Phase Precipitation and Phase Stability in Nimonic 263

J.-C. ZHAO, V. RAVIKUMAR, and A.M. BELTRAN

Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermodynamic
calculations were employed to study the phase stability and phase precipitation in the Ni-based
superalloy Nimonic 263. The major precipitates at temperatures below 900 ⬚C were gamma-prime
and eta (Ni3Ti), with the eta phase starting to precipitate at the expense of the gamma-prime phase
after prolonged annealing. The eta precipitates had a thin-plate morphology and formed a regular
Widmanstätten pattern. They had a fixed orientation relationship with the fcc matrix. Very fine
particles of M23C6 also precipitated intragranularly, and they had a cube-on-cube orientation relation-
ship (OR) with the fcc matrix. Intragranular precipitation of a very fine cylindrical MC carbide was
also observed. Grain-boundary (GB) precipitates were mostly M23C6, with a small fraction of MC.
Based on the experimental results, a time-temperature-transformation (TTT) diagram was constructed.
The experimental results were compared to thermodynamic predictions, and good agreement was
observed. The calculations correctly predicted almost all the major phases and their stability tempera-
ture ranges. The experimental and calculation results, together, depict a clearer picture of phase
stability in the alloy.

I. INTRODUCTION behavior in order to build a time-temperature-transformation

NIMONIC 263[1] is a wrought Ni-based superalloy
which has found application in gas turbines because of its
attractive creep strength and good oxidation resistance. Its
nominal composition is 19 to 21Co, 19 to 21Cr, 5.6 to 6.1Mo,
1.9 to 2.4Ti, ⱕ0.6Al, ⱕ0.6Fe, 0.04 to 0.08C, and the balance
Ni. (All compositions are in weight percent throughout this
article, unless otherwise stated.) This alloy is precipitation
hardened; however, only limited information is available in
the literature on its precipitation behavior.[2,3] Several phases
have been reported: gamma-prime (␥ ⬘),[2,3] eta (␩),[2,3]
M23C6,[2,3] and M6C.[2] The crystal structures and lattice
parameters of the phases are listed in Table I.[4,5] The ␥ ⬘-
Ni3(Ti,Al) phase has an L12 crystal structure (cP4), and the
␩-Ni3Ti phase has a complex hexagonal structure (hP16).
The M23C6 phase has an fcc structure (cF116), whereas the
M6C phase has a diamond cubic crystal structure (cF112),
but their lattice parameters are very close. Hicks and Heap[2]
studied two versions of the alloy using optical microscopy
and replica electron microscopy along with hardness evalua-
tions. They derived a C-curve for the ␩-phase formation
based on microstructure data and observed that the ␩ phase
did not form at temperatures ⱖ925 ⬚C. In addition, Hicks
and Heap observed dissolution of the ␥ ⬘ phase at ⬃900 to
925 ⬚C, which is consistent with the results of Ratna and
Sarma,[3] who, based on transmission electron microscopy
(TEM) examination of thermal-fatigue samples, reported a
dissolution temperature of ␥ ⬘ in the vicinity of 900 ⬚C.
Singh and Singh[6] studied the work-hardening behavior of
Nimonic 263, but did not examine the microstructures in
detail. The aim of the present investigation on Nimonic 263
is two-fold: (1) to provide more data on the precipitation
J.-C. ZHAO, Materials Scientist, is with Corporate Research & Develop-
ment, General Electric (GE) Company, Schenectady, NY 12301. V.
RAVIKUMAR, Materials Scientist, is with the GE John F. Welch Jr. Tech-
nology Center, Bangalore, Karantaka 560-066, India. A.M. BELTRAN,
formerly Manager, Materials and Processes Engineering, GE Power Sys-
tems, Schenectady, NY 12345, is retired.
Manuscript submitted June 16, 2000.
(TTT) diagram; and (2) to study the phase stability by inte-
grating phase-precipitation information with thermodynamic
calculation results.
II. EXPERIMENTAL AND CALCULATION
PROCEDURES
Test samples of about 7 ⫻ 20 ⫻ 20 mm in size were cut
from a piece of wrought commercial Nimonic 263. The
composition of the alloy as analyzed by a microprobe was,
in wt pct, 20.1Co, 19.6Cr, 5.7Mo, 2.1Ti, 0.4Al, 0.5Fe, and
0.06C. (The carbon content was not analyzed, and this value
was based on the manufacturer’s nominal composition.) The
piece had been rolled and solution annealed. To ensure that
the starting piece was in the solution-annealed condition, an
extra solution annealing was performed at 1150 ⬚C for 2
hours in air and was water quenched. Precipitation annealing
was performed at 750 ⬚C, 850 ⬚C, and 900 ⬚C for 1, 2, 5,
8, 26, 50, 100, 300, and 1000 hours in air. Several additional
annealing conditions at longer time periods were also
employed, in order to assess the C-curve for the ␩ phase.
To prepare TEM thin foils, thin sheets were cut out of
the heat-treated pieces using a low-speed diamond saw and
were mechanically thinned down to about 50 to 100 ␮m in
thickness using a SiC and diamond–embedded polishing
media. Discs of 3 mm in diameter were punched out of the
thin sheets and electropolished to perforation with an 80 pct
methanol and 20 pct perchloric acid electrolyte at ⫺45 ⬚C
and 20 V, using a double-jet electropolisher.
The TEM characterization of selected samples was per-
formed on a PHILIPS* EM 430 operating at 300 keV. Energy
*PHILIPS is a trademark of Philips Electronic Instruments Corp., Mah-
wah, NJ.
dispersive X-ray microanalysis was performed using a Link
Pentafet energy-dispersive spectrometer (EDS) with an ultra-
thin window, controlled using the Link eXL system.
High-resolution scanning electron microscopy (SEM) was

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 32A, JUNE 2001—1271

 Table I. Crystal Structure of the Phases Discussed in the Article
Basic Crystal Pearson
Phase Major Composition Structure Symbol Space Group Lattice Parameter, nm
␥⬘ (Ni,Co)3(Ti,Al) ordered fcc cP4 Pm 3 m a0 ⫽ 0.3561 to 0.3568
(L12)
␩ (Ni,Co)3Ti hexagonal hP16 P63/mmc a0 ⫽ 0.5093 to 0.5118
(D024) c0 ⫽ 0.8307 to 0.8348
MC (Ti,Mo)C fcc cF8 Fm 3 m a0 ⫽ 0.4300 to 0.4700
M23C6 (Cr,Mo)23C6 fcc cF116 Fm 3 m a0 ⫽ 1.048 to 1.080
M6C* (Co,Ni)3Mo3C diamond cubic cF112 Fd 3 m a0 ⫽ 1.085 to 1.175
␮* (Co,Ni)7Mo6 rhombohedral hR13 R3m a0 ⫽ ⬃0.904
*Not observed in the present study.

performed on a JEOL* S-450 microscope with a field-emis-

*JEOL is a trademark of Japan Electron Optics Ltd., Tokyo.

sion gun operating at 5 to 10 keV. The SEM samples were

first mounted and polished. They were then etched in a
solution with 3 parts glycerol, 3 parts HCl, 1 part HNO3,
and 1 part HF for 15 to 30 seconds, in order to reveal the
␥ ⬘ phase by etching it preferentially without attacking the
␥ matrix. This new etching solution was developed by trial
and error, and it worked very well.
Thermodynamic calculations were performed to predict
the phase stability in the alloy using the Thermo-Calc[7]
program and a NiFe database established by Thermo-Tech.[8]
No modification was made to the database, and the only
input to the calculations was the alloy composition.

III. EXPERIMENTAL RESULTS

Since 38 samples of different heat-treatment conditions
were to be analyzed, and it is much less time-consuming to
make SEM bulk samples than TEM thin foils, SEM is more
desirable than TEM. To make sure that high-resolution SEM
characterization of ␥ ⬘ can be used to substitute for TEM
observations, a consistency check was made using samples
heat-treated at 750 ⬚C, 850 ⬚C, and 900 ⬚C for 50 hours.
The TEM results of these samples will be described later.
In addition, TEM was employed to study the ␥ ⬘-to-␩
transformation.
Before the results of the precipitation-annealed samples
are presented, it should be mentioned that MC carbide string-
ers were observed in the as–solution-annealed condition.

A. The SEM Characterization

High-resolution SEM characterization was performed on
samples of all the 38 heat-treatment conditions, but only
selected images are shown. High-resolution SEM images of
samples annealed at 750 ⬚C and 850 ⬚C for 1 hour are
shown in Figures 1(a) and (b), respectively, in which the ␥ ⬘
precipitates appeared dark since they were etched out. There
was little or no indication of ␥ ⬘ precipitation at 750 ⬚C
(Figure 1(a))—if ␥ ⬘ particles were present, they were cer-
tainly below 10 nm in size. There was a clear indication
of ␥ ⬘ precipitation at 850 ⬚C (Figure 1(b)). There was no
indication of ␥ ⬘ precipitates in the sample annealed at 900
⬚C for 1 hour.
Fig. 1—High-resolution SEM images of samples heat treated at (a) 750
⬚C and (b) 850 ⬚C for 1 h showing very little indication of ␥ ⬘ in (a) and
a clear indication of ␥ ⬘ in (b).
The progression of the ␥ ⬘ precipitation at 750 ⬚C is shown
in Figures 1(a), 2(a), 2(b), and 3(a) for 1, 2, 8, and 50 hours,
respectively. There were some very fine ␥ ⬘ precipitates in
a sample annealed for 2 hours (Figure 2(a)). The ␥ ⬘ precipita-
tion can be clearly seen in a sample annealed for 8 hours

1272—VOLUME 32A, JUNE 2001 METALLURGICAL AND MATERIALS TRANSACTIONS A