number of different alloys ranging from Fe-Ni-Cr types to
nickel-base superalloys. These data show that, in general, once the chromium content exceeds
25-30%, corrosion activity stabilizes.

Figure 8 shows a comparison of both linear and parabolic extrapolations of data acquired for
INCONEL alloy 740 and INCONEL alloy 617 under the same conditions as shown in Figure 6.
Based upon 4000 hour data, these extrapolations show that INCONEL alloy 617 is not projected
to meet the design criterion of less than 2mm of corrosion attack in 200,000 hours whereas
INCONEL alloy 740 is, even if an eventual linear progression rate is assumed.

FABRICATION CONSIDERATIONS

Fabricability is a key consideration in the design of a material to be used for assembly of

power boilers components. Weldability was demonstrated via assembly of a beveled butt joint
using 6.4mm plate and 0.093” matching filler wire with the manual gas tungsten arc welding
(GTAW) technique. The plates were joined in the solution annealed and aged condition to
simulate field construction of repair operations. A post-weld aging treatment was also applied.
The weldment was completed using a current setting of 185A, with voltage at 14V using 100%
Ar at 30 CFH as the shielding gas and a 0.125” diameter, 2% thoriated tungsten electrode with a
travel steep of ~2-4 inches per minute. Table 6 shows room temperature tensile results for

608
transverse samples from the assembled joint. Specimens passed a 2T face bend in the as-welded
condition; specimens tested in the post-weld aged condition failed the 2T bend but passed a 4T
bend.

1000.00 Blough and Stanko

[5]
Castello, et al [6]
Average Thickness Loss
(Microns/1000 Hours) /Baker and Smith [7]
100.00

10.00

1.00
0 10 20 30 40 50
Mass % Cr

Figure 7. Cross section loss (depth of attack) for high temperature alloys exposed
at 700°C in laboratory flue gases (0.25% SO2) with alkali sulfate-oxide coatings
applied to the sample surface, as a function of chromium
content.
[5]: N2-14%CO2-10%H2O-3.6%O2-0.25%SO2, , 10% alkali sulfates
[6]: N2-15%CO2-3.5%O2 -0.25%SO2, 10% alkali sulfates
[7]: N2-15%CO2-3.5%O2 -0.25%SO2, 10% alkali sulfates

609
 10000
INCONEL alloy 617

Maximum Attack, Microns

INCONEL alloy 740

1000 617 Linear Projection

740 Linear Projection

740 Parabolic Projection

100

10
100 1000 10000 100000 1000000

Time, Hours

Figure 8. Depth of attack results for INCONEL alloy 617 and INCONEL alloy
740 samples tested in a simulated flue gas mixture comprised of N2 - 15% CO2 -
3.5% O2 - 0.25% SO2 at 700°C with a salt coating applied which was comprised of
5% Na2SO4-5% K2SO4-90%(Fe2O3-Al2O3-SiO2 in 1:1:1 ratio).

Table 6. Room Temperature Tensile Results for Manual GTAW Weldments

Made Joining 6.4 mm (0.25”) Commercial Plate Using 0.093” Diameter
Experimental Wire. The As-Produced Base Material (Hot-Rolled and Solution
Annealed) Was First Aged at 800°C (1472°F)/4 Hours, Welded and Then Aged
after Welding at 800°C (1472°F)/4 Hours.

0.2% Yield Ultimate Tensile

Strength Strength Elongation
Sample MPa (ksi) MPa (ksi) %
1 738 (107) 1100 (159.5) 18.2
2 757 (109.8) 1079 (156.5) 14.8

CONCLUSIONS

1.) INCONEL alloy 740 successfully surpasses the established strength design target defined as
aim stress rupture life exceeding 100,000 hours at 750°C and 100Mpa.
2.) INCONEL alloy 740 as defined for the purposes of this study exhibits standard gamma prime
growth kinetics. At higher temperatures and longer times, η-phase formation occurs with a
Widmanstatten morphology.
3.) INCONEL alloy 740 exhibits favorable resistance to coal ash corrosion in laboratory tests
designed to simulate boiler conditions.
4.) INCONEL alloy 740 can be readily welded using GTAW and argon shielding. In the aged,
welded and aged condition, the room temperature tensile properties approached those of the
base material.

610
 REFERENCES

1. S. Zhao, J. Dong, X. Xie, G. D. Smith and S. J. Patel, “Thermal Stability Study on a New Ni-
Cr-Co-Mo-Nb-Ti-Al Superalloy,” presented at the 10th International Symposium on
superalloys, Seven Springs, PA, September 19-23, 2004.
2. N. D. Evans, P. J. Masiasz, R. W. Swindeman and G. D. Smith, “Microstructure and Phase
Stability in INCONEL alloy 740 during Creep,” Scripta Materiala, 51 (2004).
3. R. A. Rapp and Y. S. Zhang, Hot Corrosion of Materials: Fundamental Studies,
JOM, Vol. 46. No. 12, 1994, p. 47.
4. J. A. Goebel, et al., Mechanisms for Hot Corrosion of Nickel-Base Alloys, Metallurgical
Transactions, Vol. 4, 1973, pp. 261-278.
5. J. L. Blough and G. J. Stanko, Fireside Corrosion Testing of Candidate
Superheater Tube Alloys, Coatings and Claddings - Phase II, CORROSION/97,
Paper No. 140, NACE International, Houston ,TX, 1997.
6. Castello, P., Guttmann, V., Farr, N.*, Smith, G., Laboratory Simulated Fuel-Ash Corrosion
of Superheater Tubes in Coal-Fired Ultra
Supercritical-Boilers, Proceedings of the EUROMAT Conference, 27-30
September 1999, München (D), Wiley-VCH Verlag - ORA/PRO 60750.
7. B. A. Baker and G. D. Smith, Corrosion Resistance of Alloy 740 as Superheater Tubing in
Coal-Fired Ultra-Supercritical Boilers, CORROSION/2004, Paper No. 04526, NACE
International, Houston, TX, 2004.

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